MICRO-CHEMISTRY OF POISONS, 
INCLUDING THEIR 
PHYSIOLOGICAL, PATHOLOGICAL, AND LEGAL RELATIONS: 
ADAPTED TO 
THE USE OF THE MEDICAL JURIST, PHYSICIAN, 
AND GENERAL CHEMIST. 
BY 
T1 v 
PROFESSOR OF CHEMISTRY AND TOXICOLOGY IN STARLING MEDICAL COLLEGE, AND OF NATURAL 
SCIENCES IN CAPITAL UNIVERSITY, COLUMBUS, OHIO. 
PHEO. G. WORMLEY, M. D., 
WITH SEVENTY-EIGHT ILLUSTRATIONS UPON STEEL. 
Atto ndpjjg- ndvra avlpimoim (fiiMsi yivstydai.—Herodotus. 
BAILLIERE BROTHERS, 520 BROADWAY. 
NEW YO RK : 
LONDON: 
H. BAILLIERE, 
Regent-St. 
/ 
PARIS: 
J. B. BAILLIERE ET FILS, 
Rub Hautefeuille. 
1867. Entered, according to Act of Congress, in the year 1867, 
THEO. G. WORMLEY, M. D., 
In the Clerk s Office of the District Court of the United States for the 
Southern District of Ohio. 
CINCINNATI: 
Printed at the Methodist Book Concern. 
R. P. THOMPSON, PRINTER. TO 
WHO, 
HER.SKILLFUL HAND, 
assisted SO LARGELY IN ITS PREPARATION, 
JhIS yOLUME 
IS 
affection a tel r ins cribed. PREFACE. 
Among the more prominent objects of the present volume 
are to indicate the limit of the reactions of the different 
tests that have heretofore been proposed, as also of those 
now added, for the detection of the principal poisons, and 
to point out the fallacies attending the reaction of each; and, 
also, to apply the microscope, whenever practicable, in de- 
termining the nature of the different precipitates, sublimates, 
etc., and to illustrate these, whenever of any practical utility, 
by drawings. 
Hitherto there have been but comparatively few attempts 
to show the limit of the reaction of the different tests for 
poisons, and in these the results have been so discrepant as 
only to lead to confusion. This discrepancy has arisen chiefly 
from the fact that the experimentalists have generally failed 
to state the exact conditions under which the tests were 
applied. Without such statement, it is obvious that these 
experiments can have little or no practical value. Thus, for 
example, if in one instance only one grain of a hundredth 
solution of the poison be examined, whilst in another one 
hundred grains of a similar solution be employed, it is obvi- 
ous that—although the degree of dilution is the same in 
both the absolute quantity of the poison present in the lat- 
ter is one hundred times greater than in the former mixture, VI 
PREFACE. 
and if either will yield a precipitate with a given reagent the 
quantity produced from the latter will he one hundred times 
greater than from the former. Similar results would be ob- 
served in different quantities of all other solutions, until the 
degree of dilution exceeded the solubility of the precipita- 
ble substance produced by the reaction, when no quantity, 
however great, of the solution would yield any precipitate 
whatever. 
As illustrative of the discrepancy that has obtained among 
observers, in regard to the limit of some of the tests that 
have been examined, may be cited the statements in regard 
to Reinsch’s test for arsenic, the limit of which is placed by 
one observer at a dilution of 80,000, whilst another fixes it 
at a dilution of 1,200,000, and others still, place it between 
these extremes. Admitting that the amount of copper, in 
regard to surface, employed by these experimentalists, was 
the same, the results can only be reconciled on the supposi- 
tion that the quantity of arsenical solution operated upon in 
the second-named instance was about fourteen times greater 
than in the first-mentioned; when, although under very dif- 
ferent degrees of dilution, the absolute quantity of arsenic 
present was about the same in both instances. 
Moreover, to give any practical value to investigations of 
this kind, the experimenter should employ the least quantity 
of the solution compatible with the application of the test. 
In most instances, especially with the aid of the microscope, 
one grain of a given solution of the poison will yield as sat- 
isfactory results as a much larger quantity, the only differ- 
ence being in the amount of precipitate produced. And in 
all cases, unless the solution be exceedingly concentrated, a 
given quantity of substance in solution in one grain of fluid 
will yield very much better results than the same quantity in PREFACE. 
VII 
a larger amount of liquid, even when in the latter instance 
the degree of dilution does not exceed the solubility of the 
preeipitahle compound produced by the reaction. Through- 
out the present treatise, the reactions of the liquid tests, with 
very few exceptions, have been referred to one grain of the 
poisonous solution. If the operator has sufficient material 
on hand to permit the examination of larger quantities, his 
results will, as a general rule, he correspondingly greater than 
those stated in the text. 
Heretofore the microscope has received but little attention 
as an aid to chemical investigations, yet it is destined to very 
greatly extend our knowledge in this department of study. 
As an evidence of the value of micro-chemical analysis, as 
the Germans first styled it, it is only necessary to state that 
it enables us by a very few minutes labor to recognise with 
unerring certainty the reaction of the 100,000 th part of a 
grain of either hydrocyanic acid, mercury, or of arsenic. 
Many instances might also be cited in which it, with equal 
facility, enables us to detect the presence of very minute 
quantities of substances, the true nature of which heretofore 
could only be determined when present in comparatively 
large quantity, and by considerable labor. 
The microscopic illustrations, all of which are original, 
were drawn from nature and transferred to steel, by her to 
whom the work is inscribed. Each was prepared only after 
an extended examination of the original under the conditions 
usually present in ordinary analysis; if under these circum* 
stances, the general form of the object illustrated differed from 
that produced from the substance in its pure state, the differ- 
ence is noted. In regard to the mechanical execution of the 
illustrations, we leave it for others to pronounce, simply VIII 
PREFACE. 
remarking that the details of many of the figures can only 
be obtained by means of a lens. 
In this connection, the author of the illustrations desires 
us to acknowledge her obligations and express her thanks to 
Mr. F. E. Jones, of Cincinnati, through whose kind encour- 
agement she was induced to undertake the execution of the 
drawings upon steel, for his many valuable suggestions and 
the interest he manifested in the work during its entire 
preparation. She would also return her thanks to Mr. J. 
E. Gavit, of Flew York, for his kind interest in the under- 
taking and progress of the work. 
In addition to the points now mentioned, those acquainted 
with the subject will find that in the consideration of nearly 
every poison, more or less has been added to our knowledge, 
either in regard to the methods of analysis, the introduction 
of more delicate or confirmatory tests, or the methods of 
separation from organic mixtures; especially in regard to the 
vegetable poisons, many of which can now be recovered from 
the blood and other organic mixtures with as much certainty 
as most of the mineral substances. It is rarely that any 
allusion is made to these contributions, the only object of the 
author having been to ascertain, according to his experiments, 
the true value of the statements of others, and add to the 
common stock of knowledge. In no instance, unless so stated, 
was the reaction of a substance deduced from a single experi- 
ment, but only from repeated experiments and, when practi- 
cable, from different samples of material. If in any instance 
the author has been misled, no one, for the cause of science, 
will rejoice more than he in the demonstration of the error. 
It was originally intended to confine the work exclusively 
to the chemistry of poisons, but in order to adapt it to a PREFACE. 
IX 
larger class of readers, it was finally determined to also con- 
sider their physiological and pathological effects, and point 
out the treatment proper for each. In the preparation of 
this part of the work, the principal existing treatises upon 
the subject, together with many of the medical journals of 
the day, were freely consulted; but to no systematic works 
is the author more largely indebted than to the very valu- 
able treatises On Poisons by Drs. Christison and Taylor 
respectively, especially in the consideration of most of the 
inorganic poisons. It has been the author’s intention, so far 
as practicable, to give due credit for all cases and matter 
derived from others. When the original article was not at 
hand, reference is always made to the work consulted, this 
rule being rigidly observed throughout the volume. 
As within the last few years some two or three different 
works have appeared illustrating more or less the microscopic 
appearances of poisons, the author may be permitted to state 
that the present volume was projected as early as 1857, and 
a prospectus announcing its plan published in March, 1861, 
at which time the drawings were about completed. 
The work is now presented to the public with the hope 
that it will not only prove useful to those specially engaged 
in the chemical investigation of poisons, hut also to the 
Medical Jurist, the Physician, and the General Chemist. 
Columbus, Ohio, April, 1867. TABLE OF CONTENTS. 
INTRODUCTION. 
Micro-Chemistry of Poisons, Definition, 33 
Import of the term Poison, .......... 34 
Application of the Microscope, 34 
Causes modifying the action of Poisons, 35 
1. Idiosyncrasy, 35 
2. Habit, 36 
3. Disease, 37 
Classification of Poisons, .......... 37 
Sources of Evidence of Poisoning, 39 
I. Evidence from the Symptoms, ........ 39 
1. The Symptoms occur suddenly, . . . . . . .39 
2. They x’apidly run their course, 42 
Diseases resembling Poisoning, 43 
Duties of Medical Attendant, ...... 43 
11. Evidence from Post-mortem Appearances, ...... 44 
Appearances rarely characteristic, 44 
Irritant Poisons, usual etfects of, 45 
Narcotic Poisons, 45 
Appearances common to Poisoning and Disease, .... 46 
Narcotico-Irritants, 45 
Redness of the Stomach, ,46 
Softening of the Stomach, ........ 46 
Points to be observed in Post-mortem Examinations, ... 47 
Ulceration and Perforation, 47 
HI. Evidences from Chemical Analysis, 48 
Importance of Chemical Evidence, 48 
Substances requiring Analysis, 49 
Precautions in regard to Analyses, ....•• 
Failure to detect Fatal Quantity, .....*• 
Value of individual Chemical Tests, 
Failure to detect Poison, 
Of Chemical Reagents, 
Of Chemical Apparatus, ........... 
Qualifications of the Analyst, TABLE OF CONTENTS. 
XII 
PART FIRST. 
lIORGAIIO POISONS. 
CHAPTER I. 
THE ALKALIES: POTASH, SODA, AMMONIA. 
General Chemical Nature, 65 
Physiological Effects, 65 
Symptoms: 66 
1. Of the Fixed Alkalies, 66 
2. Of Ammonia, 66 
Period when Fatal, 67 
Treatment, 69 
Fatal Quantity, 68 
Post-mortem Appearances, . 69 
Nitrate of Potash and other Alkaline Salts, 70 
Chemical Properties of the Alkalies, 71 
Distinguished from each other, 71 
General Chemical Nature, 72 
Section I.—Potash. 
Section I.—Potash. 
Density of Solutions of Potash, 73 
Special Chemical Properties, 78 
1. Bichloride of Platinum Test, 74 
2. Tartaric Acid, and Tartrate of Soda, ...... 76 
8. Carhazotic Acid, 79 
Other Reagents, 80 
Spectrum Analysis, 80 
Separation from Organic Mixtures, 81 
Quantitative Analysis, 82 
Section ll.—Soda. 
Section ll.—Soda. 
General Chemical Nature, 83 
Density of Solutions of Soda, 83 
Special Chemical Properties, 84 
1. Antimoniate of Potash Test, ....... 84 
Coloration of Flame, 84 
2. Polarised Light, 85 
Behavior with Carhazotic Acid, 87 
“ “ Tartaric “ ....... 87 
“ “ Bichloride of Platinum, 87 
Separation from Organic Mixtures, 88 TABLE OF CONTENTS. 
General Chemical Nature, 88 
Section 111.—Ammonia. 
Density of Solutions of Ammonia, 88 
Special Chemical Properties, .......... 89 
1. Bichloride of Platinum Test, 89 
2. Tartaric Acid, and Tartrate of Soda, ...... 90 
3. Carbazotic Acid, ......... 91 
4. Nessler’s Test, 92 
Sonnenschein’s Test, ......... 94 
Separation from Organic Mixtures, ........ 95 
Antimoniate of Potash, 94 
Quantitative Analysis, ........... 96 
CHAPTER 11. 
the MINERAL ACIDS: SULPHURIC, NITRIC, HYDROCHLORIC. 
General Nature and Effects, 97 
Section I.—Sulphuric Acid. 
History, 98 
Symptoms, 98 
Period when Fatal, 99 
Fatal Quantity, .......... 101 
Treatment, 101 
Post-mortem Appearances, .......... 102 
General Chemical Nature, ' . .104 
Density of Solution of Sulphuric Acid, 105 
Special Chemical Properties, .......... 106 
2. Nitrate of Strontia, ......... HI 
1. Chloride of Barium Test, ....... 107 
3. Acetate of Lead, . . . . . . . . . 112 
4. Vera trine, 112 
Separation from Organic Mixtures, ........ 113 
Other Reactions, . . , . . . . . . 113 
Suspected Solutions, ......... 113 
Contents of the Stomach, . . . . . . . . .117 
Quantitative Analysis, . . . . , . . . . . .119 
From Organic Fabrics, 119 
Section ll.—Nitric Acid. 
Section II.—Nitric Acid. 
Symptoms, 120 
Period when Fatal, 122 
Treatment, 122 
Fatal Quantity, 122 XIV 
TABLE OF CONTENTS. 
Post-mortem Appearances, 122 
General Chemical Nature, 124 
Density of Solutions of Nitric Acid, 125 
Special Chemical Properties, 125 
1. Copper Test, 126 
2. Gold Test, 127 
8. Iron Test, 128 
4. Indigo Test, 129 
5. Brucine Test, 181 
6. Narcotine, and lodine Tests, 132 
Separation from Organic Mixtures, 134 
Schaffer’s, and Horsley’s Tests, 133 
Suspected Solutions, 134 
Contents of the Stomach, 136 
Quantitative Analysis, 137 
From Organic Fabrics, 137 
Section 111.—Hydrochloric Acid. 
Section 111.—Hydrochloric Acid. 
Symptoms, 139 
Period when Fatal, 139 
Treatment, ............. 141 
Fatal Quantity, 140 
Post-mortem Appearances, 141 
General Chemical Nature, 141 
Density of Solutions of Hydrochloric Acid, 142 
Special Chemical Properties, 143 
1. Nitrate of Silver Test, 144 
2. Nitrate of Suboxide of Mercury, 145 
Separation from Organic Mixtures, 146 
3. Acetate of Lead, 146 
Suspected Solutions, 146 
Contents of the Stomach, 148 
Quantitative Analysis, 149 
From Organic Fabrics, 148 
CHAPTER 111. 
OXALIC AND HYDROCYANIC ACIDS, AND PHOSPHORUS. 
Section I.—Oxalic Acid. 
History, 
Symptoms, 150 
Period when Fatal, 152 
Treatment, 
Post-mortem Appearances, .......... 154 
Fatal Quantity, 152 
General Chemical Nature, .......... 155 TABLE OF CONTENTS. 
XV 
Special Chemical Properties, .......... 156 
1. Nitrate of Silver Test, ........ 156 
2. Sulphate of Lime, ......... 158 
B. Chloride of Barium, ......... 159 
4. Nitrate of Strontia, ......... 160 
5. Acetate of Lead, 161 
Separation from Organic Mixtures, . . . . . . . . 168 
6. Sulphate of Copper, 162 
Suspected Solutions, 163 
Contents of the Stomach, ........ 164 
Quantitative Analysis, .......... 167 
The Urine, 166 
Section ll.—Hydrocyanic Acid. 
Section II.—Hydrocyanic Acid, 
Hist°ry, 167 
Symptoms, 169 
Period when Fatal, 171 
Treatment, 278 
1 ost-mortem Appearances, 174 
Fatal Quantity, 172 
Chemical Properties, 175 
General Chemical Nature, 175 
Special Chemical Properties, . . • • - - • . . .176 
1. Nitrate of Silver Test, . 177 
2. Iron Test, • • .180 
3. Sulphur Test, 183 
Relative Delicacy of these Tests, ....... 185 
Separation from Organic Mixtures, ........ 187 
Other Reactions, 186 
Examination for the Vapor, 187 
Method by Simple Distillation, 188 
Distillation with an Acid, ........ 189 
From the Blood and Tissues, 190 
Quantitative Analysis, . . . . . . . . . . .192 
Failure to detect the Poison, 191 
Section 111.—Phosphorus. 
Hist°ry, 192 
Symptoms, 292 
Period when Fatal, 193 
Treatment, 295 
Fatal Quantity, 194 
Posh-mortem Appearances, 196 
Chemical Properties, ..... ... 197 
General Chemical Nature, . . . . .197 
Solubility, , 197 XVI 
TABLE OF CONTENTS. 
Special Chemical Properties, 198 
1. Mitscherlich’s Method for Detection, 200 
2. Hydrogen Method, 203 
3. Lipowitz “ 205 
Phosphoric Acid, 206 
General Chemical Nature, 206 
Preparation, 206 
Special Chemical Properties, 206 
1. Nitrate of Silver Test, 206 
2. Sulphate of Magnesia, 207 
3. Molybdate of Ammonia, 208 
Separation of Phosphorus from Organic Mixtures, 210 
Other Reactions, ......... 210 
Mitscherlich’s Method, ......... 211 
Lipowitz Method, .......... 212 
Hydrogen “ 213 
Recovery as Oxide of Phosphorus, 213 
Failure to detect the Poison, ....... 214 
Quantitative Analysis, ........... 214 
CHAPTER IV. 
CHAPTER IV. 
ANTIMONY. 
History, 216 
Tartar Emetic, 216 
Composition, 216 
Symptoms, . 216 
Period when Fatal, 218 
Treatment, ............. 220 
Fatal Quantity, 219 
Post-mortem Appearances, 220 
General Chemical Nature, . . .221 
Special Chemical Properties, .......... 222 
Solubility, ........... 221 
1. Sulphuretted Hydrogen Test, 222 
2. Acetate of Lead, 224 
3. Zinc Test, 225 
4. Copper Test, 225 
5. Antimonuretted Hydrogen, 227 
Fallacies, 230 
Action of the Mineral Acids, 231 
Other Reactions, 232 
“ Caustic Alkalies, 232 
Separation from Organic Mixtures, 233 
Suspected Solutions, . 233 
Quantitative Analysis, 237 
From the Tissues, 236 TABLE OF CONTENTS. 
CHAPTER V. 
AESENIC. 
I. Metallic Arsenic. 
History and Chemical Nature, 28 
Physiological Effects, 2^9 
Special Chemical Properties, 2^9 
Compounds of Arsenic, 2^9 
11. Arsenious Acid. 
History and Varieties, 2^9 
Symptoms, 2^7 
Period when Fatal, 
Fatal Quantity, 2^ 
Treatment, 
Post-mortem Appearances, . . . - • • • • • 2^B 
Antiseptic Properties, ..••••••• 
General Chemical Nature, 299 
Special Chemical Properties, ...•••••• 20^ 
Of Solid Arsenious Acid, 208 
Solubility, 2^9 
253 
Vaporisation, 
Sublimation, 29^ 
Of Solutions of Arsenious Acid, 2jB 
Reduction, 2^0 
1. Ammonio-Nitrate of Silver Test, ...••• 209 
2. Ammonio-Sulphate of Copper, 
3. Sulphuretted Hydrogen, 299 
4. Reinsch’s Test, 299 
5. Marsh’s Test, 278 
Bloxam’s Method, 292 
Other Reactions, ... 
1. Lime-water, 
’ 004 
904 
2. lodide of Potassium, 295 
3. Bichromate of Potash, 29^ 
Separation from Organic Mixtures, . . • • • • • ‘ 299 
4. Potash and Sulphate of Copper, 295 
Suspected Solutions, 299 
, r 9Q7 
Vomited Matters, 
Contents of the Stomach, 297 
From the Tissues, ....•••••• 299 
Fresenius and Babo’s Method, 899 
Method of Danger and Flandin, ...•••• 9j 
“ “ Duflos and Hirsch, 999 
From the Urine, 
By Distillation, °99 
J J 0/17 
2 XVIII 
TABLE OF CONTENTS. 
Failure to Detect the Poison, 307 
Detection after Long Periods, 308 
Quantitative Analysis, .......... . 309 
111. Arsenic Acid. 
General Chemical Nature, 310 
Physiological Effects, 311 
Special Chemical Properties, 311 
1. Sulphuretted Hydrogen Test, 312 
2. Ammonio-Sulphate of Copper, 314 
3. Nitrate of Silver, .......... 315 
4. Reinsch’s Test, .......... 315 
5. Ammonio-Sulphate of Magnesia, ....... 316 
Other Reactions, . . . 317 
Quantitative Analysis, ..... ...... 317 
CHAPTER VI. 
CHAPTER VI. 
MERCURY. 
General Properties, .319 
Physiological Effects, ... ........ 319 
Combinations, ............ 319 
Corrosive Sublimate, 320 
Symptoms, 320 
Composition, 320 
Period when Fatal, 323 
Fatal Quantity, . 324 
Treatment, . . 324 
Post-mortem Appearances, ........... 325 
General Chemical Nature, .......... 327 
Solubility, 327 
Special Chemical Properties, . . . • • • • • • 328 
In the Solid State, ........... 328 
Of Solutions of Corrosive Sublimate, ........ 331 
1. Ammonia Test, ......... 831 
2. Potash and Soda, .......... 332 
3. lodide of Potassium, ........ 333 
4. Sulphuretted Hydrogen, 334 
5. Chloride of Tin, ......... 336 
6. Copper Test, ........... 337 
7. Nitrate of Silver, ......... 343 
Other Reagents, .......... 344 
Separation from Organic Mixtures, 844 
Suspected Solutions, 345 
Vomited Matters, .......... 346 
Contents of the Stomach, 346 
From the Tissues, 348 TABLE OF CONTENTS 
From the Urine, 351 
Quantitative Analysis, . • 
Failure to Detect the Poison, 351 
CHAPTER VII. 
CHAPTER VII. 
LEAD, COPPER, ZINC. 
Section I.—Lead. 
Section I.—Lead. 
History and Chemical Nature, 354 
Physiological Effects, 355 
Acetate of Lead, 355 
Symptoms, 355 
Period when Fatal, 356 
Treatment, .357 
Fatal Quantity, .......... 357 
Post-mortem Appearances, .......... 357 
General Chemical Nature, 358 
Special Chemical Properties, .......... 359 
Solubility, ........... 358 
In the Solid State, 359 
Gf Solutions of Acetate of Lead, . . . . . . , . 360 
1. Sulphuretted Hydrogen Test, ....... 361 
2. Sulphuric Acid, 363 
3. Hydrochloric Acid, 364 
4. lodide of Potassium, . . . , . . . . • 365 
5. Chromate of Potash, 366 
6. Potash and Ammonia, ......... 367 
7. The Alkaline Carbonates, ........ 367 
8. Oxalate of Ammonia, ......... 368 
9. Zinc Test, 368 
Separation from Organic Mixtures, . 369 
Other Reagents, .......... 369 
Suspected Solutions. .......... 369 
Contents of the Stomach, . . . . . . . • 370 
From the Tissues, . . . . . . . . . .371 
The Urine, 372 
Quantitative Analysis, ' 372 
Section ll.—Copper. 
History and Chemical Nature, 373 
Combinations, .......... 374 
1 hysiological Effects, 375 
Sulphate of Copper and Verdigris, . . . . . • .374 
Symptoms, 375 
Period when Fatal, 376 
Fatal Quantity, .......... 377 XX 
TABLE OF CONTENTS. 
Treatment, 377 
Post-mortem Appearances, ' 373 
Chemical Properties, 378 
In the Solid State, 378 
Of Solutions of Salts of Copper, 379 
1. Sulphuretted Hydrogen Test, 379 
2. Ammonia, .......... 381 
B. Potash and Soda, 382 
4. Ferrocyanide of Potassium, 383 
5. Iron Test, 384 
6. Platinum and Zinc Test, ........ 385 
7. Arsenite of Potash, 386 
8. Chromate of Potash, 386 
9. Ferricyanide of Potassium, 387 
10. lodide of Potassium, 387 
Detection of the Acid, 388 
Separation from Organic Mixtures, 388 
Suspected Solutions, 388 
Contents of the Stomach, 889 
From the Tissues, 390 
Quantitative Analysis, ........... 391 
The Urine, 391 
Section lll.—Zinc. 
History and Chemical Nature, 892 
Sulphate of Zinc, 393 
Chloride of Zinc, 394 
Symptoms, 394 
Treatment, 396 
Post-mortem Appearances, . .... t ... 396 
Chemical Properties of Salts of Zinc, ........ 397 
In the Solid State, 397 
When in Solution, ............ 398 
1. Sulphuretted Hydrogen Test, 398 
2. Potash and Ammonia, 400 
3. Ferrocyanide of Potassium, 400 
4. Ferricyanide of Potassium, ........ 401 
6. Oxalic Acid, .......... 402 
6. Chromate of Potash, ......... 402 
7. Phosphate of Soda, ......... 403 
Separation from Organic Mixtures, 404 
Detection of the Acid, ......... 403 
Contents of the Stomach, ......... 404 
From the Tissues, 405 
Quantitative Analysis, 405 TABLE OF CONTENTS. 
XXI 
PART SECOND. 
VEGETABLE POISONS. 
INTRODUCTION. 
p PAGE. 
general Nature of Vegetable Poisons, 409 
Reparation from Complex Organic Mixtures, 410 
1. Method of Stas, ..... ..... 411 
2. Rodgers and Girdwood’s Method, 416 
3. Method of Uslar and Erdmann, ....... 417 
4. Process of Graham and Hofmann, ...... 419 
5. Method by Dialysis, . . . . . . . . . 420 
CHAPTER I. 
CHAPTER I. 
VOLATILE ALKALOIDS: NICOTINE, CONINE. 
Section I.—Nicotine. (Tobacco.) 
Section I.—Nicotine. (Tobacco.) 
JJistory> 
Preparation, , 400 
Symptoms, . . ' ‘ ‘ ’ .424 
Period when Fatal, 426 
Fatal Quantity, 427 
Treatment, 427 
Postmortem Appearances, . .427 
eneral Chemical Nature, 428 
Solubility, ........ . . 428 
Special Chemical Properties, 429 
1. Bichloride of Platinum Test, ....... 430 
2. Corrosive Sublimate, 432 
3. Carbazotic Acid, 433 
4. lodine in lodide of Potassium, ...... 434 
5. Terchloride of Gold, 435 
6. Bromine in Bromohydric Acid, 436 
7. Tannic Acid, 436 
Other Reagents, 437 
Reparation from Organic Mixtures, . . .437 
Suspected Solutions and Contents of the Stomach, . . . 438 
From the Tissues, 440 
From the Blood, 440 
General Method of Distillation, 442 XXII 
TABLE OF CONTENTS. 
Section lll.—Conine. (Conium Maculatum.) 
History, 443 
Preparation, 444 
Symptoms, 444 
Treatment, 446 
Post-mortem Appearances, . 446 
General Chemical Nature, 447 
Special Chemical Properties, ......... 448 
Solubility, 448 
1. Terchloride of Gold Test, 450 
2. Carbazotic Acid, 451 
3. Corrosive Sublimate, ......... 451 
4. lodine in lodide of Potassium, 451 
5. Bromine in Bromohydric Acid, 452 
6. Nitrate of Silver, 453 
7. Tannic Acid, 453 
Other Reagents, 454 
Fallacies, 454 
Separation from Organic Mixtures, 455 
t 
CHAPTER 11. 
CHAPTER 11. 
OPIUM AND SOME OF ITS CONSTITUENTS. 
I.—Opium. 
History and Chemical Nature, 457 
Symptoms, 458 
Period when Fatal, 460 
Fatal Quantity, .......... 461 
Treatment, 463 
Post-mortem Appearances, 465 
Physical and Chemical Properties, 465 
ll.—Morphine. 
History and Preparation, 466 
Symptoms, 467 
Period of Death and Fatal Quantity, 468 
Treatment and Post-mortem Appearances, ....... 470 
General Chemical Nature, 470 
Special Chemical Properties, 473 
Solubility, 471 
In the Solid State, 473 
Of Solutions of Salts of Morphine, 473 
1. Potash and Soda Tests, 473 
2. Ammonia, 474 TABLE OF CONTENTS. 
3. Nitric Acid, 475 
4. lodic Acid, 476 
5. Sesquichloride of Iron. ........ 477 
6. lodide of Potassium, 478 
7. Chromate of Potash, 479 
8. Terchloride of Gold, 479 
9. Bichloride of Platinum 480 
10. lodine in lodide of Potassium, 480 
11. Bromine in Bromohydric Acid, ...... 481 
12. Carhazotic Acid, 481 
13. Chlorine and Ammonia, ........ 482 
Other Reagents, 482 
Relative Value of the Preceding Tests, . 483 
lll.—Meconic Acid. 
History, 483 
Preparation, ......... .... 483 
Physiological Effects, 484 
General Chemical Nature, 484 
Special Chemical Properties, 485 
Solubility, . . 484 
1. Sesquichloride of Iron Test, .....•• 486 
2. Acetate of Lead, 488 
3. Chloride of Barium, ........ 489 
4. Hydrochloric Acid, ......... 490 
5. Nitrate of Silver, 490 
6. Ferricyanide of Potassium, ........ 491 
7. Chloride of Calcium, ........ 491 
Other Reagents, .......... 492 
Suspected Solutions and Contents of the Stomach, 492 
separation of meconic acid and morphine from organic mixtures. 
Meconic Acid, ........... 493 
Morphine, 495 
Porphyroxine, ........... 498 
Prom the Tissues, . 500 
Examination for Morphine alone, ...... 499 
Prom the Blood, . . .... 500 
The Urine, . ’ . . .503 
Failure to Detect the Poison, 503 
Quantitative Analysis of Morphine, 504 
History, . ..... 504 
IV.—Narcotine. 
Preparation, , . 505 
Physiological Effects, 505 XXIV 
TABLE OF CONTENTS. 
Chemical Properties, 505 
1. Potash and Ammonia Tests, 507 
2. Sulphuric Acid and Nitrate of Potash, 608 
3. Acetate of Potash, 509 
4. Chromate of Potash, . 510 
5. Sulphocyanide of Potassium, 510 
6. Chloride of Gold, 511 
7. lodine in lodide of Potassium, 511 
8. Bromine in Bromohydric Acid, 512 
10. Carhazotic Acid, . . 513 
9. Ferrocyanide of Potassium, ........ 512 
Other Reagents, 518 
V.—Codeine. 
History, . ... ......... 513 
Preparation, 514 
Physiological Effects, ........... 514 
Chemical Properties, ........... 514 
1. Potash and Ammonia Tests, 516 
2. lodine in lodide of Potassium, 517 
3. Bromine in Bromohydric Acid, ....... 517 
4. Sulphocyanide of Potassium, 518 
5. Bichromate of Potash, 518 
6. Chloride of Gold, ......... 518 
7. Bichloride of Platinum, 519 
8. Carhazotic Acid, 519 
9. Nitric Acid and Potash, ........ 519 
Other Reagents, 520 
VI. —Narceine. 
History and Preparation, 520 
Physiological Effects, ........... 521 
Chemical Properties, 521 
1. lodine in lodide of Potassium Test, . . .' . . 522 
2. Bromine in Bromohydric Acid, 523 
3. Chloride of Gold, 523 
4. Bichloride of Platinum, 523 
5. Carhazotic Acid, 524 
6. Bichromate of Potash, ......... 524 
Other Reagents, ......... 524 
VII. —Opianyl. 
History, 524 
Preparation, .......... 524 
Physiological Effects, 525 TABLE OF CONTENTS. 
XXV 
Chemical Properties, ........... 525 
!• lodine in lodide of Potassium Test, 526 
2. Bromine in Bromohydric Acid, .....•• 526 
3. Sulphuric Acid and Heat, 521 
Other Reagents, 528 
CHAPTER 111. 
NUX VOMICA, STRYCHNINE, BRUCINE. 
I. Nux Vomica. 
History and Composition, . . . . . . . . . 529 
Symptoms, 529 
Period when Fatal, 531 
Treatment, . 582 
Post-mortem Appearances, 532 
Fatal Quantity, .......... 632 
Chemical Properties, ........... 533 
11. Strychnine. 
History, 584 
Preparation, 535 
Symptoms, . 536 
Period when Fatal, 541 
Fatal Quantity, .......... 542 
Treatment, 543 
Post-mortem Appearances, .......... 546 
General Chemical Nature, 548 
Solubility, 549 
Special Chemical Properties, 550 
In the Solid State, 550 
°f Solutions of Strychnine, ......... 551 
1- Potash and Ammonia Tests, ........ 552 
2. Color Test, 553 
3. Sulphocyanide of Potassium, . . . . . ' - 566 
4. lodide of Potassium, 567 
5. Bichromate of Potash, 567 
6. Chloride of Gold, 570 
7. Bichloride of Platinum, ......•• 571 
8. Carbazotic Acid, 572 
10. lodohydrargyrate of Potassium, 578 
9. Corrosive Sublimate, 572 
, IP Perricyanide of Potassium, 574 
12. lodine in lodide of Potassium, . . . . • • 575 
13. Bromine in Bromohydric Acid, 576 
14. Physiological Test, 576 
Other Reagents, 578 XXVI 
TABLE OF CONTENTS 
Separation from Organic Mixtures, 579 
From Nux Vomica, ......... 579 
Suspected Solutions and Contents of the Stomach, .... 579 
Method by Dialysis, ........ 582 
From the Tissues, 586 
The Blood, 587 
From the Urine, .......... 590 
Quantitative Analysis, 593 
Failure to Detect the Poison, 591 
111. Brucine. 
History and Preparation, 593 
Physiological Effects, ........... 594 
General Chemical Nature, .......... 594 
Special Chemical Properties, ......... 595 
Solubility, ........... 595 
1. Potash and Ammonia Tests, . . . ‘ . . . . . 596 
2. Nitric Acid and Chloride of Tin Test, 597 
3. Sulphuric Acid and Nitrate of Potash, 598 
4. Sulphocyanide of Potassium, 599 
6. Bichromate of Potash, ......... 600 
6. Bichloride of Platinum, 600 
7. Terchloride of Gold, 601 
8. Carbazotic Acid, ......... 602 
9. Ferricyanide of Potassium, 602 
10. lodine in lodide of Potassium, 603 
11. Bromine in Bromohydric Acid, ....... 603 
Separation from Organic Mixtures, . . • • • • • • 604 
Other Keactions, 604 
CHAPTER IV. 
CHAPTER IV. 
ACONITINE, ATROPINE, DATURINE. 
Section I.—Aconitine. (Aconite.) 
Section I.—Aconitine. (Aconite.) 
History and Preparation, 606 
Symptoms, 608 
Period when Fatal, .......... 610 
Treatment, ............. 612 
Fatal Quantity, 610 
Post-mortem Appearances, 613 
Chemical Properties, 614 
Of Solutions of Aconitine, 616 
Solubility, 616 
1. Potash and Ammonia Tests, 616 
2. Terchloride of Gold Test, 617 
3. Carbazotic Acid, 617 TABLE OF CONTENTS. 
XXVII 
4. lodine in lodide of Potassium, ....... 617 
5. Bromine in Bromohydric Acid, ...... 618 
Other Reagents, .......... 618 
Fallacies of Preceding Tests, . 618 
Physiological Test, 619 
eparation from Organic Mixtures, ........ 619 
Suspected Solutions and Contents of the Stomach, .... 619 
From the Blood, 620 
Section II.—Atropine. (Belladonna.) 
Section II.—Atropine. (Belladonna.) 
History, 621 
Preparation, 622 
Symptoms, 623 
Treatment, 628 
Post-mortem Appearances, .......... 628 
Chemical Properties, 628 
0f Solutions of Atropine, 629 
Solubility, 629 
!• Potash and Ammonia Tests, 680 
2. Bromine in Bromohydric Acid Test, 630 
3. Carbazotic Acid, .......... 631 
4. Terchloride of Gold, ........ 632 
5. lodine in lodide of Potassium, 633 
Other Reagents, ......... 633 
Physiological Test, 633 
eparation from Organic Mixtures, ........ 634 
Suspected Solutions and Contents of the Stomach, .... 634 
From the Blood, . 636 
Section 111.—Daturine. (Stramonium.) 
History and Preparation, 636 
Symptoms, 637 
Treatment, . _ _ 640 
Post-mortem Appearances, ....... . . . 640 
Chemical Properties, 640 
Reparation from Organic Mixtures, . . . 641 
CHAPTER V. 
CHAPTER V. 
VERATRINE, SOLANINE. 
Section I.—Veratrine. (White Hellebore.) 
History and Preparation, 643 
ymPt°ms.—Veratrum Album, 645 
Veratrum Viride, 646 
Veratrine, 647 XXVIII 
TABLE OF CONTENTS. 
Treatment, 648 
Post-mortem Appearances, 648 
Chemical Properties, 648 
Of Solutions of Yeratrine, . 651 
Solubility, 650 
1. Potash and Ammonia Tests, 651 
2. Sulphuric Acid Test, 652 
8. Chloride of Gold, 653 
4. Bromine in Bromohydric Acid, ....... 654 
5. lodine in lodide of Potassium, ...... 655 
6. Carbazotic Acid, 655 
7. Bichromate of Potash, ........ 655 
Separation from Organic Mixtures, . 656 
Other Reagents, 656 
Contents of the Stomach, 656 
From the Blood, .......... 657 
Section II.—Solanine. (Nightshade.) 
Section ll.—Solanine. (Nightshade.) 
History, 657 
Preparation, 657 
Symptoms, 658 
Treatment, 660 
Post-mortem Appearances, .......... 660 
Chemical Properties, 660 
Of1 Solutions of Solanine, 662 
Solubility, 661 
1. Potash and Ammonia Tests, 663 
2. Sulphuric Acid Test, N . . 663 
3. lodine in lodide of Potassium, ....... 665 
4. Chromate of Potash, 665 
5. Bromine in Bromohydric Acid, 666 
Other Reagents, 666 
Separation from Organic Mixtures, . 667 ILLUSTRATIONS UPON STEEL. 
PtG. 1 
PLATE I. 
2. 
3. 
4. 
6. 
6. 
Ton grain Potash, in the form of nitrate or chloi’ide, -j- Bichloride of 
Platinum, X 225 diameters. 
TTcr grain Potash, as nitrate, -(- Tartaric Acid, X 100 diameters. 
vhf grain Potash, as chloride, -f- Tartrate of Soda, X 80 diameters. 
grain Potash, as nitrate, -|- Carbazotic Acid, X 40 diameters. 
tut grain Ammonia, as chloride, -f- Carbazotic Acid, X 40 diameters. 
A grain Soda, Carbazotic Acid, X4O diameters. 
PLATE 11. 
Pig. 1. 
2. 
3. 
4. 
5. 
6. 
2V xtt grain Soda, -f- Antimoniatc of Potash, X 100 diameters. 
To grain Soda, -)- Tartaric Acid, X 40 diameters. 
TOoo grain Soda, as chloride, + Bichloride of Platinum, X 40 diameters. 
too grain Sulphuric Acid, -f- Chloride of Barium, X 100 diameters. 
Hydrofluosili01c Acid, -(- Chloride of Barium, X 100 diameters. 
Too grain Sulphuric Acid, T Nitrate of Strontia, X 15 diameters. 
Pro. 1. 
PLATE 111. 
2. 
3. 
4. 
5. 
6. 
Tiro grain Hydrochloric Acid, -f Acetate of Lead, X 40 diameters. 
Toiler grain Oxalic Acid, on spontaneous evaporation, X 80 diameters. 
TOVO grain Oxalic Acid, -(- Chloride of Calcium, X 225 diameters. 
Toil grain Oxalic Acid, -f- Chloride of Barium, X 80 diameters. 
tot grain Oxalic Acid, -f- Nitrate of Strontia, X 125 diameters, 
xuo grain Oxalic Acid, -j- Acetate of Lead, X 80 diameters. 
Pig. 1. 
To 000 grain Hydrocyanic Acid vapor, -J- Nitrate of Silver, X 222 diameters. 
TooVoo grain Hydrocyanic Acid vapor, -f- Nitrate of Silver, X 125 diameters. 
Totto' grain Phosphoric Acid, -j- Ammonia-Sulphate of Magnesia, X 80 
diameters. 
Tartar Emetic, from hot supersaturated solution, X 40 diameters. 
Arsenious Acid, sublimed, X 125 diameters. 
Toil grain Arsenious Acid -I- Ammonio-Nitrate of Silver, X 15 diameters. 
29 
PLATE IV. 
2. 
3. 
4. 
5. 
6. ILLUSTRATIONS UPON STEEL. 
XXX 
PLATE V. 
Fig. 1. Tlra grain Arsenic Acid, -f- Ammonia-Sulphate of Magnesia, X 75 di- 
“ 2. Corrosive Sublimate, sublimed, X4O diameters. 
“ 3. yum grain Lead, -f- diluted Sulphuric Acid, XBO diameters. 
ameters. 
11 4. To‘o grain Lead, -f- diluted Hydrochloric Acid, XBO diameters. 
“ 5. -2go o grain Lead, lodide of Potassium, XBO diameters. 
“ 6. TuVu grain Zinc, -f Oxalic Acid, XBO diameters. 
PLATE VI. 
Fig. 1. grain Nicotine, -f- Bichloride of Platinum, X 40 diameters 
“ 2. Tij7 grain Nicotine, -f- Corrosive Sublimate, X4O diameters. 
“ 8. joins' grain' Nicotine, -f Carbazotic Acid, X 40 diameters. 
“ 4. Coninb, pure, -|- vapor of Hydrochloric Acid, X4O diameters. 
“ 5. Tuu grain Conine, -f- Carbazotic Acid, X4O diameters. 
“ 6. Tuu grain Morphine, -)- Potash or Ammonia, X4O diameters. 
PLATE VII. 
Fig. 1. Tuu grain Morphine, -)- lodide of Potassium, X4O diameters. 
“ 2. Tuu grain Morphine, -f- Chromate of Potash, XBO diameters. 
“ 3. T-i_ grain Morphine, -j- Bichloride of Platinum, XBO diameters. 
“ 4. TI(J grain Meconic Acid, -f~ Chloride of Barium, XBO diameters. 
“ 5. i grain Meconic Acid, -f- Hydrochloric Acid, X 75 diameters. 
“ 6. yJit grain Meconic Acid, -)- Perricyanide of Potassium, X4O diameters 
PLATE VIII. 
Fig. 1. Yirtr grain Meconic Acid, -)- Chloride of Calcium, X 75 diameters. 
“ 2. Tuuu grain Narcotine, -j- Potash or Ammonia, X4O diameters. 
“ 3. grain Narootine, Acetate of Potash, XBO diameters. 
“ 4. yijo grain Codeine, -f- lodine in lodide of Potassium, X4O diameters. 
“ 5. yum grain lodide of Codeine, from alcoholic solution, X 75 diameters, 
“ 6* iio grain Codeine, -f- Sulphocyanide of Potassium, X4O diameters. 
PLATE IX. 
Ftq. 1, yum grain Codeine, -j- Bichromate of Potash, X4O diameters. 
“ 2. yuo grain Codeine, -j- lodide of Potassium, X4O diameters. 
“ 3. ycto o’ grain Narceine, -j- lodine in lodide of Potassium, X 40 diameters, 
“ 4. yJq grain Narceine, -f- Bichromate of Potash, X4O diameters. 
“ 5. yum grain Opianyl, -j- lodine in lodide of Potassium, X4O diameters. 
“ 6. yum grain Opianyl, -)- Bromine in Bromohydric Acid, X4O diameters. ILLUSTRATIONS UPON STEEL. 
XXXI 
PLATE X. 
IQ- 1- tvo grain Strychnine, -(- Potash or Ammonia, X4O diameters. 
too grain Strychnine, -f Sulphocyanide of Potassium, X 40 diameters. 
( too grain Strychnine, -f- Bichromate of Potash, X 40 diameters. 
£ 0000 grain Strychnine, + Bichromate of Potash, X 80 diameters. 
( tooo grain Strychnine, -|- Chloride of Gold, X 40 diameters. 
Tooo grain Strychnine, -f Bichloride of Platinum, X 40 diameters. 
PLATE XL 
Fir l i 
t( ToVo gram Strychnine, + Carbazotic Acid, X 80 diameters. 
( too grain Strychnine, -)- Corrosive Sublimate, X 40 diameters. 
( too grain Strychnine, -[- Ferricyanide of Potassium, X 40 diameters. 
( tooo grain Strychnine, -f- lodine in lodide of Potassium, X 80 diameters. 
( J' too grain Brucine, -f- Potash or Ammonia, X4O diameters. 
too grain Brucine, Sulphocyanide of Potassium, X4O diameters. 
PLATE XII. 
too grain Brucine, Bichromate of Potash, XBO diameters. 
tooo grain Brucine, Bichloride of Platinum, X4O diameters. 
( too grain Brucine, -f- Ferricyanide of Potassium, X 40 diameters. 
Too grain Atropine, Potash or Ammonia, XlO diameters. 
too grain Atropine, -|- Bromine in Bromohydric Acid, X 75 diameters. 
(j- Toooo grain Atropine, -f- Bromine in Bromohydric Acid, X 125 diameters. 
PjQ 1 1 . 
o' o' TT>s’ grain Atropine, -f~ Carbazotic Acid, XBO diameters. 
u ’ too grain Atropine, -|- Chloride of Gold, XBO diameters. 
(( Too grain Veratrine, -(- Chloride of Gold, X 40 diameters. 
I( too grain Veratrine, -)- Bromine in Bromohydric Acid, X 80 diameters. 
ug’ Solanine, from alcoholic solution, XBO diameters. 
too grain Solanine, as sulphate, on spontaneous evaporation, X 80 
diameters. 
PLATE XIII. MICRO-CHEMISTRY OF POISONS 
INTRODUCTION. 
DEFINITION ; APPLICATION OF THE MICROSCOPE IMPORT OF THE 
Term POISON ; MODIFYING CIRCUMSTANCES CLASSIFICATION 
OF POISONS SOURCES OF EVIDENCE OF POISONING: 
EVIDENCE FROM SYMPTOMS FROM POST-MORTEM 
APPEARANCES FROM CHEMICAL ANALYSIS. 
By the term Miceo-Chemistey of Poisons, we understand 
the study of the chemical properties of poisons as revealed by 
tbe aid of the microscope. Although the scope of the present 
is not limited to this department of the subject, yet as that 
ranch of the science forms a main element of the treatise, 
We have designated it by that title. 
The instrument requisite for investigations of this kind may 
em comparatively simple; and but little accessory apparatus 
Yill be required. The stage of the instrument should be suffi- 
ciently large to receive a watch-glass having a diameter of not 
ess Bian two inches. Object-glasses of only low power are 
usually required. Very often an amplification of from thirty 
0 foity diameters will answer the purpose best, but more fre- 
quently, perhaps, a power of about seventy-five will be the 
ost satisfactory, while in some few instances an amplifica- 
-I,(^n about two hundred and fifty will be required. The 
jectives best suited for these powers are the inch and a half, 
W° inch, and one-fifth inch, respectively. In these in- 
stigations, as in all others with the microscope, the lowest 
iplification that will reveal the true character of the object 34 
INTRODUCTION. 
examined, will be the most satisfactory. A polarising appa- 
ratus will sometimes be necessary to determine the true nature 
of an object; and in some instances a micrometer will be found 
useful to ascertain the absolute size of the object. 
In applying the microscope to the examination of the result 
of a chemical reagent upon a suspected solution, a single drop 
of the liquid, placed in a watch-glass or upon a glass slide, is 
treated with a very small quantity of the reagent, added by 
means of a pipette, and the mixture, with as little agitation as 
possible, transferred to the stage of the instrument. If, as is 
sometimes the case, the crystalline deposit produced by the 
reagent be readily broken up by agitation, the watch-glass 
containing the drop of fluid to be examined, is placed on the 
stage of the instrument before the addition of the reagent. In 
many instances, as will be noticed hereafter, the formation of a 
precipitate is much facilitated by stirring the mixture with a 
glass rod. Should the mixture evolve fumes injurious to the 
object-glass, a flat watch-glass having a ground edge is selected, 
and this covered by a piece of very thin glass. Any special 
directions in regard to the use of this instrument, will be pointed 
out hereafter, as occasion may require. 
A Poison is any substance which, when introduced into the 
body and being absorbed, or by its direct chemical action, or 
when applied externally and entering the circulation, is capable 
of producing deleterious effects. There is no doubt but all 
poisons are to a greater or less extent absorbed into the cir- 
culation. In fact, with most of them this is certainly a condi- 
tion essential to the production of their effects; yet it would 
appear that in the action of some substances, which produce 
local chemical changes, death, in some instances at least, can 
only be referred to the effects of the changes thus produced. 
The mineral acids and caustic alkalies are the principal poisons 
which have a direct chemical action upon the parts with which 
they are brought in contact. This action is due to a mutual 
affinity existing between the agent and the tissue. In this 
respect, the action of these substances differs from that of cer- 
tain heated liquids, such as boiling water, which are inert at 
ordinary temperatures, but which, simply on account of their CAUSES MODIFYING THE ACTION OF POISONS. 
35 
condition, induce a chemical change in the part to which they 
aie applied, without themselves being chemically concerned in 
the change. When applied externally, some poisons are ab- 
sorbed by simply being brought in contact with the unbroken 
skin; whilst others do not enter the circulation unless applied 
to an abraded or wounded surface. 
Poisons differ greatly in regard to the quantity necessary to 
prove injurious. Thus the fiftieth part of a grain of aconitine 
has seriously endangered the life of an adult, while on the 
other hand, an ounce of sulphate of magnesia may generally 
3e administered with impunity; yet in large quantities the 
latter substance has in several instances caused death, and is 
strictly a poison, although not commonly reputed as such. As 
yet we know of no substance that is poisonous in all propor- 
tions. Any of the most powerful poisons may be administered 
lu certain quantities without producing any appreciable effect, 
and most of them may be so employed as to constitute valuable 
remedial agents. 
In medico-legal inquiries, the leading idea connected with 
the term poison, is whether the given results are directly 
tiaceable to the substance and the intention with which it 
was employed. 
Poisons not only differ from each other in regard to the 
quantity necessary to destroy life, but the effects of the same 
substance may be much modified by circumstances, and even 
substances which to most persons are harmless may, on ac- 
count of certain peculiarities of constitution, produce deleteri- 
ous effects. 
Causes which modify the effects of Poisons.—Among the 
causes which may modify the effects of poisons, may, in this 
connection, be mentioned Idiosyncrasy, Habit, and a Diseased 
ktate of the System. 
1. Idiosyncrasy, or a peculiarity of constitution, may vari- 
Uouslj modify the effects of substances. Thus to some persons 
oidinary medicinal doses of certain drugs, such as opium or 
uieicury, produce violent symptoms, and even death. In other 
instances, substances which to most persons are harmless, and 
even ordinary articles of food, produce symptoms of irritant 
3* 36 
INTRODUCTION. 
poisoning. This has been observed in the eating of certain 
kinds of fish, honey, pork, veal, and mutton. In still another 
form of idiosyncrasy, there is a diminished susceptibility to the 
action of cei’tain substances, which to most persons are active 
poisons. This peculiarity of constitution is very rare, and is 
most generally observed in regard to the action of mercury and 
opium. Dr. Christison relates an instance, in which a gentle- 
man, unaccustomed to the use of opium, took without injury 
nearly an ounce of good laudanum. 
2. Habit may render certain poisons harmless in doses, 
which to most persons would prove rapidly fatal. The influ- 
ence of habit is daily seen in the use of opium, tobacco, and 
alcohol; and it is well known that certain other agents when 
administered medicinally, in frequently-repeated doses, after a 
time lose their ordinary effects. Persons accustomed to the use 
of opium, have taken daily, for long periods together, quan- 
tities of laudanum that would prove fatal to several persons 
unaccustomed to its use. Although this influence has princi- 
pally been observed, as remarked by Dr. Christison, in regard 
to the action of certain organic poisons, especially such as act 
on the brain and nervous system; yet it seems now to be fully 
established that certain persons in Styria accustom themselves 
even to the eating of arsenic in doses of several grains daily, 
and continue the practice for many years without experiencing 
any of the usual effects of the poison. The statements formerly 
made by Dr. Tschudi and others in regard to the existence of 
this practice, have been discredited by most writers on toxi- 
cology; but the accounts more recently published by Dr. Ros- 
coe, as quoted by Dr. Taylor (Med. Jur., Amer. ed., 1861, 
p. 693), and the direct observations of Dr, Maclagan, of Edin- 
burgh (Chemical News, London, July, 1865, p. 36), while on 
a visit to Styria, seem to leave no doubt whatever of its ex- 
istence. In one of the cases observed by Dr. Maclagan, the 
individual, a muscular young man, aged twenty-six years, 
swallowed in connection with a very small piece of bread, five 
grains of genuine powdered arsenious acid, or white arsenic, 
which he stated was about the quantity he was in the habit of 
taking twice a week. In the urine passed by this individual 37 
CLASSIFICATION OF POISONS. 
two hours afterward, as also in that passed after twenty-six 
hours, Dr. Maclagan detected a very notable quantity of arsenic. 
It is but proper to observe, that the experience of most medical 
practitioners in the use of this substance, does not accord with 
the results of this Styrian practice. 
3. Disease.—ln certain diseased conditions of the system, 
there is a diminished susceptibility to the action of certain 
poisons ; whilst in others, there is an increased susceptibility, 
even to the action of the same substance. Thus in tetanus, 
hydrophobia, mania, and delirium tremens, .quantities of opium, 
which in ordinary states of the system would be fatal, may often 
be administered with beneficial effects. In a case of tetanus 
related by Dr. Watson (Practice of Physic), something over 
four ounces of laudanum were taken on an average daily, for 
twenty days; after which the patient recovered. The same 
writer quotes another instance of the same affection, in which 
an ounce of solid opium was taken, in divided doses, daily, for 
twenty-two days. So also, in inflammation of the lungs, enor- 
mous doses of tartar emetic have been given with advantage. 
On the other hand, in cases in which there is a predisposition 
fo apoplexy, an ordinary dose of opium may cause death. In 
like manner, in certain diseases, there is an increased suscepti- 
bility to the action of mercury and other mineral substances. 
Classification of Poisons.—Most recent writers on this 
subject have adopted the arrangement of poisons, according to 
the symptoms they produce, into three classes, namely, Irri- 
tants, Narcotics, and Narcotico-Irritants. Since, however, 
there are many poisons, the effects of which are subject to 
gieat variation, and others which according to their ordinary 
effects, might with equal propriety be placed in one or another 
of these classes, this classification is open to objection; never- 
theless, it is, perhaps, the best, for practical purposes, yet 
proposed. 
Irritant Poisons, as a class, produce irritation and inflam- 
mation of the stomach and bowels, attended or followed by 
mtense pain in these parts, tenderness of the abdomen, and 
violent vomiting and purging, the matters evacuated being often 
tinged with blood. Some of the members of this class, such as 38 
INTRODUCTION. 
the mineral acids and caustic alkalies, also possess corrosive 
properties, and accordingly occasion, in addition to the effects 
just mentioned, more or less disorganization of the mouth, 
throat, oesophagus, and stomach. The action of these sub- 
stances, if not too dilute, is immediate, and is attended with a 
sense of burning heat in the parts with which they come in 
contact. When highly diluted, any of the corrosive poisons 
may act by simply inducing irritation and inflammation. 
The irritant poisons may be divided into three sections, 
according to the kingdom of nature to which they belong, 
namely, mineral, vegetable, and animal. The first section is 
much the largest, and embraces, with the exception of some 
gaseous substances, all strictly inorganic poisons. Gramboge 
and cantharides, are, respectively, examples of the second and 
third sections. 
Narcotic Poisons are such as act principally on the brain 
and spinal marrow, more especially on the former. They 
induce headache, vertigo, stupor, impaired vision, delirium, 
insensibility, paralysis, convulsions, and coma. This class con- 
tains comparatively few substances, the principal of which are 
Opium and Hydrocyanic acid. Several of the poisonous gases 
belong to this class. 
Narcotico-Ireitants partake, as indicated by their name, 
of the action of both the preceding classes. Thus, they may 
produce, as a result of their irritant action, nausea, pain in the 
stomach, vomiting, and purging; and as a result of their action 
on the nervous system, stupor, delirium, paralysis, coma, and 
convulsions. Some of them, however, do not usually produce 
well-marked symptoms of irritation; and all of them produce 
their most marked effects on the nervous system. A few, such 
as strychnine and brucine, act chiefly on the spinal cord, and 
produce violent tetanic convulsions, without any other prom- 
inent symptom. All the members of this class, which is quite 
numerous, are derived from the vegetable kingdom. 
In referring the symptoms in a given case to the action of 
either of the above classes, it must not be forgotten, as already 
intimated, that the members of each do not always produce the 
same effects. Thus arsenic has occasioned symptoms similar to SYMPTOMS AS EVIDENCE OF POISONING. 
39 
those of narcotic poisoning; whilst opium has produced effects 
resembling poisoning by an irritant. 
Sources of Evidence op Poisoning. 
_ The medical evidence in cases of poisoning, is derived 
chiefly from—l. The symptoms; 2. The post-mortem appear- 
ances; and, 3. Chemical analysis. 
1. Evidence from the Symptoms. 
In forming an opinion in a case of suspected poisoning, the 
niedical examiner should acquaint himself with, not only the 
special character of the symptoms present, but also, as far as 
piacticable, the previous health and habits of the patient, when 
°oa or drink was last taken, whether in taking it any peculiar 
faste or odor was observed, and whether others partook of the 
same food. 
Among the characters of the symptoms of poisoning usually 
nientioned by writers on this subject, the most constant are— 
The symptoms arise suddenly, and soon after the taking of 
00c j drink, or medicine; and, 2. They rapidly prove fatal. 
1. The symptoms occur suddenly, and soon after the taking of 
So>ne solid or liquid. The greater number of poisons, when 
a cen m fatal quantity, manifest their action either immediately 
within a short period, the symptoms of but few being de- 
ayed, under ordinary circumstances, much beyond an hour. 
. anT instances might be cited, in which a knowledge of the 
fnne that elapsed between the taking of food or drink and the 
appearance of the suspected symptoms, was in itself sufficient to 
ctermine that they were really due to natural causes and not 
e^*ec^8 °I poison. In considering this relation, however, 
not be overlooked that the interval between the taking 
a poison and the first appearance of symptoms, not only 
ants with each substance, but the time, as well as the char- 
j ctei of the symptoms of the same poison, may be more or 
wV f^ec^ circumstances, such as quantity, the state in 
lc administered, condition of the stomach, combination 40 
INTRODUCTION. 
with other substances, and, as already mentioned, a diseased 
state of the system. Thus strychnine, when taken in fatal 
quantity, has produced violent symptoms within five minutes 
afterwards, and they usually appear within thirty minutes, yet 
they have been delayed, in one instance at least, for two hours 
and a half. It is well known that antimony, arsenic, lead, and 
various other poisons, when taken into the system in repeated 
small doses, may give rise to effects wholly different from those 
usually produced by a single poisonous dose of the substance. 
As a general rule, poisons act more speedily when taken 
in the state of solution than in the solid form. On the other 
hand, a full stomach, and, according to Dr. Christison, sleep, 
may delay the action of certain substances. That the action 
of one poison may be modified by the presence of another, is 
well illustrated by the following case. A man, aged twenty- 
nine years, swallowed three grains of strychnine, one drachm 
of opium, and an indefinite quantity of quinine. When seen 
by a physician twelve hours afterwards, he only complained of 
feeling “queer.” But there was extreme cerebral excitement; 
the pulse quick, full and strong; pupils contracted; the whole 
face of a deep-red color; tongue tremulous and covered with a 
brownish-white fur; surface of the body hot, with profuse per- 
spiration; body and limbs in violent tremor, and at intervals 
spasmodic action of all the muscles, alternating with compara- 
tive quiet and drowsiness, from which he was easily roused. 
Upon the administration of full emetic doses of sulphate of 
zinc, opium was freely ejected. One hour later, the patient 
became quite drowsy, but when roused would start violently 
and remain delirious for some minutes. In two hours more, 
complete stupor suddenly supervened and continued, with but 
little change till death, which occurred forty hours after the 
mixture had been taken. (Chicago Medical Journal, Novem- 
ber, 1860.) How far the first appearance and character of 
the symptoms of a particular poison may depart from their 
ordinary course, can be learned only from a comparison of 
well-authenticated cases. In this respect, our knowledge at 
present in regard to the effects of very many substances, is 
extremely limited, and there is no reason to believe that in SYMPTOMS AS EVIDENCE OF POISONING. 
41 
legard to any, we have as yet met with the greatest deviation 
possible. 
In this connection, it must also be borne in mind that there 
are certain natural diseases, the symptoms of which resemble 
more or less those of poisoning, and which may appear sud- 
denly at any time. In fact, some of these diseases, such as 
aP°plexy and perforation of the stomach, are more likely to 
occur soon after the taking of food than at any other period. 
Instances of this kind, however, are of rare occurrence, and 
the subsequent history of the case will usually enable the prac- 
titioner to determine without difficulty its true nature. Nev- 
ertheless, cases have occurred, the nature of which could only 
be established by the post-mortem appearances and chemical 
analyses. 
When two or more persons, who have eaten of the same food, 
fle suddenly seized with violent symptoms, there is, of course, 
increased reason for suspecting the presence of a poison. This 
circumstance has in some instances at once revealed the source 
°f the poison. Results of this kind, however, may be due 4o 
an unwholesome or diseased condition of the food; or to its 
having accidentally become contaminated with a poisonous 
metal, such as copper, lead, or zinc, during its preparation. 
On the other hand, several persons may partake of the same 
meal, or even of the same food, and poison have been design- 
edly introduced only into the portion intended for a particular 
individual. Thus in a case in which we were recently con- 
sulted, and which will be referred to hereafter, a family of sev- 
eial persons having mush and milk for supper, the mush was 
placed on the table in one dish, while the milk was distributed 
the usual places of sitting, in bowls. Into one of the bowls 
strychnine had been introduced, and its intensely bitter taste 
as? perhaps, the only circumstance that saved the life of the 
peison for whom it was intended; only, however, to become 
e victim a few days afterwards of a fatal quantity, under a 
,orm in which its taste was entirely concealed. In another 
mstance, the plum-pie served for dinner was furnished to the 
SeVcial members of the family, on separate plates; under the 
must of one of the pieces, arsenic had been placed, and proved INTRODUCTION. 
fatal to the person who ate it. From what has already been 
stated, it is obvious that several persons may even partake of 
the same poisoned food, and the results be very different. Dr. 
Beck quotes several striking examples of this kind. 
Lastly, in inquiries of this kind it must be remembered 
that poisons may be introduced into the system in other ways 
than with food, drink, or medicine. Thus poisoning by the ex- 
ternal application of the substance, is not of unfrequent occur- 
rence; the same is also true of the inhalation of certain vapors 
and gases. Instances of this kind, however, are usually the 
result of accident. Several instances are recorded, in which 
poisons were criminally introduced into the rectum and vagina; 
and Dr. Christison cites a case, in which a fatal quantity of 
sulphuric acid was poured into the mouth of an individual 
while asleep. 
2. The symptoms rapidly run their course.—The duration of 
the symptoms of poisoning, like their appearance, is subject to 
great variation, even with regard to the same substance. Some 
few poisons, as hydrocyanic acid, nicotine, and conine, usually 
prove fatal within a few minutes, and most of them within com- 
paratively short periods. Yet, as just intimated, great differ- 
ences have been observed even in regard to the action of the 
same substance. Thus the fatal period of hydrocyanic acid 
has been protracted for several hours; whilst, on the other 
hand, arsenic, which on an average perhaps, does not prove 
fatal in less than twenty-four hours, has caused death in less 
than two hours. As a general result, a large dose of a given 
substance will prove more rapidly fatal than a small one, yet 
this is by no means always the case. Half a grain of strych- 
nine has caused the death of an adult in less than twenty 
minutes, while in a case in which between five and six grains 
were taken, death was delayed for six hours; and, even larger 
quantities than the last mentioned have been followed by 
recovery. 
The vegetable poisons as a class, usually, either prove fatal 
within at most a very few days, or the patient entirely recovers; 
but many of the mineral substances do not unfrequently cause 
death until after the lapse of several days. In fact, many of the SYMPTOMS AS EVIDENCE OF POISONING. 
43 
members of the latter class, may give rise to secondary effects, 
which may extend through an interval of many weeks, or even 
months. The usual period within which each of the more com- 
mon poisons proves fatal, and how far it has departed from its 
ordinary course, will be pointed out hereafter in the special 
consideration of the individual substances. 
In considering the duration of the symptoms in a case of 
snspected poisoning, it must be remembered that the symptoms 
°f some natural diseases, not only closely resemble those of cer- 
tain kinds of poisoning, but also run their course with equal 
rapidity. In most instances, however, a careful examination of 
the symptoms, with a full history of the case, when this can be 
obtained, will enable the medical practitioner to form a correct 
diagnosis; but cases not unfrequently occur the true nature of 
which can only be established by the post-mortem appearances 
aml chemical analysis. 
The diseases most likely to give rise to symptoms re- 
sembling irritant poisoning are, cholera, inflammation of the 
stomach and bowels, and perforation of the stomach; and 
those that may simulate narcotic poisoning—apoplexy, inflam- 
mation of the brain, and organic diseases of the heart. Chol- 
eia has been mistaken for poisoning by arsenic, and on the 
other hand, arsenical poisoning has been mistaken for that 
msease. The same has also been true in regard to apo- 
-1 exy and opium poisoning. The symptoms of disease of 
e homfl, in the rapidity of their action, may closely resemble 
e effects of hydrocyanic acid and of nicotine. The true na- 
ture of some of the foregoing diseases is readily revealed upon 
ssectmn; but others, like the poisons with whose symptoms 
ey may be confounded, leave no well-marked morbid ap- 
pearances. 
In the examination of a case of suspected poisoning, the 
medical attendant should obtain as far as possible a full history 
? the progress of the symptoms and their relation to the tak- 
mg of food, drink, or medicine. All suspicious articles of this 
me should be collected; and if vomiting has occurred, the 
matters ejected should also be collected and their character 
n°ted. .4U articles thus obtained should be sealed up, if solid, 44 
INTRODUCTION. 
in clean white paper, and if liquid, in clean glass jars, dis- 
tinctly labeled, and preserved for future examination, the col- 
lector being careful not to permit any such article to pass out 
of his possession until delivered to the proper person. 
A chemical examination of some of these articles may at 
once reveal the true nature of the symptoms. It need hardly 
be remarked, that a failure to discover poison under these cir- 
cumstances, will by no means be conclusive evidence that a 
poison had not been taken. On the other hand, the detection of 
poison in a remnant of food or medicine taken by the person, 
will not of itself be conclusive proof that a poison had been 
taken. Symptoms of poisoning have been feigned and poison 
put into articles of this kind for the purpose of charging another 
with an attempt to murder. The existence of this fact can, of 
course, only be determined by the attending circumstances. A 
few years since we were engaged in a case in this city in which 
it clearly appeared that a man maliciously put a large quantity 
of white arsenic into an alcoholic medicine he was using, and 
actually swallowed sufficient of the mixture to produce serious 
symptoms; he then charged his wife with the poisoning. 
2. Evidence from Post-mortem Appearances. 
There are but very few instances in which the post-mortem 
appearances are peculiar to poisoning. Nevertheless, this part 
of the evidence should always be very carefully considered, for 
when taken in connection with the symptoms and other circum- 
stances, it may fully establish the true character of a case, 
which would otherwise be doubtful. In death from natural dis- 
ease, a post-mortem examination may at once discover the fact. 
However, appearances of ordinary disease may be present, and 
death have resulted from the effects of poison. Several in- 
stances, in which coincidences of this kind existed, might be 
cited. The presence of some few poisons, as opium and hydro- 
cyanic acid, may sometimes be recognised by their odor; and 
others, when in the stomach, by their color or botanical charac- 
ters. It is a popular belief, that great lividity of the body and 
rapid decomposition always attend and are characteristic of MORBID APPEARANCES OF POISONING. 
45 
death from poisoning; but these results are rarely produced, 
ar*d are by no means peculiar. 
Some poisons leave no appreciable morbid changes in the 
dead body; and of those that usually do, the appearances are 
subject to great variety, and in many instances similar to the 
effects of ordinary disease, or even the results of cadaveric 
changes. The mineral acids and caustic alkalies usually leave 
most marked evidence of their action, and in some instances 
this is quite characteristic. 
The irritant poisons as a class usually produce irritation 
and inflammation of one or more portions of the alimentary 
canal, the effects being sometimes confined to the stomach, 
'cvli ile at others they extend to a greater or less extent through- 
-ollt the entire canal. In some instances the coats of the 
s oroach become ulcerated and softened, and even perforated. 
°isons of this class, however, may cause death without leaving 
ariy discoverable change in the body. This has been the case 
en in respect to some of the more acrid and corrosive sub- 
stances. In several instances of poisoning by arsenic, which 
generally produces strongly marked appearances in the stomach 
and bowels, nothing abnormal was found upon dissection. In 
the minute examination of the tissues of the alimentary canal, 
1 • Baillou advises the inspection to be made under transmit- 
ted light. 
Narcotic poisons in some instances produce more or less dis- 
tention of the veins of the brain, but in others they leave no 
marked morbid appearances, and in none are the appearances 
peculiar. According to Orfila, the lungs almost always present 
Vlcl and black spots; and their texture is more dense and less 
ClePitant. These appearances, however, may result from ordi- 
iniry causes. In some few instances there has been more or 
Ss irritation of the alimentary canal; but this condition was 
|iiost probably induced by the vehicle in which the poison was 
~en, or the remedies subsequently administered. 
Narcotico-irrHants partake in the nature of their effects of 
0 1 the preceding classes. Thus, they may produce irritation 
even ulceration of portions of the alimentary canal, and 
JllbCstion of the lungs and of the veins of the brain and its 46 
INTRODUCTION. 
membranes. But in most instances, the morbid changes are 
not well marked. 
The usual morbid changes produced by the individual 
poisons, will be pointed out hereafter; but in this connection 
may be briefly mentioned some of the appearances which may 
be equally produced by ordinary disease or cadaveric changes 
and by poisoning. 
Appearances common to Poisoning and Disease.—Redness of 
the stomach and intestines as the effect of poisoning, can not in 
itself be distinguished from that arising from natural disease. 
This condition is not only frequently the result of active dis- 
ease; but it has often been observed immediately after death 
in cases in which during life there were no indications of 
derangement of the stomach or bowels. Moreover, various 
pathologists have observed that pseudo-morbid redness of the 
mucous membrane of the stomach sometimes makes its appear- 
ance several hours after death. Dr. Christison is of the opinion 
that an effusion under the villous coat of the stomach, and 
incorporation with its substance, of dark brownish-black blood, 
is characteristic of violent irritation, if not of the effects of 
poison alone. It is well known that colored substances within 
the stomach, and the contact of this organ after death with the 
adjacent parts, may cause it to become more or less colored. 
But these appearances are readily distinguished from the effects 
of poison. 
Softening of the stomach is another appearance which may 
give rise to embarrassment. When due to the action of poison, 
it is usually accompanied by other appearances which readily 
distinguish it from the effects of ordinary disease or post- 
mortem changes. Dr. Carswell has shown that this condition 
is not unfrequently produced by the chemical action of the 
gastric juice after death. He also observes, that in softening 
of the mucous membrane of the stomach as the result of inflam- 
matory action, the tissue is always more or less opake, and the 
action attended by one or more of the products of this patho- 
logical state; whereas in post-mortem softening, the tissue is 
always transparent, and the action never attended with serous 
effusion or other concomitants of inflammation. MORBID APPEARANCES OF POISONING. 
Ulceration and perforation of the stomach, are not unfre- 
fluently produced by corrosive poisons, but they, especially the 
latter, are rarely met with as the result of the action of the 
Slmple irritants. As the effect of natural disease or post- 
mortem action, they are not uncommon. In many instances 
these appearances, as the result of poisoning, can only be dis- 
tinguished from those arising from other causes, by a history of 
the symptoms during life, or the detection of poison in the tis- 
sues or other parts of the body. This distinction is usually well 
marked in the action of the mineral acids and caustic alkalies. 
Perforation of the stomach has not unfrequently occurred 
from gelatinisation of its tissues, and in cases in which during 
hfe there was no evidence of a diseased state of that organ. 
These appearances have been chiefly observed in cases of 
Vlolent or sudden death. It was formerly believed that this 
condition was always a morbid process, and characteristic of a 
special disease. But, since the researches of modern patholo- 
Sl§ts have shown that the gastric juice has the property of 
dissolving the dead stomach, and that many of these lesions 
have undoubtedly been due to the action of that fluid after 
flcath, there is little doubt that they may all be referred to 
post-mortem changes. When the gastric juice escapes through 
Ihe aperture thus produced, it may, as has often been the case, 
exert its solvent action upon the adjacent organs. As these ap- 
pearances are unattended by signs of irritation, they are 
Usually readily distinguished from the effects of poisoning. 
muld, however, a perforation of this kind occur in a case in 
vvhich prior to death the stomach was affected with signs of 
it might be impossible from the appearances alone to 
etermine the true character of the perforation. 
Perforation of the oesophagus and of the intestines as the 
result of poisoning, is not at all likely to occur. In fact, there 
seems to be only one instance of the former, and none of the 
a er, on record. But these conditions, as the result of disease, 
ave often been observed; and they have even resulted from 
le action of the gastric juice after death. 
Points to he observed in post-mortem examinations.—All 
Uvestigations of this kind should be made in the presence of 48 
INTRODUCTION. 
the proper law officer; and it is well for the examiner to have 
the assistance and corroboration of another physician. All 
appearances observed, whether abnormal or otherwise, should 
be fully written down at the time of their observance. The 
length of time the person has been dead; how long lie survived 
the first symptoms; and the condition of the body in respect to 
external appearances, should as far as practicable be learned 
and carefully noted. In the dissections, the condition of the 
entire alimentary canal, and of all the organs essential to life, 
should be minutely examined; in the female, the vagina and 
uterus should also be inspected. The stomach with its con- 
tents, and a portion of the small intestines, properly ligatured, 
should be removed from the body. The condition of these 
organs, and the nature of their contents, may then be exam- 
ined. In some instances, however, it is best not to open these 
organs until they are delivered to the chemist. A portion of 
the liver and of the blood, should also be removed for chemical 
analysis. Although some of the poisons may be recovered by 
chemical analysis ‘from various other portions of the body, as 
from the spleen, kidneys, heart, and even from the muscles; 
yet it is rarely necessary to reserve for this purpose, any parts 
other than those already specified. 
All the organs and the blood thus removed should be col- 
lected in separate, clean glass vessels, great care being taken 
that none of the reserved substances at any time be brought in 
contact with any substance that might afterwards give rise to 
suspicion. Before passing out of the sight of the examiner, the 
bottles should be securely sealed and fully labeled. They 
should then be retained in his sole possession until delivered to 
the proper person. 
3. Evidence from Chemical Analysis. 
Importance of chemical evidence.—ln most charges of pois- 
oning, the final issue depends upon the result of a chemical 
analysis. In fact, in many instances in which the evidence 
from symptoms, post-mortem appearances and moral circum- 
stances, is very equivocal or in part wanting, a chemical VALUE OF CHEMICAL ANALYSIS. 
49 
examination may at once determine the true cause of death. 
It must he remembered, however, that a person may die from 
the effects of poison and not a trace of its presence be discov- 
erable in any part of the body; while on the other hand, the 
mere discovery of a poison in the food or drink taken or in the 
body after death, is not in itself positive proof that it occa- 
sioned death. 
It has been claimed, that a failure to detect poison in the 
dead body, by proper chemical skill, was evidence that death 
VVas the result of some other cause; hut this claim is entirely 
groundless. The symptoms and pathological appearances, at 
least in connection with moral circumstances, are often suffi- 
Clent m themselves to fully establish death from poisoning; and 
a number of convictions have very properly been based on 
these grounds in instances in which chemical evidence was 
wanting, and even when it had entirely failed. There are a 
number of organic poisons which at present can not be recog- 
nised by chemical tests; and instances are recorded in which 
death resulted from large quantities of some of the poisons most 
easy of detection, and not a trace could be discovered in any 
Part of the body. It is obvious that the discovery of minute 
Places of such poisons as are used medicinally, could not, inde- 
pendent of symptoms and other circumstances, be regarded as 
evidence of poisoning. 
Substances requiring analysis.—The substances that may 
nectly become the subject of chemical analysis, in a case of 
inspected poisoning, are: the pure poison in its solid or liquid 
®tate; suspected articles of food or medicine; matters ejected 
the body by vomiting or purging; the urine; suspected 
®°lids found in the stomach or intestines after death; the con- 
-11 sof the stomach or bowels; any of the soft organs of the 
OcV 7as the liver, spleen, etc.; and the blood. 
sometimes it is only necessary to examine one of the above- 
mentioned substances; but in many instances, two or more of 
require examination. If a poison be thus detected, it 
sometimes become necessary to examine substances other 
lan those specified, in order to determine its real source. The 
ence of poisoning is, of course, most complete when the 
4 50 
INTRODUCTION. 
poison is recovered from some of the soft organs of the body, 
after it has been absorbed. So also, the proof will be more 
direct when the poison is detected in the contents of the 
stomach or intestines, than in articles of food or medicine. 
Precautions in regard to analyses.—When called to make a 
chemical examination of any suspected material, the analyst 
should obtain, as far as practicable, a knowledge of the symp- 
toms, and, if death has taken place, of the post-mortem ap- 
pearances, observed in the suspected case: since these, when 
known, will generally enable him to decide at least to which 
class of poisons the substance belongs, and in some instances 
will even indicate with considerable certainty the individual 
substance. He may thus, by following these indications in the 
analysis, save much labor, and—which in many instances is of 
much more importance—be enabled to fully establish the pres- 
ence of poison when present in quantity too minute to be rec- 
ognised under other circumstances. It must not be forgotten, 
however, that irritant poisons have produced symptoms resem- 
bling those induced by some of the narcotics, and that the lat- 
ter may produce symptoms of irritant poisoning. 
So also, before applying any chemical test to a suspected 
solid or liquid, its quantity—of the former by weight and of the 
latter by measure—should be accurately determined. In the 
application of the reagents, the very least quantity of the ma- 
terial that will answer the purpose, should, at least at first, be 
employed for each test. In like manner, in the preparation of 
complex mixtures, the residual solution should be reduced to 
the very smallest volume compatible with the application of the 
tests that it may become necessary to apply. There is little 
doubt, that in many of the reported instances of non-detection 
of poisons, the failures have resulted from a neglect of this 
point. It should always be borne in mind, that a given quan- 
tity of a poison, when in solution in a small quantity of fluid, 
may yield with a given reagent, perfectly characteristic results; 
whereas if the solution be but slightly more dilute, the reaction 
may entirely fail. Thus, the hundredth part of a grain of nico- 
tine in one grain of water, yields with bichloride of platinum, 
a copious and rather characteristic crystalline precipitate, while VALUE OF CHEMICAL ANALYSIS. 
51 
the same quantity in ten grains of that liquid yields no precip- 
itate whatever. 
In the preparation of the contents of the stomach and of 
the solid organs of the body, it is often advisable to employ 
ordy about one-half or two-thirds of the matter for the first 
examination. This proportion will perhaps in all cases, at 
least in regard to mineral poisons, suffice to show the poison if 
present, while in case of accident, the analysis could be 
repeated. When, however, the analyst has perfect confidence 
m his ability to go safely through with the examination, it is 
perhaps best not to make this division of matter, at least in the 
investigation for certain organic poisons. The minute quantity 
°I poison usually taken up by the blood, especially in the case 
°f the alkaloids, renders it necessary to operate upon compara- 
tively large quantities of this fluid, and to conduct the exam- 
ination with extreme care. 
When the symptoms or attending circumstances do not point 
t° a particular poison or at least to the class to which it belongs, 
] 18 obvious that a division of the matter submitted for exam- 
ination becomes absolutely necessary. Under these circum- 
stances, great care should be exercised not to subject the matter 
to any process that would preclude the possibility of examining 
i any poison for which it might afterwards become necessary 
to look. 
It need hardly be observed that during investigations of this 
md, the examiner should never lose sight of the suspected 
Material, except when it is in some secure place; and the 
Neatest possible care should be taken that it is not brought in 
c°ntact with any substance the nature of which is not fully 
understood. A neglect of these directions may prove fatal to 
e results of a chemical examination. The careful analyst 
feed not be cautioned against hasty conclusions in regard to the 
ebavior of reagents. 
After the presence of a poison is fully established, it is in 
most instances only necessary to be able to state the probable 
amount present,* but sometimes it is necessary to determine its 
®xact quantity. In all cases in which it is practicable, it 
ost to determine the actual amount recovered ; but it not 52 
INTRODUCTION. 
occurs, especially in the detection of absorbed 
poison, that the quantity present is so small as not to admit 
of a direct quantitative analysis. Under these circumstances, 
we may often, by accurately noting the volume of solution 
obtained and observing the comparative reaction of several 
tests, estimate very closely the strength of the solution, and 
from this deduce within narrow limits the amount of the poison 
present. 
It was formerly claimed that unless a quantity of poison suf- 
ficient to destroy life was found in the dead body, the chemical 
evidence of poisoning was defective. But it is now a well- 
known fact, that a person may die from the effects of a large 
dose, and very little or even not a trace of the noxious agent 
remain in the body at the time of death. As any of the poison 
remaining in its free state in the stomach at the time of death, 
has had no part in producing the fatal result, it is obvious that 
to recover a fatal quantity from that which had been absorbed, 
and which was really the cause of death, even granting that 
none had been eliminated from the body with the excretions, 
would require an analysis of the entire body and the recovery 
of every atom of the poison from that complex mass—the first 
of which is impracticable and the second impossible. It is 
only, therefore, in cases in which more than a fatal dose 
remains in the body at death, that we are able to recover suf- 
ficient to destroy life. Moreover, as already intimated, the 
amount of poison in the body at death, is in itself no index 
whatever of the actual quantity taken. 
Value of individual chemical Tests.—The result of a chem- 
ical examination will depend, at least in a great measure, upon 
how far we are acquainted with reactions peculiar to the sub- 
stance under consideration; the delicacy of these reactions; and 
in many instances, our ability to separate the substance from 
foreign matter. There is usually no difficulty in recognising 
the presence of any of the mineral poisons, even when present 
only in minute quantity; but the case is very different in re- 
gard to the detection of many of the organic poisons. For the 
recognition of many poisons, we are at present familiar with 
several tests, the reaction of each of which is characteristic VALUE OF CHEMICAL ANALYSIS. 
53 
°f the substance; while for the detection of others we are 
acquainted with only one such reaction; there are others still, 
for which we have no specific reagent, but whose presence 
can be fully established by the concurrent result of several 
lests; lastly, there are some organic poisons for the detection 
°f which, at present, there is not even known any combination 
°f chemical reactions by which they can be detected. Some 
°f the poisons of the last-mentioned class, may, in the form of 
leaves, seeds or roots, be recognised by their botanical char- 
acters; and others, by their peculiar physiological effects, espe- 
cially when these are taken in connection with some of their 
general chemical properties. Among the poisons that can be 
readily detected when in their pure state, there are some which 
when present, even in quite notable quantity, in complex 
organic mixtures, adhere so tenaciously to the foreign organic 
Matter, that it is difficult or impossible to separate them in a 
state sufficiently pure to determine their presence. 
For the detection of all the poisons considered in the pres- 
cnt volume, with the exception of aconitine, we are acquainted, 
Under certain conditions, with one or more special chemical 
1 ©actions; and most of them, especially by the aid of the 
Microscope, can now be recognised with absolute certainty, and 
even separated from complex organic mixtures, in quantities 
which not long since would have appeared perfectly fabulous. 
'jFus, at present we can recognise by chemical means, when in 
its pure state, the presence of the 10,000 th part of a grain, and 
ln s°iiie instances even less, of either arsenic, mercury, strych- 
Miie, hydrocyanic acid, or atropine, with absolute certainty. 
does not however follow, that quantities as small as these 
hen present in complex mixtures can be recovered and their 
Mature then established. It is a popular idea, and indeed a 
V(irJ fair inference from the statements of some writers, that 
■f 1 / 
e quantity of a substance that can be recognised by chemical 
Means in its pure state, represents that which can be detected 
Mider all circumstances. But this is a great error, since the 
quantity that can thus be recognised and the amount necessary 
? Present in a complex mixture to enable us to separate 
a quantity, may differ many hundreds and even thousands of INTRODUCTION. 
times: the difference usually being in proportion to the com- 
plexity of the mixture. 
From what has already been stated, it is obvious that in 
determining the nature of a suspected substance, it is not 
enough that it yields affirmative reactions with a given number 
of reagents; but we must know that one or more of these taken 
singly or two or more of them taken in connection, are peculiar 
to the substance. Thus aconitine can be precipitated by sev- 
eral different reagents, yet none of these reactions taken singly 
nor several of them taken in connection, when obtained from 
small quantities of organic mixtures, will fully establish the 
presence of this alkaloid, since there are many other organic 
substances which yield similar results. We have, however, 
for the detection of this poison, a delicate and characteristic 
test in its peculiar physiological effects. Again, morphine 
yields certain results with several different reagents, yet neither 
of these taken singly, when obtained from small quantities of 
amorphous organic mixtures, is characteristic of this poison; 
but the concurrent action of two or more of them will fully 
establish its presence, since there is no other substance known 
that possesses these several properties in common with mor- 
phine. When, however, we have even a very minute quantity 
of this poison in its crystalline state, then one or more of these 
tests taken singly, may be characteristic, since most of the fal- 
lacious substances are uncrystallisable. It frequently happens 
that a test of this kind is applied under conditions in which the 
substance having reactions similar to that of the suspected sub- 
stance could not be present, when, of course, an affirmative 
reaction is specific. 
The true nature of a reaction that is common to several 
substances, can in some instances be readily determined by 
means of the microscope. Thus, a solution of nitrate of silver, 
when exposed to several different vapors, becomes covered with 
a white film; but hydrocyanic acid is the only one in the action 
of which the film is crystalline, and this is characteristic even 
with the reaction of the 100,000 th part of a grain of the acid. 
A substance may yield a peculiar crystalline precipitate at one 
degree of dilution, while at another, the precipitate may not be VALUE OF CHEMICAL ANALYSIS. 
55 
characteristic, as illustrated in the action of bromine with 
atropine, which yields from one grain of a 20,000 th or stronger 
pure solution, a specific crystalline deposit, while from solutions 
hut little more dilute, the result is not peculiar. 
So also, the true nature of a reaction, may in some instances 
he determined by submitting the result to a subsequent test. A 
shp of clean copper, when boiled in a hydrochloric acid solution 
°f either arsenic, mercury, antimony, or of several other metals, 
becomes coated with the metal; but when the coated copper is 
heated in a reduction-tube, arsenic is the only substance that 
will yield a sublimate of octahedral crystals, and mercury the 
only one that will furnish metallic globules. Some tests can be 
successfully applied only to comparatively pure solutions, whilst 
others can be thus applied to very complex mixtures. The 
°opper test for arsenic and mercury, just mentioned, yields in 
uiany instances much the same results with complex mixtures 
as With pure solutions. But this result, is true only in regard 
a few tests for the detection of mineral substances. 
In examining a suspected substance or solution, it is usually 
best, especially when the quantity of material is limited, to be- 
gm with the most characteristic test, after which if it produces 
an affirmative result, one or more corroborative tests should be 
employed. In many instances, the positive reaction of a single 
ffist, obtained from even a very small fractional part of a grain 
°f the poison, may in a chemical point of view, be as con- 
elusive of its presence, as the result of any number of tests 
applied to any quantity of the substance however great. Yet, 
I°r medico-legal purposes, it is always best, if sufficient material 
)Q at hand, to confirm the results by several tests, and when 
practicable, show the presence of the poison by two or more 
methods. 
If any of the corroborative tests thus applied, should fail, 
we should be able to account for the failure. This may be due 
f° want of delicacy on the part of the reagent or the presence 
. s°me substance, such as a free acid, an alkali or other for- 
eiB'u matter, which prevents its normal action. For the same 
! eas°u, if the test first applied should fail, we should be cautious 
111 c°ucluding the entire absence of poison, unless we are fully 56 
INTRODUCTION. 
acquainted with the conditions under which the test was applied. 
Thus it has just been stated, that copper becomes coated with 
arsenic when boiled in a mixture of that metal and hydrochloric 
acid, but we may have an impure mixture of this kind in which 
the metal will not be deposited, even when present in large 
quantity. In fact, here is no test that will produce with a 
given substance, the same results under all conditions. In the 
special consideration of the individual tests, the conditions under 
which they may fail, as well as the fallacies to which they are 
liable, and the limit of each for pure solutions, will as far as 
practicable be pointed out. 
The behavior of a test the reaction of which taken alone has 
no positive value, is often important in directing the application 
of other tests. A solution of iodine produces a distinct reaction 
even with the 100,000 th part of a grain of strychnine, when in 
solution in one grain of water ; yet as this reaction is common 
to most of the alkaloids and other organic substances, the mere 
production of a precipitate would not establish the presence of 
the alkaloid in question. Should, however, this test under 
proper conditions fail, it would follow that the suspected solu- 
tion did not contain even the 100,000 th part of its weight of 
the alkaloid, and therefore that it would be useless to apply any 
less delicate test for this poison to the solution. 
Failure to detect a poison.—Numerous instances are reported 
in which persons died from the effects of poison, and none was 
discovered by chemical analysis in the body after death. This 
result has most frequently been observed in poisoning with 
organic substances, but it has happened when mineral poisons, 
and even those which are most easily detected by chemical 
tests, had been taken in large quantity. 
A failure of this kind, may be due to any of the following 
circumstances: 1. The poison may have been one of the organic 
substances which can not at present be recognised by chemical 
tests. 2. The quantity present in the part examined may have 
been so minute as under the circumstances not to admit of re- 
covery, or at least in a state sufficiently pure to permit its true 
nature to be established. 3. It may have been removed from 
the stomach and intestines, by vomiting and purging or by VALUE OF CHEMICAL ANALYSIS. 
57 
absorption. 4. The absorbed poison may have been carried out 
°f the system with the excretions. 5. If volatile, like hydro- 
cyanic acid and some few other poisons, it may have been dis- 
Slpated in the form of vapor. 6. It may" have undergone a 
chemical change in the living body, or, especially if of organic 
cngm, have been decomposed in the dead body if far advanced 
putrefaction. 
The period in which a poison may be entirely expelled from 
Ibe stomach by vomiting, is subject to great variation. Dr. 
Christison cites two instances of poisoning by arsenic, in which 
death ensued under much vomiting in five hours, and in one of 
which none of the poison could be detected either in the con- 
sents or tissue of the stomach, and in the other, only the fif- 
teenth part of a grain was recovered. In two other instances 
°f like poisoning, in which death took place in eight hours, 
after one ounce and nearly two ounces respectively, had been 
taken, not a trace of the noxious agent was discovered in the 
stomach. On the other hand, Orfila mentions a case, in which 
aisenic was detected in the contents of the stomach of an indi- 
vidual who had vomited almost incessantly for two entire days, 
in a case which we examined not long since, in which 
there had been almost incessant vomiting for thirty-two hours, 
|brty-two grains of the same poison were recovered; it having 
een taken in the form of “fly-powder,” and much of it existing 
111 solid state attached to the mucous membrane of the organ. 
Similar results have been observed in regard to the removal 
of * 
poison from the stomach and bowels by absorption, even in 
Cases in which there was neither vomiting nor purging. Com- 
paiatively large quantities of some of the organic poisons, have 
aPparently thus disappeared within a very few hours. In a 
of poisoning by strychnine, in which about six grains had 
611 taken and death ensued in six hours, most careful anal- 
Ses, V Dr. Reese, of Philadelphia, of the contents of the 
8 °mach, and of a portion of the small intestines, failed to 
the presence of a trace of the poison. So also, in a case 
qj Polsoning by not less than two ounces of laudanum, Dr. 
iustxson tailed to detect morphine in the contents of the 
aiach, although the person survived the taking of the poison 58 
INTRODUCTION. 
only five hours. Some of the mineral poisons may remain in 
the contents of the living stomach and intestines for several 
days. Thus Dr. Geoghegan found arsenic in the contents of the 
colon after twelve days. 
After a poison has been absorbed and carried into the tis- 
sues of the body, it is sooner or later eliminated from the body 
with the different excretions, more especially with the urine. 
Many instances are recorded in which death took place with 
the usual rapidity from the effects of large doses of the most 
easily detected mineral poisons, and there was a failure to dis- 
cover the poison in any part of the body. Orfila concluded 
from his investigations, that arsenic, mercury, and the mineral 
poisons generally, were under ordinary circumstances, entirely 
eliminated from the living system, in about fifteen days, and 
this view has been sustained by the observations of others. 
The period of entire elimination, however, is subject to consid- 
erable variation: it has been limited to a few days, while on 
the other hand, some of the mineral poisons have been detected 
in the urine so long as three weeks and even longer, after they 
were taken into the stomach. 
There is no longer any doubt that the vegetable poisons, 
such as the alkaloids, enter the blood by absorption, in part at 
least, in their unchanged state, and are thus conveyed to the 
tissues; but hitherto there has generally been a failure to 
recover them from the blood and tissues, even under apparently 
the most favorable circumstances. We have recovered all the 
poisons of this class considered in the present treatise, from the 
blood of poisoned animals, but that they should always be re- 
covered, even under favorable conditions, from the blood of the 
poisoned human subject, we will not pretend to assert; still, 
with improved methods of analyses and the aid of the micro- 
scope, there is little doubt that failures of this kind will become 
less frequent. 
In regard to the effects of chemical changes and decomposi- 
tion in removing poison beyond the reach of analysis, it may be 
remarked that some of the organic poisons, especially when of 
a volatile nature, may undergo a change of this kind in the 
dead body after very short periods. In a case of suicide by CHEMICAL REAGENTS. 
59 
Hydrocyanic acid, quoted by Professor Casper, no trace of it was 
round in the stomach twenty-six hours after death, but there was 
Present a considerable quantity of formic acid, as the result of 
metamorphosis of the original poison. In like manner, this 
same poison may be converted into hydrosulphocyanic acid, 
during the process of putrefaction. So also, phosphorus, by 
combining with oxygen, is sooner or later converted into one or 
niore of the acid oxides of phosphorus; this conversion may even 
he completed in the living body. It need hardly be remarked, 
that when a chemical antidote has been administered, none of 
the poison may remain in its uncombined state or the form in 
which originally taken, in the stomach. 
On the other hand, some of the vegetable alkaloids may 
1 eniain in their unchanged state in the dead body and other 
decomposing organic mixtures, for at least some months. Al- 
though the metallic poisons may undergo chemical changes, even 
the living body, yet as the metals themselves are indestructi- 
(h the compounds thus produced, may in some instances be 
recovered even after many years. 
0/ chemical reagents.—Only those having practical experi- 
ence in the matter, know the difficulty of obtaining at least cer- 
tain reagents and chemicals, in a state of absolute purity. The 
nnpnrity may in some instances be an ordinary poison and even 
c°nsist of the very substance suspected to be present in the 
I'natters submitted for examination j while in others, it may be of 
a Mature that will very much modify or altogether prevent the 
ri°i mal reaction of the reagent, or give rise to results which may 
readily be attributed to some other cause. Thus, in one of the 
Methods for the detection of arsenic, the principal chemicals 
employed are sulphuric acid and zinc, yet that metal is not 
jtifreqaently present as an impurity in each of these chemicals, 
dmnties of this kind, generally consist of inorganic substances, 
are chiefly confined to inorganic reagents. Although, under 
inary circumstances, there would be no probability of a re- 
aß’ent containing any of the organic poisons, such as strychnine, 
and the like, still an impurity of a reagent used for 
detection of any of these poisons, might readily lead to 
rioneous conclusions. 60 
INTRODUCTION. 
The analyst should never accept any reagent or chemical as 
pure, until he has fully established its purity for himself; and if 
there be any possibility of its having become changed since last 
examined, the examination should be repeated. This latter pre- 
caution is necessary since reagents, when frequently used for 
general analyses, are quite liable to become more or less con- 
taminated; and some reagents may even speedily undergo spon- 
taneous changes. All liquid reagents should be preserved in 
hard German-glass bottles, and handled only by means of per- 
fectly clean pipetts. If poured from the mouth of the bottle, it 
is difficult to control the amount used; and moreover, the portion 
left adhering to the neck of the bottle, may by the action of the 
atmosphere, become changed, and afterwards fall back into the 
solution, and thus contaminate it. It need hardly be added, that 
no other than perfectly pure distilled water should be used for 
the solution of reagents, and in all chemical operations. 
In applying a reagent to a suspected solution, it should be 
borne in mind, that the results may be much modified by the 
quantity employed. In some instances, a very slight excess of 
reagent may entirely prevent the formation of a precipitate which 
would otherwise take place. Thus a solution of morphine, when 
treated with a given quantity of caustic potash, may yield a 
copious crystalline deposit, while with slight excess of the re- 
agent, it may yield no precipitate whatever. On the other hand, 
a deficiency of reagent may produce results very different from 
those occasioned by other quantities. A limited quantity of 
sulphuretted hydrogen throws down from a solution of corrosive 
sublimate a white precipitate; while excess of the reagent pro- 
duces a hlach deposit. Any quantity of reagent above that 
necessary to produce the desired result, is an excess and may 
do harm, if only by diluting the mixture. 
All apparatus employed in contact with the suspected sub- 
stance under examination, should either be of glass or of well- 
glazed porcelain, and be washed with scrupulous care. In fine, 
any article about to be thus employed, whose purity is not en- 
tirely above suspicion, should be rejected. 
Qualifications of the analyst.—A chemico-legal investigation 
of this nature, as well remarked by Prof. Otto in regard to the 61 
QUALIFICATIONS OF THE ANALYST. 
detection of arsenic, should be intrusted only to an experienced 
chemist. He should not only be acquainted with the principles 
involved in the analysis, but know from experience how to per- 
l°un it in all its details, and be able to defend his conclusions 
from any objections that might arise at a subsequent trial. If 
ho be unacquainted with the details of the analysis of the special 
poison under consideration, he should familiarise himself with 
from by repeated experiments upon known and minute quantities 
°f the substance suspected to be present, under conditions similar 
to those under which it is supposed to exist. To point out the 
Methods by which the presence of any of the poisons therein 
considered may be fully established, and give directions whereby 
those having only a limited knowledge of practical chemistry 
may acquaint themselves with the details of the analysis, are 
among the objects of the following pages. 
In the special consideration of the different poisons, they 
yh be grouped together, in accordance with their chemical rela- 
tions or for convenience, rather than in regard to their physio- 
§ical effects. They will be discussed mider two general Parts 
0 the work: Part First will contain the inorganic poisons, with 
ich will be included Hydrocyanic and Oxalic acids; Part 
cond will be confined to the consideration of vegetable poisons. PART FIRST. 
inorganic poisons. INORGANIC POISONS. 
CHAPTER I. 
THE ALKALIES: POTASH, SODA, AMMONIA. 
General Chemical Nature.—ln their general chemical 
Uature the alkalies, potash, soda and ammonia, and their salts, 
f°rm a quite natural and distinct group of compounds.* When 
111 s°lution, either in their uncombined state or as protocarbon- 
alos, they have a strong alkaline reaction, immediately restoring 
10 blue color of reddened litmus-paper. They differ from most 
other metallic oxides in being freely soluble in water; the same 
18 also true in regard to many of their salts, especially their sul- 
P uirets and carbonates. From their aqueous solutions, they are 
*ot Precipitated under any condition by either sulphuretted hy- 
r°gen, sulphuret of ammonium or carbonate of soda; whereas all 
metals are precipitated by one or more of these reagents. 
us difference of behavior is due to the fact that the sulphurets 
aud carbonates of the alkalies are freely soluble, whilst the cor- 
responding salts of all other metals are insoluble in water. Nor 
0 fhe alkalies precipitate each other when in solution in their 
e state; and the same is true, with very few exceptions, in 
ebaid to their salts. As potash and soda, and their salts, unlike 
Unitionia and its salts, are not dissipated upon the application 
eat, they are called fixed alkalies. 
-Physiological Effects. Although the alkalies and many of 
11 salts are highly poisonous, yet they have very rarely been 
Ham J,]1 Present consideration of the distinguishing properties of the above- 
°f alkalies, the properties of the very rare substance lithia, as well as those 
Win v. recently-diseovered and exceedingly rare alkalies, ccesia and rubidia, 
11 entirely omitted. 66 
THE ALKALIES. 
administered criminally or taken for the purpose of suicide. 
They have, however, not unfrequently been taken by accident 
and produced fatal results. As the effects of the different alka- 
lies upon the animal economy are very similar in their nature, 
they will in this respect be considered together; but treated of 
separately when considering their chemical properties. 
Symptoms. 1. Of the fixed Alkalies.—When a strong solu- 
tion of either of these compounds or of their carbonates, is 
taken into the mouth, the individual immediately experiences a 
nauseous acrid taste, and there is rapid disorganisation of the 
mucous membrane of the parts with which it comes in contact. 
On account of the immediate and exceedingly acrid taste of 
these substances, the solution is sometimes rejected from the 
mouth without any portion of it being swallowed. If the solu- 
tion be swallowed, it gives rise to a sense of burning heat and 
constriction in the fauces, oesophagus and stomach, followed by 
violent vomiting of mucus matters, which sometimes contain 
blood. These symptoms are generally followed by intense pain 
in the stomach, tenderness of the abdomen, bloody purging, 
great muscular prostration, and sometimes convulsions. The 
pulse becomes rapid, small and thready; the skin covered with 
cold perspiration; and the mouth, tongue and throat, inflamed 
and swollen. If the patient survive a few days, there may be 
sloughing of the fauces, which may end in stricture of the 
oesophagus, and thus death finally take place from starvation. 
Death has in some instances resulted from inflammation and 
obstruction of the air-passages. 
2. Of Ammonia.—The effects produced by strong solutions of 
ammonia, as aqua ammonite 7 are much the same as those of the 
fixed alkalies and their carbonates; but, in some instances, it is 
even more severe in its action. With very few exceptions, 
instances of poisoning by this substance have been the result of 
accident; and in some of these death took place with great 
rapidity. In a case of poisoning by a solution of this kind 
taken with suicidal intent, quoted by Dr. Stilld, the symptoms 
were collapse, serous and bloody purging, bloody vomiting, ex- 
cruciating pain in the abdomen, and death in six hours. If the 
patient survive the primary effects of this poison, he is less PHYSIOLOGICAL EFFECTS. 
67 
likely to die from secondary effects than in poisoning by the 
fixed alkalies. 
The vapor of ammonia, even when largely diluted with 
atinospheric air and inhaled, produces violent dyspnoea, severe 
pain in the throat, irritation and inflammation of the air-pas- 
SaSes and lungs, and in some instances death. In the related 
case of a druggist, who accidentally inhaled the fumes of am- 
monia from a broken carboy, there was corrosion of the mucous 
membrane of the mouth and nostrils, great difficulty of breath - 
lng, feeble and irregular pulse, and a bloody discharge from the 
mouth and nose. These effects were followed by a most violent 
mtack of bronchitis, during which the patient could not speak 
foe several days; but he ultimately recovered. The injudicious 
Use °f this vapor for the purpose of rousing persons from a state 
°f insensibility, has in several instances been followed by fatal 
results. 
Ihe carbonates of ammonia, of which there are several, are 
intense in their action than a solution of the free alkali, 
eir intensity diminishing in proportion to the increase of car- 
bonic acid. 
Period when fatal.—In poisoning by either of the above 
substances, death may take place within a short period from the 
immediate effects of the poison; or the patient may recover 
r°m the primary irritation and ultimately die from secondary 
results months or even years after the substance had been taken. 
a case described by Mr. Dewar, a little boy who swallowed 
? mistake about three ounces of a strong solution of carbonate 
. P°tash, died from its effects in Uvelve hours afterwards. 
\ Med. and Surg. Jour., xxx, 309.) In another instance, 
a ed by Dr. Cox, a small quantity of deliquesced carbonate 
, P°tmh, proved fatal in twenty-four hours, to a child aged 
three years. 
. ffie other hand, two sisters, aged respectively twelve and 
ixteen years, took by mistake about half an ounce of subcar- 
a a.e °f potash each. Violent symptoms immediately ensued, 
m the case of the elder continued with little interruption for 
o - *wo m°nths, when death took place. In the case of the 
61 ’ le symptoms abated after a few days; but they again 68 
THE ALKALIES. 
returned, and finally proved fatal after the lapse of nearly three 
months. (Beck’s Med. Jur., ii, p. 524.) In a case recently 
reported by Dr. Deutsch, a solution estimated to contain about 
half an ounce of caustic potash, did not prove fatal until after a 
period of twenty-eight weeks. And in another, a quantity of 
impure carbonate of soda produced stricture of the gullet, of 
which the patient died two years and three months after having 
taken the poison. Sir C. Bell even relates a case of this kind, 
in which death did not take place until after the lapse of twenty 
years. 
Solutions of ammonia have proved rapidly fatal. In a case 
related by Plenck, a quantity of liquor ammonia poured into the 
mouth of a man who had been bitten by a mad dog, caused 
death in four minutes. (Christison on Poisons, p. 194.) A case 
in which a solution of this kind proved fatal in six hours, has 
already been cited. Dr. Taylor records the case of a gentleman 
who died in three days, from the effects of a solution of ammonia 
administered to him by mistake. (On Poisons, p. 331.) The 
vapor of ammonia applied to the nostrils of a lad laboring under 
a fit of epilepsy, induced bronchitis which proved fatal in forty- 
eight hours. In a somewhat similar case, death ensued on the 
third day. 
Fatal quantity.—lt is impossible at present to state with any 
degree of certainty the smallest quantity of either of the sub- 
stances under consideration that might prove fatal. In most 
instances the effects will depend rather upon the degree of con- 
centration under which the substance is taken, than the absolute 
quantity. In an instance recorded by Dr. Taylor (Op. cit., p. 
328), one ounce and a half of the common solution of potash of 
the shops, proved fatal to an adult, in seven weeks. The quan- 
tity of the caustic alkali taken in this case, did not perhaps 
exceed forty grains, which is the smallest fatal dose we find 
recorded. There are not less than four cases reported, two of 
which have already been cited, in which half an ounce of the 
carbonate of potash proved fatal: in all of these, as in the pre- 
ceding case, death was due to the secondary effects of the poison. 
Solutions of ammonia have also proved fatal when taken in 
small quantity. Thus this event has happened in at least two 69 
POST-MORTEM APPEARANCES. 
instances, in which not over two drachms had been taken. 
Instances of recovery from this substance, however, have been 
°f more frequent occurrence than from the fixed alkalies. A 
man swallowed by mistake, three drachms of a strong solution 
°f ammonia and as much of the sesquicarbonate, dissolved in 
Uvo ounces of oil ; but under appropriate treatment he recovered 
in about eight days. (Wharton and Stille’s Med. Jur., p. 502.) 
In another case, a boy aged two years, took half an ounce of 
A eiT pungent spirits of hartshorn, and recovered. Instances are 
uiso related in which recovery took place, even after more than 
an ounce of the solution had been taken. 
Treatment.—The antidote for poisoning by any of the free 
nlkalies or their carbonates, is the speedy administration of a 
solution of some of the mild vegetable acids—such as acetic 
acid in the form of diluted vinegar, or the juice of any of the 
ucid fruits—by which the poison will to a certain extent be 
Neutralised. Large quantities of olive oil have in some in- 
stances been administered with advantage. This substance may 
convert the alkali into a soap, and thus prevent its caustic action. 
arge draughts of milk may also be used with benefit. In pois- 
ing by the vapor of ammonia, Dr. Pereira recommends the 
Umalation of the vapor of acetic or of dilute hydrochloric acid. 
Tost-mortem Appearances.—These will depend in a great 
lllGasure upon the length of time the patient survived the taking 
0 the poison. In acute cases, the mucous membrane of the 
pmts with which the substance comes in contact is more or less 
being inflamed and broken up in patches; some- 
uies there is extravasation of disorganised blood upon the walls 
?j e organs thus affected, which causes them to present a blu- 
-1 °r black appearance. This appearance is sometimes well 
Nuuked in the mouth. In some instances, large portions of the 
Nucous membrane of the mouth, oesophagus and stomach, are 
entirely removed. 
°llls % a solution of carbonate of potash, the appearances were 
lllCh the same as those just described. Thus, the mucous 
*Nembrane of the pharynx and oesophagus was almost entirely 
esti oyed, and dark blood extravasated beneath the pulpy mass; 70 
THE ALKALIES. 
in the stomach, the mucous membrane was destroyed in two 
places, and these patches covered with clotted blood. Similar 
appearances were found in the case that proved fatal in twenty- 
four hours. 
In the case of poisoning by ammonia quoted above, which 
proved fatal in three days, the lining membrane of the trachea 
and bronchi was softened and covered with layers of false mem- 
brane ; while the larger bronchial tubes were completely ob- 
structed by casts of this membrane. The mucous membrane of 
the gullet was softened, and the lower end of the tube completely 
destroyed. The anterior wall of the stomach contained an aper- 
ture about an inch and a half in diameter, through which the 
contents of the organ had escaped. 
In chronic cases, the lower portion of the oesophagus and 
the stomach are frequently much contracted. The walls of the 
stomach are often thickened, and the lining membrane wholly 
destroyed. An ulcerated and gangrenous state of the mucous 
membrane of the stomach and intestines, has also been observed. 
And in some instances, other of the abdominal organs have been 
much disorganised. In Dr. Deutsch’s case, the mucous mem- 
brane of the lower portion of the oesophagus was found so 
greatly thickened, that the opening into the stomach was nearly 
obliterated. 
Nitrate of Potash. This salt, commonly known by the 
name of saltpetre or nitre, has in several instances been taken 
by accident, with fatal results. To produce serious effects, how- 
ever, it requires to be taken in large quantity, such as half an 
ounce or more. The symptoms usually observed are severe 
burning pain in the stomach and abdomen, nausea, vomiting and 
purging, followed by coldness of the extremities, tremors and 
collapse. The effects of large doses have, however, been subject 
to considerable variation. 
In a case recorded by Dr. Beck, a dose of this salt taken in 
mistake for Glauber’s salt, proved fatal to an aged man, in half 
an hour • and in an instance cited by Orfila, one ounce caused 
death in three hours. A man, who took three ounces and a 
half of the salt at a dose, apparently suffered but little for five CHEMICAL PROPERTIES. 
71 
hours, when he suddenly fell out of his chair and expired. Be- 
covery has in several instances taken place, even after so much 
as vo ounces of the salt had been taken. 
The treatment consists in the speedy removal of the poison 
from the stomach, and the subsequent exhibition of demulcents. 
chemical antidote is known. 
After death, the stomach has been found highly inflamed, 
mottled with dark-colored patches, and the mucous membrane 
partially detached. Similar appearances have also been observed 
ln the small intestines. In at least one instance, the coats of 
the stomach were perforated by a small opening. 
The Tartrate, Sulphate and Binoxalate op Potash have 
also destroyed life. The noxious effects of the last-mentioned 
salt, however, chiefly depend upon the oxalic acid which it 
contains. 
Chemical Properties op the Alkalies. 
Distinguishing properties.—Solutions of the caustic alkalies, 
aie distinguished from those of their carbonates, by the latter 
effervescing, from the escape of carbonic acid gas, when acted 
upon by hydrochloric or any of the strong acids. Sulphate op 
m\(U\EsiA, at ordinary temperatures, throws down from solutions 
°f the protocarhonates of the fixed alkalies a white precipitate ; 
whereas with the bicarbonates, it produces no precipitate. This 
1 eagent fails to precipitate solutions of either of the carbonates 
°f ammonia. 
Nitrate op Silver produces in solutions of the fixed caustic 
alxes, a brown precipitate, which is insoluble in excess of the 
._ 15 while in a solution of ammonia, it produces a somewhat 
Similar precipitate, readily soluble in excess of the alkali; when, 
11 more, the reagent is not added in excess, the ammoniacal 
0£ .°n frifr to yield a precipitate. Solutions of the carbonates 
mther of the alkalies, yield with this reagent a yellowish- 
-1 ® precipitate, which in the case of the fixed alkalies is insol- 
e m excess of the alkaline salt, while that from either of 
e carbonates of ammonia is soluble in excess of the alkaline 
°mp°und. The precipitation of the bicarbonates by this reagent, 72 
POTASH. 
is attended with effervescence, due to the escape of carbonic 
acid, but this result is not observed in the case of the protocar- 
bonates. 
Corrosive Sublimate throws down from solutions of the 
fixed alkalies, a bright yellow precipitate, which is insoluble in 
excess of the alkali; from the protocarbonates a reddish-brown; 
but in solutions of the bicarbonates it produces no precipitate. 
With ammonia and its carbonates, this reagent produces a white 
precipitate, which is somewhat soluble in excess of the alkaline 
solution, especially in the presence of ammoniacal salts. 
The different alkalies will now be separately considered, in 
regard to their chemical nature and reactions, and the methods 
by which they may be recovered from organic mixtures. 
Section I.—Potash. 
General Chemical Nature.—Potash is a compound of the 
elements potassium and oxygen (KO); in combination with one 
equivalent of water, it forms the hydrate of potash (KO, HO); 
known also by the names potassa fusa and caustic potash. This 
compound, when pure, is a white solid, but as usually met with 
in the shops in the form of little sticks, it has a greyish or 
brownish color, due to the presence of foreign matter. When 
exposed to the air, it deliquesces and slowly absorbs carbonic 
acid, becoming changed into the carbonate of potash. 
Caustic potash dissolves, with the evolution of heat, in about 
half its weight of water • it is about equally soluble in alcohol. 
Its solubility in alcohol enables us to separate it from many of 
its salts, such as the proto- and bi-carbonates, nitrate and sul- 
phate, which are insoluble in this liquid. An aqueous solution 
of caustic potash changes an infusion of violets or of red cab- 
bage to green, an infusion of tumeric to reddish-brown, and 
immediately restores the blue color of reddened litmus, even 
according to Harting, when the alkali is dissolved in 75,000 
parts by weight of water. A saturated aqueous solution of pure 
caustic potash has a density of about 2, and contains about 70 
per cent, of the anhydrous alkali. SPECIAL CHEMICAL PROPERTIES. 
73 
The following table, by Dalton, indicates approximately the 
per cent. of anhydrous potash (KO) in solutions of the alkali of 
e different given specific gravities;— 
STRENGTH OF AqUEOUS SOLUTIONS OF POTASH. 
———- 
sp- gr. 
PER CENT. 
SP. GR. 
PER CENT. 
1-78... 
56-8 
51-2 
46-7 
42-9 
39-6 
36-8 
34-4 
32-4 
1-36 
29-4 
26-3 
23-4 
19-5 
16-2 
13-0 
9-5 
4-7 
1-68.. 
1-33 
1-60. 
1-28 
1-52.. 
1*23 
1-47.. 
1-19 
1-44.. 
1 *15 
1-42.. 
1 *71 
1-39... 
1-06 
Potash, in its action upon animal tissues, is the most de- 
structive of the alkalies. When rubbed between the fingers, by 
* 8 chemical action on the skin, it imparts a soapy feel. It 
Jlns soluble compounds with many of the constituents of the 
tissues; and it may dissolve and perforate the coats of 
e stomach, even more readily than the mineral acids. 
The salts of potash are colorless except those in which the 
constituent acid is colored; and they generally crystallise with- 
.watcr of crystallisation, in which they differ in most 
from the corresponding salts of soda. With very few 
Xceptions, they are freely soluble in water. 
Special Chemical Properties.—Potassium compounds when 
cated upon a clean platinum wire, in the reducing blow-pipe 
e? impart a violet color to the outer flame. This reaction 
be entirely masked by the presence of even a small quan- 
S°^a? which gives a strong yellow color to the outer 
hll like manner, an alcoholic solution of potash or of any 
hs salts, burns with a violet flame; but this reaction is also 
sCßied by the presence of soda. 
p account of the solubility of most of the compounds of 
there are but few reagents that precipitate it from 
stro only when the solution is comparatively 
Before applying any liquid test for the detection of 
s °t either of the alkalies, the absence of metallic oxides 74 
POTASH. 
other than those of the alkalies, should be established. This 
may be done by treating a small portion of the solution, acidu- 
lated with hydrochloric acid, with sulphuretted hydrogen ; an- 
other, and neutral portion, with sulphuret of ammonium; and a 
third portion, with carbonate of soda: when, if these reagents 
fail to produce a precipitate, it follows that the metallic oxides 
mentioned are absent. 
In applying a liquid reagent, a drop of the suspected solu- 
tion may be placed in a watch-glass, and a small portion of the 
reagent added by means of a pipette. The mixture may then 
be examined by the microscope. If there be no immediate 
precipitate, it must not be concluded that the base in question 
is entirely absent 5 but the mixture should be allowed to stand, 
even in some instances for several hours, before deciding the 
entire absence of the substance. 
In the following examinations of the behavior and limit of 
the different tests for the alkali under consideration, solutions of 
the chloride of potassium and of nitrate of potash, were chiefly 
employed. The fractions indicate the fractional part of a grain 
of anhydrous potash, under the form of the salt employed, in 
solution in one grain of pure water 5 and the results, unless 
otherwise stated, refer to the behavior of one grain of the solu- 
tion, treated in the manner described above. 
1. Bichloride of Platinum. 
Bichloride of platinum throws down from solutions of salts 
of potash, when not too dilute, a yellow precipitate of the 
double chloride of platinum and potassium (KCI, PtCl2), which, 
either immediately or after a very little time, becomes converted 
into beautiful octahedral crystals. Solutions of the free alkali 
should be treated with slight excess of hydrochloric acid, before 
the addition of the reagent. From dilute solutions, the presence 
of a little free hydrochloric acid, or of strong alcohol, facilitates 
the formation of the precipitate. 
The precipitate is soluble in about one hundred and eight 
parts by weight of pure water at the ordinary temperature, but 
it is much more freely soluble in hot water; it is somewhat less SPECIAL CHEMICAL PROPERTIES. 
75 
soluble in water containing a trace of hydrochloric acid, and 
almost wholly insoluble in absolute alcohol. One part by weight 
°f anhydrous potash or its equivalent in the form of a salt, 
yields 5*2 parts of the double salt. 
f* sV grain of potash in the form of chloride of potassium, in 
solution in one grain of water, yields with the reagent an 
immediate yellow crystalline precipitate, which very soon 
increases to a copious deposit. On stirring the mixture 
with a glass rod, it leaves lines of crystals where the rod 
has passed over the watch-glass. 
The same amount of potash in the form of nitrate, 
yields about the same results. 
2 i • 
Tow grain as chloride: crystals are immediately perceptible, 
and soon there is a fine crystalline deposit, which under 
the microscope presents the appearance represented in 
Plate I, fig. 1. When the potash is in the form of nitrate, 
the precipitate is a little more slow in forming, and does 
o not become quite so abundant. 
2To grain: in about two minutes there is a perceptible pre- 
cipitate, and after a little time a quite good crystalline 
deposit. If the mixture be stirred, it yields streaks of 
granules. From the nitrate of potash, the precipitate is 
*n°re slow to form and does not become so abundant, the 
crystals being confined to the border of the mixture. A 
200 th solution of the nitrate yields only about the same 
results as a 250 th solution of the chloride. 
4. __i__ 
50 o gram: in about ten minutes crystals appear around the 
margin of the mixture; these increase, and in about three- 
quarters of an hour, there is quite satisfactory deposit scat- 
tered through the body of the drop. Stirring the mixture 
does not seem to facilitate the formation of the deposit. The 
forms of the crystals are much the same as illustrated above. 
A 400 th solution of the nitrate yields only about the 
same reaction as a 500 th solution of the chloride. A 500 th 
solution of the nitrate, however, will yield a perceptible 
deposit after standing about an hour. In these experi- 
ments, concentration of the mixture from evaporation, was 
guarded against, perhaps, however, not perfectly. 76 
POTASH. 
Harting placed the limit of this test, when applied to a solu- 
tion of the nitrate, at one part of anhydrous potash in 205 
parts of water (Gmelin’s Handbook, iii, p. 15). Lassaigne 
fixed the limit for sulphate of potash, at one part of the alkali 
in 200 parts of water (Jour. Chim. Med. 8, 527). And for the 
acetate, Pettenkofer placed the limit at one part of potash in 
500 parts of water, after standing from twelve to eighteen hours; 
but, he states, when common salt is present, the reaction is lim- 
ited to one part of the alkali in 100 parts of water, or even less 
(Gmelin, x, 276). Neither of these observers, however, state 
the quantity of solution employed in the experiment. 
Fallacy.—Bichloride of platinum also produces a similar yel- 
low crystalline precipitate in solutions of salts of ammonia. The 
absence of these salts should, therefore, be established before 
concluding that the precipitate consists of the potassium com- 
pound. This may be done, by adding some hydrate of lime or 
caustic potash to a small portion of the suspected solution and 
heating the mixture, when if it contain an ammoniacal salt, the 
odor of this alkali will be evolved. Or, the precipitate produced 
by the platinum reagent, may be heated to redness, when the 
potassium compound will leave a residue of chloride of potassium 
and metallic platinum, which when treated with a small quan- 
tity of hot water and the filtered liquid acted upon by a solution 
of nitrate of silver, will yield a white precipitate of chloride of 
silver, due to the presence of the alkaline chloride; whereas, 
the ammonium compound will leave upon ignition a residue of 
only metallic platinum, which, of course, will yield no precipi- 
tate with nitrate of silver. 
2. Tartaric Acid, and Tartrate of Soda. 
Tartaric acid, when added in excess to somewhat strong solu- 
tions of potash and of its salts, produces a white crystalline 
precipitate of tartrate of potash (KO, HO, C 8H4O10). From 
somewhat dilute solutions, the precipitate is slow in appearing; 
in such cases, its formation is much facilitated by agitation, as 
also by the addition of alcohol. The precipitate is soluble in 
the mineral acids, and free alkalies and their carbonates; if SPECIAL CHEMICAL PROPERTIES. 
77 
therefore, either of these substances be' present in excess, the 
of the precipitate will be entirely prevented. The 
Piecipitate is insoluble in free tartaric and acetic acids. 
When a solution of a salt of potash is treated with free tar- 
acid, it is obvious that the acid of the salt is set free, 
thus: K0,N05 + 2HO; C 8H4O10* = KO, HO, C 8H4O10 + HO, N05. 
le acid thus set free, may in a measure redissolve the tar- 
*la,te of potash produced by the reagent, especially if it be one 
0 the stronger acids. This elimination of the acid may be 
pi evented by using the reagent in the form of a solution of the 
ocid tartrate of soda, as first recommended by Mr. Plunkett 
\ tiern. Gaz., xvi, 217). Under these conditions, there would 
simply be an interchange of acids and bases, the soda elimi- 
ated from the tartaric acid combining with the acid set free 
0111 the potash. This reagent is readily prepared by dividing 
strong solution of tartaric acid into two equal parts, exactly 
neutralising one of them with pure carbonate of soda, and then 
adding the other. 
the following investigations, a very strong solution of 
6 tartaric acid, and a saturated solution of the acid tartrate 
j seda, were employed as the reagents. 
To grain of potash in the form of chloride or nitrate, yields 
With free tartaric acid, an immediate crystalline precipi- 
tate, which soon increases to a very good deposit. The 
tartrate of soda produces much the same results, except 
perhaps, the precipitate is somewhat more copious; the 
general forms of the crystals, however, are quite different, 
o neutral tartrate of soda produces no precipitate. 
ion grain: crystals immediately begin to separate, and after 
a little time there is a good crystalline deposit. Plate I, 
fig* 2, represents the usual forms of the crystals produced 
the pre Sl^U °fthe semicolon (0 when employed in chemical formula throughout 
express WOIU will imply that the multiplication of the figure preceding the 
implies1011* ceases at that point. Thus, the above expression (2 HO; CBH4O]0), 
Water c^elnicat equivalent of a compound, consisting of two equivalents of 
°ther hi 1 W one ecluivalent of anhydrous tartaric acid (CBH4oln). On the 
tiine i,, i ’ when it is desired to not stop such multiplication, and at the same 
e°mma ff e that two or more compounds are in intimate union, the sign of the 
O) will be employed. 78 
POTASH. 
by free tartaric acid. Tartrate of soda produces a some- 
what more abundant precipitate. 
3. -2s“o grain: in a few moments crystals appear, and very soon 
there is a quite satisfactory deposit. With the tartrate of 
soda and chloride of potassium, the precipitate is some- 
what more prompt in appearing. Plate I, fig. 3, repre- 
sents the forms of crystals usually produced by the soda 
reagent. 
4. ywo grain as chloride: within a few minutes granules ap- 
pear ; these soon become crystalline, and after a little time 
there is a quite satisfactory crystalline and granular de- 
posit. From the nitrate of potash, the precipitate sepa- 
rates much more slowly, and is chiefly confined to the 
border of the mixture; under the microscope, however, 
the reaction is quite satisfactory. After standing about 
half an hour, either of these solutions yields a quite good 
deposit of crystals having the forms illustrated above. 
When tartrate of soda is employed as the reagent, the 
precipitate is much more prompt in appearing, particu- 
larly from a solution of chloride of potassium. 
5. yiir grain as chloride: after about ten minutes, small gran- 
ules form along the margin of the mixture, and after some 
minutes more, there is a quite distinct granular and crys- 
talline deposit. With the soda reagent, granules and 
crystals appear within about four minutes, and there is 
soon a very satisfactory deposit. 
(1- T7cro“o grain of the chloride, with tartrate of soda: in about 
five minutes, crystals are just perceptible; and in about 
ten minutes, the deposit is quite distinct, but confined to 
the border of the drop. The crystals have the forms 
illustrated above, some of them being quite large. 
of potassium is the most favorable form of the alkali for the 
application of either of the above reagents. Pettenkofer placed 
the limit of the reaction of free tartaric acid, for solutions of 
the acetate of potash, at one part of the anhydrous alkali in 
from 700 to 800 parts of water, after standing from twelve to 
From the above statements it is obvious, that the chloride 
eighteen hours. SPECIAL CHEMICAL PROPERTIES. 
79 
Fallacy. These reagents also produce similar crystalline 
Precipitates from solutions of ammonia. The absence of this 
'dkali may be established in the manner indicated under the 
preceding test. 
3. Carbazotic Acid. 
A strong alcoholic solution of Carbazotic or Picric acid, 
wpen added in excess to solutions of potash and of its salts, 
Produces a yellow precipitate of carbazotate of potash (KO, 
9i2^N3H2013), which is insoluble in excess of the precipitant and 
111 aleohol. The precipitate contains 17*66 per cent, of anhy- 
dr°us potash. 
* grain of potash in the form of chloride or nitrate, yields 
an immediate amorphous precipitate, which in a few mo- 
ments becomes converted into a mass of long regular 
yellow crystalline needles, some of which extend entirely 
0 across the drop of liquid. 
Tiro grain: crystals immediately begin to form, and in a very 
little time the drop becomes a mass of very long slender 
g 1 yellow needles, Plate I, fig. 4. 
TTo grain: in a few moments, crystals begin to form, and 
after a little time, a very good deposit of long needles. 
scTo grain: much the same results as in 3. From the nitrate 
°f potash, the precipitate is not so prompt to form, nor is 
*t as abundant as in the case of the chloride. 
0. i . 
7 s'o grain in the form of chloride, yields after a little time a 
g Perfectly satisfactory crystalline deposit. 
17o'o'o grain: after a few minutes, crystalline needles appear 
along the margin of the drop; after about fifteen minutes, 
the deposit becomes quite satisfactory, especially when 
examined by the microscope. 
Th 11 applyin? reagent it should be added in large excess. 
a^Uh *Cn grains of a 500 th solution of the alkaline salt, when 
upon by a drop or two of the reagent yield no precipitate, 
be r some time; but if an equal volume of the reagent 
aech it produces a precipitate within a few moments. 
(ulacies.—Carbazotic acid also throws down from solutions 
aiinnonia and very strong solutions of soda, yellow crystal- 80 
POTASH. 
line precipitates. The microscope, however, will readily enable 
us to distinguish the potash precipitate by its crystalline form, 
from that of either of these substances. (Compare figs. 5 and 
6, Plate I.) The reagent also produces yellow precipitates, 
some of which are crystalline, with many organic substances, 
especially the vegetable alkaloids. So also, it occasions precip- 
itates with certain other metallic oxides; but the absence of 
these, as already pointed out, should be established before ap- 
plying the test. 
In applying this test it must be remembered, that a very 
strong alcoholic solution of the reagent when added in certain 
proportion to pure water, may yield a yellow crystalline precip- 
itate of free carbazotic acid. The forms of these crystals, how- 
ever, readily distinguish them from the potash compound. In 
a 500 th or stronger solution of the alkali, this distinction is 
very apparent to the naked eye; and in more dilute solutions, 
it is readily established by the microscope. 
In addition to the above, there are several other reagents 
that precipitate potash, only, however, from concentrated solu- 
tions. 
Hydropluosilicic acid in excess produces in solutions of 
the alkali, a transparent gelatinous precipitate of the silicoflu- 
oride of potassium, which is insoluble in hydrochloric acid. In 
concentrated solutions this reaction is very satisfactory. A 
50th solution of the alkali in the form of chloride, yields after 
a time, only a slight flocculent deposit. 
Perchloric acid produces in similar solutions, a white 
crystalline precipitate of perchlorate of potash. So also, a 
concentrated solution of Sulphate op Alumina, when added to 
concentrated solutions of the alkali previously acidulated with 
hydrochloric acid, precipitates crystals of the double sulphate 
of alumina and potash, or common alum. 
Spectrum ANALYSIS.—This, as first applied by Professors 
Kirchoff and Bunsen, is by far the most delicate method yet 
discovered for the recognition of potassium—as well as of 
sodium and many other volatile metals. It consists in intro- 
ducing a small portion of the caustic alkali, or any of its salts SEPARATION FROM ORGANIC MIXTURES. 
81 
containing a volatile acid, into the flame of a Bunsen gas-burner 
and allowing the rays of the colored flame to pass through a 
pnsm. The refracted rays are then examined by means of a 
small telescope, when, in the case of potassium, two distinct 
lines, one having a red color and the other indigo-blue, will be 
observed, which are characteristic of this metal. The authors 
this method, estimated that it would reveal the reaction of 
the 65,000 th part of a grain of potassium, and the 195,000,000 th 
Part of a grain of sodium. (For the details of this method, see 
Quart. Jour. Chem. Soc., Oct., 1860; also, Fresenius’ Qual. 
Analysis, London, 1864.) 
Although spectrum analysis has very largely extended the 
scope of chemical research, enabling us in a few seconds to 
meet the presence of the most minute traces of many metals, 
and bringing to light substances of which heretofore we had no 
nowledge; yet as it gives no indication whatever as to the 
Quantity of the substance present, it is still doubtful whether it 
be of any practical value in chemico-legal investigations, 
least for the detection of the fixed alkalies, since these are 
80 universally distributed through the tissues and juices of both 
auirnal and vegetable structures. 
Separation from Organic Mixtures. 
When the suspected solution is highly colored or contains 
much organic matter, the tests for either of the alkalies cannot 
satisfactorily applied directly to the mixture. If the solu- 
jun has a soapy feel, a strong alkaline reaction, and is destitute 
the odor of ammonia, even when a small portion of it is 
botli hydrate of lime, the presence of one or other, or 
the fixed alkalies, or of their carbonates may be inferred. 
caib ltller the fixed alkalies may be separated from their 
°uates and organic matter, by evaporating the mixture on 
er~kath utmut dryness and digesting the cooled residue 
its 1 a^S°Aite alcohol, which will dissolve the free alkali, while 
S°lvCadrb°nates, uther salts if present, will remain undis- 
vnl 6 " le utcuholic solution is then concentrated' to a small 
le7 and if strongly alkaline and nearly colorless, at once 
6 82 
POTASH. 
neutralised with hydrochloric acid, and examined by the appro- 
priate reagents. If however, it contains much organic matter, 
before being tested, it should be evaporated to dryness, the 
residue incinerated at not above a dull red heat until the 
organic matter is entirely destroyed, and the cooled mass dis- 
solved in water; the aqueous solution is then examined in the 
ordinary manner. 
Although the alkaline carbonates in their pure state, are 
almost wholly insoluble in absolute alcohol, yet the presence of 
certain kinds of organic matter renders them slightly soluble in 
this menstruum. A small quantity of these salts may, therefore, 
be extracted along with the caustic alkali in the above opera- 
tion. To ascertain the presence of fixed alkaline salts in the 
residue from which the free alkali was extracted by alcohol, 
the mass is incinerated in the manner directed above, and the 
cooled residue dissolved in distilled water. 
Another method recommended for the recovery of the fixed 
alkalies and their carbonates from complex organic mixtures, 
is to evaporate the solution to dryness, incinerate the dry mass, 
and then separate the free alkali from its carbonate by means 
of absolute alcohol. This method has the advantage of at once 
destroying the organic matter, but the charring of this converts 
more or less of the free alkali into carbonate, the quantity thus 
converted depending upon the relative amount of organic matter 
present. The amount of free alkali, therefore, furnished by 
this method would be somewhat less than originally existed; 
while by the preceding process, the estimate of this substance 
might be somewhat too high. 
Quantitative Analysis.—The quantity of potash present 
in pure solutions of the free alkali or of its carbonates, may be 
estimated by precipitating it in the form of the double chloride 
of platinum and potassium. For this purpose, the alkali is 
converted into chloride, by the addition of hydrochloric acid, 
and the somewhat concentrated solution treated with slight 
excess of bichloride of platinum. When the precipitate has 
completely deposited, the mixture is concentrated on a water- 
bath, to near dryness, and the cooled residue washed with SODA: GENERAL CHEMICAL NATURE. 
83 
stiong alcohol, which will remove the excess of reagent added. 
16 residue, consisting of the double salt, is then collected on 
a filter of known weight, washed with a little more alcohol, 
riecb and weighed. Every 100 parts by weight of the double 
i thus obtained, represent 22-5 parts of caustic potash 
V HO): or 28-25 parts of anhydrous carbonate of potash 
(Ko, C02). 1 
In all investigations of this kind, the original solution pre- 
sided for examination should be carefully measured, and a 
bDen portion set apart for the quantitative analysis. From 
0 amount of poison discovered in this, the entire quantity 
piesent, may, of course, be readily deduced. 
Section ll.—Soda. 
General Chemical Nature.—This alkali, in the form of 
yt iate of soda, or caustic soda (NaO, HO), is a white opake, 
powerfully alkaline, caustic substance, which when exposed to 
air> absorbs water and carbonic acid, becoming converted 
? Cai’fionate of soda. In its chemical action upon the tissues, 
!s somewhat less energetic than the potash compound. It is 
j. * So^fifie in water, with the evolution of heat, yielding a 
q,* y caustic liquid. The aqueous solution, according to 
contains the following per cent, of anhydrous 
sohg according to the different specific gravities of the 
strength of aqueous solutions of soda. 
Sp- 6R. 
PER CENT. 
SP. GR. 
PER CENT. 
1-428.. 
30-22 
26-59 
22-96 
20-55 
18-73 
16-92 
14-50 
1-1Q4 
12-69 
10-87 
8-46 
6-64 
4-83 
2-41 
1-20 
1 3/5.. 
1-162 
1'327.. 
1 -1 93 
1-298.. 
1-0Q4 
1-277. 
1-067 
1-257.. 
1 033 
1-228.. 
1 -01 fi 
~ 
P h 
e salts of soda are colorless, unless containing a colored 
acid. rpi . . ° . 
-‘-ftey are readily soluble in water, and more disposed 84 
SODA 
than the corresponding compounds of potash, to unite with 
water of crystallisation. The crystallised protocarbonate, as 
also several other salts, contains ten equivalents of water of 
crystallisation. Many of its salts speedily effloresce when ex- 
posed to the air. 
Special Chemical Properties. When caustic soda, or 
any of its salts, is heated in the inner blow-pipe flame, it com- 
municates a strong yellow color to the outer flame, even when 
only a minute quantity of the alkali is present. The presence 
of potash, even in large quantity, does not obscure this reac- 
tion. The same coloration is,developed when an alcoholic solu- 
tion of the alkali is burned. By spectrum analysis, as already 
indicated, the reaction of the merest traces of soda may be 
recognised. 
On account of the free solubility of the compounds of soda, 
there are but few reagents that precipitate it even from con- 
centrated solutions. In fact—besides the coloration of flame— 
antimoniate of potash and Polarised Light are about the only 
tests at present known, whereby small quantities of this alkali 
can be recognised. 
In the following investigations, solutions of pure caustic 
soda were employed. The fractions refer to the fractional part 
of a grain of the anhydrous alkali, NaO, in solution in one grain 
of water; and the results, to the behavior of one grain of the 
solution. 
1. Antimoniate of Potash. 
A solution of this reagent is prepared by supersaturating 
warm water with the pure salt, and filtering the liquid when 
perfectly cold. The solution should always be freshly prepared 
when required for use. 
Antimoniate of potash throws down from somewhat concen- 
trated solutions of soda and of its neutral salts, a white crystal- 
line precipitate of antimoniate of soda (NaO, Sb05). The forms 
of the crystals produced, depend very much upon the strength 
of the solution. If the solution has an acid reaction, it should 
be carefully neutralised with potash before the addition of the 
reagent, since otherwise, free antimonic acid, or biantimoniate SPECIAL CHEMICAL PROPERTIES. 
85 
°f potash may be precipitated. The reaction of the reagent is 
not prevented by the presence of moderate quantities of salts 
°f potash, excepting the carbonate, in which the soda com- 
pound is more readily soluble than in pure water. 
2? grain of soda, in one grain of water, yields with the 
reagent an immediate deposit of small granules and rect- 
angular plates; at the same time, irregular, and tooth- 
shaped crystals, as represented in the upper left portion 
of Plate 11, fig. 1, float upon the surface of the mixture. 
To grain yields an immediate crystalline precipitate, con- 
sisting principally of small elongated rectangular plates, 
as represented in the lower portion of Plate 11, fig. 1. 
TTo grain: an immediate deposit consisting chiefly of small 
octahedral crystals, as illustrated in the right-hand por- 
tion of fig. 1, Plate 11. 
• 2TO grain: almost immediately very small granules appear, 
and soon there is a quite good crystalline deposit of small 
_ plates and octahedrons. 
Q 1 
’ ' To~o grain: after a little time, small crystals can be seen 
with the microscope; after several minutes, a very satis- 
factory deposit to the naked eye. If the mixture be 
stirred with a glass rod, it yields lines of granules along 
the path of the rod, and a more copious deposit. 
Trroo grain; on stirring the mixture, crystals become per- 
ceptible to the microscope, in about five minutes; in about 
fifteen minutes, they become quite obvious to the naked 
eye; and after about half an hour, there is a perfectly 
satisfactory crystalline deposit. 
Antimoniate of potash fails to precipitate potash and am- 
even from concentrated solutions; but it produces pre- 
ipitates in solutions of many other metals: the absence of 
esc, therefore, must be established before concluding that the 
llecipitate consists of the soda compound. 
2. Polarised Light. 
TP" 
(Cl -S which was first suggested by Prof. Andrews 
lemical Gaz., x, 378), is founded upon the fact that the 86 
SODA 
bichloride of platinum, and also the double chloride of potas- 
sium and platinum, when placed in the dark field of the 
polariscope, have no depolarising action, whereas the double 
chloride of sodium and platinum, possesses this property in a 
remarkable degree. 
To apply this test, its author recommended the following 
method; Having removed other bases by the ordinary methods 
and converted the alkalies into chlorides, a drop of the solu- 
tion is placed on a glass slide and a very small quantity of a 
dilute solution of the bichloride of platinum added, avoiding as 
far as possible an excess. This mixture is evaporated by a 
gentle heat till it begins to crystallise, then placed in the field 
of a microscope furnished with a good polarising apparatus. 
On turning the analyser till the field becomes perfectly dark, 
and carefully excluding the entrance of light laterally, the 
crystals remain invisible if only the potash compound or the 
reagent alone, be present, while the presence of the slightest 
trace of soda is at once indicated by the beautiful display of 
color of its platinum double salt. Prof. Andrews states that in 
this manner he obtained a distinct reaction from a quantity of 
chloride of sodium representing only about the 825,000 th part 
of a grain of the anhydrous alkali. 
In applying this method, instead of evaporating the mixture 
by the application of heat, it is best to allow it to evaporate 
spontaneously, as it thus yields much larger crystals of the 
double soda salt. 
1. if,wo grain of soda in the form of chloride, in one grain of 
water, when treated with a very small quantity of the 
reagent and allowed to evaporate spontaneously, leaves 
a good deposit of long, irregular crystals of the double 
compound, Plate 11, fig. 8. This deposit under the 
polariscope, furnishes a beautiful display of prismatic 
colors. 
2. rdTirw grain: quite a number of fine crystals, which in the 
field of the polariscope yield very satisfactory results. 
3. rWWo grain, usually yields several quite distinct and sat- 
isfactory crystals. Sometimes the deposit is in the form 
of thread-like groups, which when broken up by the point SPECIAL CHEMICAL PROPERTIES. 
87 
of a needle, form small crystalline plates. In this manner, 
these thread-like masses, may readily be distinguished 
from depolarising shreds of dust, which are sometimes 
present. 
sWotoTo grain: with the least possible quantity of reagent, 
yields a few small depolarising crystalline plates. Even 
the 1,000,000 th part of a grain of the alkali, will some- 
times yield quite distinct results. 
Before applying this test, the examiner should be certain 
Biat any potash present is entirely converted into chloride, 
otherwise he may be led into error. 
Cakbazotic Acid.—lt is usually stated by writers on this 
Sldiject, that this reagent produces no precipitate even in con- 
centrated solutions of soda, whereby this alkali is distinguished 
potash; but this is not the fact. Thus, one grain of a 
solution of the former alkali, yields with the reagent, 
nithin a little time, a quite copious crystalline deposit, Plate I, 
6; and a similar quantity of a 100 th solution, yields after a 
Buie, a quite distinct crystalline reaction. Solutions but little 
sponger than the first-mentioned, become converted into a mass 
0 Crystals by the reagent. 
Tl " . ® 
J-He crystalline form of the soda precipitate, will usually 
® to distinguish it from the potash compound, as also from 
produced in solutions of ammonia. 
Tartaric Acid produces in very concentrated solutions of the 
a_b especially if the mixture be stirred, a white crystalline 
precipitate of tartrate of soda. In one grain of a 10th solu- 
°f the alkali, the reagent produces, on stirring the mixture, 
01 a few minutes, a mass of groups of bold crystals, Plate 11, 
' One grain of a 25th solution, under the same circum- 
cos, yields after ten or fifteen minutes a quite satisfactory 
ilstalline deposit. If this mixture be not stirred, it fails to 
yield r ' 
j. a precipitate even after several hours. Solutions but 
G Riore dilute than this, fail to yield a precipitate under any 
C * 10n whatever, even after many hours. 
of Platinum fails to precipitate even the most 
°Hcentrated solutions of soda. 88 
AMMONIA. 
Separation from Organic Mixtures.—This may be effected 
in the same manner as already pointed out for the recovery of 
potash [ante, p. 81). 
Section lll.—Ammonia. 
General Chemical Nature.—Ammonia, in its pure state, 
is a gaseous compound of Nitrogen and Hydrogen (NH3), hay- 
ing a very pungent odor and powerfully alkaline reaction. The 
gas is readily absorbed by water, which is thereby increased 
in volume and diminished in density; at a temperature of 50°, 
according to Davy, this fluid takes up about 670 times its vol- 
ume of the gas, and then has a density of 0’875. A solution 
of this kind constitutes the aqua ammonia of the shops. Ac- 
cording to Sir H. Davy, the following table exhibits the per 
cent, by weight, of real ammonia in pure aqueous solutions of 
different specific gravities:— 
STRENGTH OF AQUEOUS SOLUTIONS OF AMMONIA. 
SP. GR. 
PER CENT. 
SP. GR. 
PER CENT. 
0-875 . 
32-30 
29-25 
26-00 
25-37 
22-07 
19-54 
17-52 
0-938 
15-88 
14-53 
13-46 
12-40 
11-56 
10-17 
9-50 
0-885 
0-943 
0-000 . 
0-947 
0-905 
0-951 
0-916 
0-954 
0-925 
0-959 
0-932 
0-963 
Aqua ammonia, when pure, is colorless, has a peculiar 
powerfully pungent odor, and a strong alkaline reaction, imme- 
diately restoring the blue color of reddened litmus-paper; on 
warming the blued paper, the red color reappears, from the 
dissipation of the alkali. On heating a solution of ammonia, 
the gas is rapidly expelled with effervescence; when the liquid 
is evaporated to dryness it leaves no residue, unless foreign 
matter be present. 
The salts of ammonia are colorless, and readily volatilised 
upon the application of heat. With few exceptions, they are SPECIAL CHEMICAL PROPERTIES. 
89 
freely soluble in water. The fixed caustic alkalies readily 
decompose them, with the evolution of free ammonia. 
Special Chemical Properties.—Solutions of free ammonia 
aie readily recognised by their peculiar odor. The salts of 
118 base, when heated on platinum foil are completely dissi- 
pated, unless they contain a fixed acid or foreign matter, in 
respect they differ from the salts of the fixed alkalies. 
aeil their solutions are treated with caustic potash or soda, 
01 with hydrate of lime, and the mixture gently warmed in a 
test-tube, the presence of the ammonia eliminated by the de- 
position, may be recognised by its odor; as also, by its 
a saline reaction upon moistened reddened litmus-paper; and 
} the production of white fumes of chloride of ammonium, 
°n a glass rod moistened with dilute hydrochloric acid is 
* u over the mouth of the tube. By suspending a slip of 
Pioistened reddened litmus-paper within the tube and closing 
s mouth, the presence of very minute traces of the alkali 
ay) at least after a time, be recognised. 
The behavior of solutions of ammonia and of some of its 
when treated with nitrate of silver, and corrosive subli- 
,atej has already been pointed out (ante, p. 71). When the 
11 is added in excess to solutions of salts of copper, the 
T m assumes a characteristic blue color. 
Ip the following investigations of the reactions of ammonia, 
*°ns of pure chloride of ammonium were employed. The 
9ru^lollS re^6r te frie amount °I pure ammonia present in one 
s°frfr°n5 which was the quantity employed for 
unless otherwise stated. 
1. Bichloride of Platinum, 
Tl ‘ 
of US rea£ent produces in neutral and slightly acid solutions 
ammonia, a yellow octahedral crystalline precipitate of the 
wj *q6 • boride of ammonium and platinum (NH4 Cl, PtCl2), 
the VlB sParinSly soluble in diluted mineral acids, and in 
Pi 10e alkalies. In appearance the precipitate closely resem- 
Ht S corresponding compound of potassium: A given quan- 
y °f ammonia in the form of chloride, yields with the reagent 90 
AMMONIA. 
a larger quantity of the double salt, than the same quantity of 
potash: one part by weight of the former yielding 18*1 parts, 
and one part of the latter only 5-2 parts of the double compound. 
1. xo grain of ammonia, in one grain of water, when treated 
with the reagent, the mixture immediately becomes con- 
verted into an almost solid mass of crystals. The pre- 
cipitate is much more copious than that from a similar 
solution of potash, but the crystals are somewhat smaller, 
and a portion of the deposit is in the form of granules. 
2. —(hr grain: in a very few moments a very copious crystal- 
line deposit. 
3. xso" grain: the precipitate begins to appear within a few 
moments, and in a little time there is a quite good octahe- 
dral deposit, very similar to that from a 100 th solution of 
potash (Plate I, fig. 1). 
4. -g-Fo grain: crystals appear in less than half a minute, and 
in a little time they are quite copious. 
5. Tan grain: in about three minutes crystals are just percep- 
tible; in about five minutes the deposit is quite satisfac- 
tory. The formation of the precipitate is somewhat 
hastened by stirring the mixture with a glass rod. 
0. xtoVo grain: in about eight minutes crystals are perceptible 
to the microscope, and soon after they become quite obvi- 
ous to the naked eye, especially along the margin of the 
mixture; after about half an hour there is a quite satis- 
factory deposit. 
Solutions but little more dilute than the last-mentioned fail 
to yield a precipitate even after many hours. 
Fallacies.—The method of distinguishing the double chloride 
of ammonium and platinum from the corresponding potassium 
compound, has already been pointed out under the special con- 
sideration of the latter (ante, p. 76). This reagent fails to pro- 
duce a precipitate even in the most concentrated solutions of 
soda 
2. Tartaric Acid, and Tartrate of Soda 
These reagents produce in neutral solutions of ammonia, 
when not too dilute, a white crystalline precipitate of tartrate SPECIAL CHEMICAL PROPERTIES. 
91 
°f ammonia (NH4O, HO, C 8H4O10)7 which in appearance is very 
Slmilar to the corresponding salt of potash, but somewhat more 
soluble in water. It is soluble in the free alkalies and in dilute 
mineral acids. 
sV grain of the alkali yields with free tartaric acid no im- 
mediate precipitate, but in a little time crystals begin to 
separate, and after a few minutes there is a very satis- 
factory deposit, the crystals having the same form as those 
from potash, Plate I, fig. 2. The acid tartrate of soda 
produces much the same results, but the form of the crys- 
tals is then similar to those illustrated in Plate I, fig. 8. 
Tott grain: after several minutes granules and small crystals 
appear, and after some minutes more, there is a quite 
good crystalline deposit, chiefly confined however to the 
margin of the mixture. With tartrate of soda, the pre- 
cipitate is more prompt in appearing and becomes more 
abundant; the forms of the crystals are then the same as 
D by this form of the reagent. 
2TO grain: after ten or fifteen minutes, some few granules 
form along the margin of the mixture; in about half an 
hour the deposit becomes quite satisfactory. The soda 
reagent produces a more prompt and satisfactory reaction. 
The formation of the precipitate from this, as well as 
from the preceding solutions, is much facilitated by stir- 
the mixture. 
son grain, yields with tartrate of soda, after stirring the 
mixture some minutes, a distinct granular deposit, which 
after a time becomes quite satisfactory. 
0£ ilere is nothing in the physical appearance of the tartrate 
ammonia to distinguish it from the corresponding precipitate 
uced from solutions of potash. 
s°hit*11 a^Co^o^c solution of carbazotic acid produces in neutral 
xons of salts of ammonia, a yellow crystalline precipitate 
caibazotate of ammonia, which is insoluble in excess of the 
1 eagent. ? 
3. Carhazotic Acid. 92 
AMMONIA. 
1. 5V grain of the alkali yields an immediate amorphous pre- 
cipitate, which in a little time becomes a mass of yellow 
crystals. The form of the crystals is quite different from 
that of those produced by the reagent from solutions of 
either of the fixed alkalies. 
2. yito grain: almost immediately crystals begin to separate, 
and in a little time there is a quite good deposit. Under 
the microscope, the crystals present the appearances illus- 
trated in Plate I, fig. 5, which readily distinguish them 
from the corresponding salts of potash and soda. 
3. -250 grain: in a few moments small rough needles begin to 
form, and very soon there is a good crystalline precipitate, 
in form quite unlike that from potash. 
4. Toir grain: in a few minutes needles begin to separate along 
the margin of the drop, and after a little time there is a 
satisfactory deposit. 
5. TTo" grain: after some minutes, small needles appear; after 
some minutes more, there is a quite satisfactory deposit 
of needles, plates and cubes, which might readily be con- 
founded with the deposit from dilute solutions of potash. 
4. Nessler’s Test. 
The author of this test has shown that when a solution of 
iodide of potassium and iodide of mercury in excess of free 
potash, is acted upon by ammonia, the latter is decomposed 
with the production of an insoluble compound, which has been 
designated tetrahydrargyro-iodide of ammonium (NHgJ, 2 HO) 
(Chemical Gazette, xiv, pp. 445, 463). 
The test fluid is prepared by dissolving 20 parts by weight 
of pure iodide of potassium in 50 parts of water, and adding 
pure iodide of mercury to the warmed mixture until it is no 
longer dissolved, which will require about 30 parts of the 
mercury salt. The double iodide of potassium and mercury 
(Hgl, KI), requires for its formation only 27-3 parts of iodide 
of mercury to 20 parts of iodide of potassium; so it seems that 
more than one equivalent of the mercury iodide will under 
these circumstances dissolve in one of the iodide of potassium. SPECIAL CHEMICAL PROPERTIES. 
93 
he cooled solution is then diluted with three times its volume 
°f pure water, and the mixture allowed to stand some hours, 
the excess of iodide of mercury will separate in its crys- 
talline form. The fluid is then filtered, and two measures of 
16 filtrate mixed with three measures of a concentrated solu- 
tion of caustic potash, and this mixture employed as the rea- 
bCnt. Jf the liquid becomes turbid upon the addition of the 
Potash solution, it should again be filtered. 
The reagent prepared as above, produces the following 
results: 
grain of ammonia as chloride, in one grain of water, 
yields a very copious, beautiful orange-colored amorphous 
precipitate, most of which dissolves, with the production 
°f a colorless solution, in excess of free ammonia, and of 
chloride of ammonium, leaving a slight, cream-colored 
residue. It is readily soluble to a colorless solution, in 
f, hydrochloric acid. 
iToTo grain, yields a quite copious precipitate, having a fine 
g orange color. 
i'oTo'o-q grain: a very good, reddish-yellow deposit. Five 
q grains of the solution, yield a fine orange precipitate. 
■r'Oomr grain: an immediate yellow turbidity, which very 
s°on assumes an orange tint, followed by a good flocculent 
Precipitate, having a light-yellow color. Ten grains of 
the solution, with a drop of the reagent, yield an almost 
Piiniediate, orange-colored muddiness, which slowly sub- 
- sides to a deposit of the same color. 
looToinr grain: an immediate cloudiness, and in a very little 
bine the mixture contains suspended flakes, which have a 
dirty-white color. Five grains of the solution yield a 
bright-yellow turbidity, and soon the mixture acquires a 
q s%ht orange tint. 
°<r°T6iigrain: after a little time, a just perceptible cloudi- 
ness. Five grains of the solution very soon assume a 
pale-yellow color, which on heating the mixture is changed 
7 a very slight orange hue. 
i. uttoToito grain: five grains of the solution after a little 
bine assume a very pale-yellow color, which on the appli- 94 
AMMONIA 
cation of heat is changed into the slightest perceptible 
tint of orange. The color of this, and other dilute solu- 
The extreme sensibility* of this test is explained by the cir- 
cumstance that 17 parts by weight of ammonia yield 559 parts 
of the mercury compound, in accordance with the following 
reaction: 
tions, is best seen by transmitted light. 
NH3 + 4 Hgl, KI + 3 KO - NHgJ, 2 HO + 7 KI + HO. 
According to the discoverer of this test, the presence of 
alkaline chlorides and oxysalts have no injurious influence upon 
the reaction of the reagent; and iodide of potassium is only 
injurious when sufficient caustic potash has not been added. 
But the reaction is not produced in the presence of cyanide of 
potassium and sulphuret of potassium, even in concentrated 
solutions of ammonia and the presence of great excess of potash. 
Phospho-molybdate of Soda, according to Sonnenschein 
(Chem. Gaz., x, 411), will readily detect the presence of one 
part of chloride of ammonium in 10,000 parts of water. The 
reagent is prepared, by igniting the yellow precipitate produced 
by adding molybdate of ammonia to an acidulated solution of 
phosphate of soda, to expel the ammonia; any molybdic acid 
reduced in this operation, is reoxidised by nitric acid, the ex- 
cess of which is expelled by heat. The residue is then dis- 
solved in carbonate of soda, the solution supersaturated with 
hydrochloric acid, and the mixture heated, after which any 
precipitate that has formed is redissolved by the addition of 
more acid. 
This liquid, when employed as a reagent, produces in 
solutions of salts of ammonia a yellow precipitate of phos- 
pho-molybdate of ammonia, which according to Sonnenschein, 
contains only 6 *747 per cent, of oxide of ammonium. The 
reagent produces a similar yellow precipitate in tolerably con- 
centrated solutions of salts of potash; but it fails to precipitate 
solutions of salts of soda. 
Antimoniate of Potash produces no precipitate, even in con- 
centrated solutions of salts of ammonia or of the free alkali. SEPARATION FROM ORGANIC MIXTURES. 
95 
Separation from Organic Mixtures. 
Unless the ammonia be present only in extremely small 
quantity or combined with an acid, the liquid will have an 
Saline reaction and give out the odor of the alkali. Ammonia 
its carbonate, may be separated from organic solutions, by 
the liquid at a moderate heat, in a retort, the beak 
0 which is provided with a perforated cork carrying a small 
De, which is bent at an obtuse angle and made to dip beneath 
. 0 Surface of a very small quantity of pure water, contained 
a well-cooled receiver. Any of the alkali or its carbonate 
present, will be vaporised by the heat and pass along with the 
aP0r °f water into the receiver; the solution thus obtained 
tested in the ordinary manner, 
th * distilling over about one-eighth of the contents of 
retort, no ammonia yet appear in the distillate, it may be 
°Ucluded that none of the free alkali or its volatile salt is 
its may however be present in the form of some of 
more fixed salts. To ascertain this, the contents of the 
1 ar° treated with strong alcohol, which will in part at 
the CoaSuUte the organic matter; the mixture is then filtered, 
rp x-i tra^e treated with caustic potash or hydrate of lime, and 
d ®d as before. Any ammoniacal salt present, will now be 
by the alkali added, with the evolution of free am- 
it ‘ will appear in the distillate. In some instances, 
a est to replace the pure water placed in the receiver, by 
Veiy dilute solution of hydrochloric acid, whereby the am- 
la will be more effectually absorbed, in the form of chloride 
01 ionium. 
If It 
tne mixture under examination contains organic matter 
*uixt S^e decomposition, this may give rise to ammonia. In 
decidUes °f this kind, it may be difficult or even impossible, to 
f-jlelCe hhe true source of the poison. If it be the contents of 
reo S^° that are thus examined, the quantity of the alkali 
its oi ’ • and Posf“m°rtem appearances, may readily decide 96 
AMMONIA. 
Quantitative Analysis.—This may be effected by precip- 
itating the alkali in the form of double chloride of ammonium 
and platinum, and treating the precipitate in the same manner 
as directed for the estimation of potash [ante, p. 82). The 
double ammonium salt contains 7*62 per cent, by weight of 
pure ammonia (NH3). 
Every 17 grains of real ammonia correspond to 52-6 grains 
of the most concentrated aqiia ammonia?, which measure a few 
drops over one fluid drachm. THE MINERAL ACIDS. 
97 
CHAPTER 11. 
the MINERAL ACIDS: SULPHURIC, NITRIC, AND HYDRO- 
CHLORIC. 
General Nature and Effects.—The above-named mineral 
acids; form a group of compounds the members of which are 
Tute similar, both in respect to their general chemical proper- 
es an(i their effects upon the animal system. They possess 
e property of acidity in the most eminent degree, such as 
Reddening blue litmus, perfectly neutralising free alkalies, and 
the salts of other acids. They are more or less 
composed when brought in contact with many of the metals, 
Sllch as zinc, iron, copper, and mercury, with the formation of 
lr respective salts. Sometimes this decomposition takes 
i cce at ordinary temperatures, but at others, only upon the 
application of heat. Most of the salts of these acids are read- 
-13 soluble in water. 
t] n eir powers to corrode and destroy organic substances, 
mineral acids stand preeminent. When brought, in their 
°mewhat concentrated state, in contact with living animal tis- 
_ > they rapidly destroy their organisation and vitality; in 
aianner they may speedily occasion death by their direct 
ol,emi? action. Due to this action, they also speedily affect 
entirely destroy various articles of clothing with which they 
m contact: this property is sometimes of considerable 
ance *n a medico-legal point of view. 
.lrQerous instances are recorded in which these substances 
tapC °n. but with few exceptions, the poison was 
In e^ler with suicidal intent or as the result of accident. 
°n tE ? r°m eip immediate and powerfully corrosive action 
p mouth, there is perhaps no poison which, for criminal 
t ses, could not be resorted to with greater safety from 
7 98 
SULPHURIC ACID. 
detection than either of these acids 5 yet cases are not wanting 
in which they were thus employed. 
Section I.—Sulphuric Acid. 
This acid has long been known under the name of oil of 
vitriol, which name it received from the fact that it was pre- 
pared from green vitriol, or sulphate of iron. As met with in 
the shops, it is a dense, powerfully acrid and corrosive, oily 
liquid, with usually a more or less brownish color. When 
brought in contact with organic substances, it speedily chars 
them. In proportion as it is diluted with water, it loses its 
oily appearance and power of acting upon organic tissues. As 
a poison, it has been principally used in the form of the com- 
mercial acid, yet instances of poisoning by sulphate of indigo, 
which is a solution of indigo in the concentrated acid, and 
by aromatic sulphuric acid of the Pharmacopoeias, have also 
occurred. 
Instances of poisoning by this acid, have been of much more 
frequent occurrence than by either of the other mineral acids. 
But, as already intimated, it has rarely been administered crim- 
inally, Of twelve cases of poisoning by this substance recently 
collected by Dr. Cozzi, in a hospital in Florence, eleven were 
the result of suicide. Dr. Christison has collected several in- 
stances in which children were murdered by the acid being 
poured down the throat. A case is also reported in which a 
man was murdered in a similar manner, while he lay asleep ; 
and another, in which it was thus administered to a woman 
while she was intoxicated. A singular practice of secretly 
throwing the acid upon persons for the purpose of disfiguring 
them or of destroying their dress, has been of not unfrequent 
occurrence, both in this country and in Europe. 
Symptoms.—The direct effects of sulphuric acid will, of 
course, depend much upon the degree of its concentration, and 
the quantity taken. When, taken in its concentrated state, all 
the soft parts of the mouth and throat are immediately more or 
less corroded and destroyed, and assume a white appearance; PHYSIOLOGICAL EFFECTS. 
99 
ancl? if the poison has been swallowed, the lining membrane of 
the oesophagus and stomach, will be acted upon in the same 
manner. These effects will be followed with intense burning 
Pain in the mouth, throat and stomach, alteration of voice, 
gaseous eructations, and violent vomiting. The vomited mat- 
ters have usually a brownish or black color, strongly acid prop- 
Gr ties, and contain disorganised membrane and blood. As the 
oase advances, there will be excruciating pain in the bowels, 
mipaired respiration, difficulty of swallowing, coldness of the 
extremities, and great prostration. The pulse becomes weak 
ami irregular, the countenance ghastly, and the body covered 
cold perspiration. The bowels are usually much consti- 
pated, and the urine scanty. The inside of the mouth and 
r°at frequently become covered with sloughs. The mental 
c duties usually remain unimpaired. 
Such are the symptoms usually observed in poisoning by 
118 acid in its concentrated state, but it is obvious that they 
may all be present in a given case. The vomiting, which 
m°st instances is either immediate or within a very short 
period, has been delayed for half an hour or longer. The 
action of the acid may be confined to the mouth, the poison 
a\ing been thrown out without any portion of it being swal- 
6(k In such cases, however, it may produce death by 
asphyxia, from the closure of the air-passages. On the other 
ha11'? le mou^l may escape the local action of the acid, it 
c mg been administered in a spoon passed back into the throat, 
111 a case cited by Dr. Taylor. If the acid has come in 
jmtact with the lips or other parts of the external skin, they 
hist present a white appearance, which afterwards becomes 
yellowish-brown. 
j Same symptoms as those just described, only that they are 
lcs ln°mpt in appearing, and the local action of the poison is 
8 violent. The extent of this difference will, of course, de- 
-11 pUP0n the degree of dilution of the acid. 
Usiic \71 W^len Fatal.—ln fatal poisoning by this acid, death 
evei t P^ace 111 fr°m twelve to thirty-six hours ; but this 
0t kas occurred within an hour, and again, it has been 100 
SULPHURIC ACID. 
delayed for weeks, and even months. Dr. Christison cites a 
case in which a child, who, while attempting to swallow strong 
sulphuric acid by mistake for water, died almost immediately, to 
all appearances from suffocation caused by contraction of the 
glottis; it was ascertained after death that none of the poi- 
son had reached the stomach (Op. cit., p. 132). Mr. Traill 
reports the case of a washerwoman, who took by mistake, a 
wine-glassful of the commercial acid, haying a specific gravity 
of 1*833, and, although actively treated, died in one hour after- 
wards. After death, a jmrforation was found in the stomach, 
and the peritoneum was greatly inflamed, from the escape of 
the acid from the stomach. An instance is also related by 
Prof. Casper, in which the poison, administered by an unnatu- 
ral mother to her own child, aged one year and a half, caused 
death, in spite of the antidotes administered, in one hour (Fo- 
rensic Medicine, ii, p. 75). These are the most rapidly fatal 
cases yet recorded. Not less than three cases, however, are 
reported, in which death occurred in hvo hours; and several, 
in which death took place in from three to five hours. 
In poisoning by this substance, as in the case of the caustic 
alkalies, the patient may recover from the immediate effects of 
the poison, and yet die from secondary causes, long periods 
afterwards. In such cases, nervous symptoms and general de- 
rangement of the assimilating organs usually manifest them- 
selves, and death is the result, either of chronic inflammation 
of the stomach and bowels, or of stricture of some part of the 
alimentary tube. Several instances are reported in which death 
did not take place until from the fifteenth to the twentieth day 
after the poison had been taken; and Dr. Beck quotes a case, 
not fatal until after the lapse of two months. In an instance 
reported by Dr. Wilson, life was prolonged for over ten months. 
During the progress of this case, the thickened lining mem- 
brane of the oesophagus came away in the form of a firm cylin- 
drical tube, eight or nine inches in length. The most protracted 
case in this respect yet recorded, is that quoted by Dr. Beck 
(Med. Jur., ii, 472), in which the patient survived the taking 
of the poison, two years, when death supervened from the 
effects of stricture of the oesophagus. ANTIDOTES. 
101 
Fatal Quantity.—The effects of given quantities of sulphuric 
aci(f? have by no means been uniform. They will be influenced 
much by the condition of the stomach, as to the presence of 
f°od, and the degree of concentration of the acid, as also, of 
course, on the promptness with which remedies are employed. 
11 many instances, it is difficult to determine exactly how much 
of the poison has been retained in the body, even when the 
quantity originally taken is accurately known, since much of it 
18 often rejected from the mouth as soon as taken. 
The smallest fatal dose yet recorded, is in a case quoted by 
r- Christison, in which half a teaspoonful or about thirty 
Wtonims of the concentrated acid, caused the death of a child 
olm year old, in twenty-four hours. The same writer quotes 
uuother instance, in which one drachm, taken by a stout young 
man, proved fatal in seven days (Op. cit., p. 181). In a case 
uh'eady mentioned, about one drachm and a half of the acid, 
Poured into the mouth of a man while asleep, caused death in 
olty-seven hours. 
On the other hand, recovery has not unfrequently taken 
place, after large doses of the acid had been swallowed. Thus, 
llQt less than two instances of this kind are related, in each of 
Yllich two ounces of the concentrated acid had been taken, 
ml Dr. Beck quotes a case, in which a man recovered after 
Vlng swallowed four ounces (whether by weight or measure 
*ot stated). This is the largest dose that we find recorded, 
°m which there was recovery. 
Treatment.—There are many substances that will perfectly 
neutralise this acid, yet on account of its very rapid local action, 
af least in its concentrated state, it is not often that chemical 
auticlotes can be administered sufficiently early to prevent seri- 
?Us mjury. Common chalk and calcined magnesia, suspended 
11 'fofo? have generally been recommended, and will answer the 
purpose very well. The alkaline carbonates, properly diluted 
nith water or milk, have also been strongly advised, and are 
perhaps preferable. In the administration of the alkaline car- 
uates, it must be remembered that they themselves in large 
anl'll^-foS? are highly poisonous. Oily emulsions, soap-suds, 
c 111 ilk alone, may be employed with advantage. 102 
SULPHURIC ACID. 
Several instances are related, in which the timely adminis- 
tration of one or other of these antidotes saved the life of the 
patient, even after very large quantities of the poison had been 
taken. The exhibition of the antidote, should always be fol- 
lowed by large draughts of tepid water or demulcent fluids, to 
promote vomiting. The whole of the acid, however, may be 
neutralised and removed from the stomach, and yet death take 
place from the effects of its primary action. On account of this 
local action, the patient is sometimes unable to swallow when 
first seen by the physician. Under these circumstances the 
poison may be withdrawn by means of the stomach-pump; but, 
for obvious reasons, this instrument should be used with great 
caution, and employed only as a final resort. 
Post-mortem Appearances.—ln poisoning by sulphuric 
acid, the pathological appearances are more frequently peculiar 
and characteristic, than, perhaps, in the action of any other 
poison. These appearances, however, will be much modified 
by the degree of concentration of the acid, and the length of 
time the patient survived after it had been taken. In the tak- 
ing of the poison it not unfrequently happens that drops of it 
become sprinkled over the face, neck, and other portions of the 
skin; in such cases, if not very protracted, these parts will 
present dark-brown spots or stains. In the case cited above 
from Casper, in which death took place in an hour, dirty- 
yellow parchment-like streaks, arising from the trickling down 
of the acid, extended from the angle of the mouth to the ear; 
similar stains were present on the arms and hands of the child. 
The tongue was white and leathery, and had no acid reaction. 
The stomach, both externally and internally, was quite grey, 
and filled with dark, bloody, acid mucus; its tissues fell to 
pieces when touched; the vena cava was moderately filled with 
a cherry-red syrupy and acid blood; and the liver and spleen 
were congested with blood of the same character; the heart con- 
tained only a few drops of blood. The tissues of the oesophagus 
were quite firm, and its mucous membrane had a greyish color, 
and an acid reaction; the larynx and trachea were normal. 
In recent cases, the mucous membrane of the tongue and of 
the mouth, is generally more or less corroded, and of a white, POST-MORTEM APPEARANCES. 
103 
but sometimes of a deep-brown color; in some instances large 
patches of this membrane are entirely destroyed. Similar ap- 
pearances are usually found in the fauces, and throughout the 
length of the oesophagus. The lining membrane of this organ, 
is sometimes much thickened and partially detached. Instances 
are recorded, however, in which the mouth and oesophagus pre- 
sented but few signs of the local action of the poison. 
The stomach generally presents a brownish or black appear- 
ance, due to the carbonising action of the acid; its bloodvessels 
are frequently much engorged with dark coagulated blood, and 
its tissues so soft as to be readily lacerated, even by the slight- 
est pressure. Sometimes this disorganisation is confined to 
patches, whilst in others, it extends in the form of lines or 
streaks; often the pylorus presents the most decided marks of 
disorganisation. The contents of the stomach are usually thick 
and have a brownish or charred appearance and a highly acid 
reaction. If the stomach become perforated, as not unfre- 
finently happens, the acid may escape and exert its chemical 
action upon the surrounding organs’; but this organ may become 
perforated and its contents not escape. The aperture of the 
perforation, usually presents a roundish appearance, and has 
diin, black, irregular edges. Sometimes there are several such 
perforations. In one instance, the perforation measured about 
three inches in diameter, and was bordered by thickened edges 
°f a dark-brown, cinder-like appearance. A few instances 
have occurred, in which there were no marks of the chemical 
action of the poison, except in the neighborhood of the per- 
foration. 
The duodenum and other portions of the small intestines, 
have in some instances presented signs of corrosion similar to 
those observed in the stomach. Instances are reported, how- 
over, in which there was little or no abnormal change in these 
ol’gans, even when the stomach was extensively disorganised. 
fa making these examinations, the inspector should not for- 
Set, that the action of the acid may be confined to the mouth 
ari(f throat, none of the poison having passed into the stomach, 
fa such cases, as also in others, the air-passages may be much 
c°i'roded and inflamed. So also, it should be remembered, that 104 
SULPHURIC ACID. 
when the acid is swallowed in its diluted state, or the stomach 
contains much food or liquid, this organ may present simply 
signs of inflammation, instead of the disorganised appearances 
described above; even when, however, the acid is much diluted, 
the inside of the stomach may present a blackened appearance. 
In a number of cases of acute sulphuric acid poisoning 
examined by Prof. Casper, the hlood had in every instance a 
cherry-red color, a more or less ropy consistency, and an acid 
reaction. Pie also relates an instance of similar poisoning, in 
which he found the pericardial and amniotic fluids of a decid- 
edly acid reaction, the person poisoned being pregnant (Foren- 
sic Medicine, ii, pp. 58, 83). In the case of another pregnant 
woman, quoted by Dr. Beck (Med. Jur., ii, 475), the amniotic 
fluid, as well as that found in the pleura, peritoneum, heart, 
and bladder of the foetus, had an acid reaction. It need hardly 
be remarked that this acid condition of the fluids of the body, 
would only be found in recent cases. 
According to Casper, the bodies of persons poisoned by this 
acid, and perhaps by the other mineral acids, remain fresh and 
without odor for an unusual length of time. He attributes this 
condition to the free acid neutralising the ammonia evolved 
during the first stages of the process of putrefaction. 
When the patient survives the primary effects of the poison 
and dies from secondary results, the appearances will, of course, 
differ from those described above. In such cases, the body is 
usually extremely emaciated, and one or more portions of the 
alimentary canal much contracted. In Dr. Wilson’s case, in 
which life was protracted for over ten months, the upper third 
of the oesophagus shone like an old cicatrix, and the lower 
two-thirds were thickened, narrowed, and very vascular; the 
stomach contained a perforation, which was surrounded with 
softened edges. 
Chemical Properties. 
General Chemical Nature. Anhydrous sulphuric acid, 
which is a compound of one equivalent of Sulphur with three 
equivalents of Oxygen (SO-d), is a very rare, white crystalline GENERAL CHEMICAL NATURE. 
105 
substance, apparently destitute of acid properties. It melts 
a clear liquid at about 65°, and boils at about 115° F., being 
lssipated in the form of a colorless vapor. It has an intense 
affinity for water, with which it unites with violence, forming 
tbe ordinary hydrated acid. 
The most concentrated form in which this acid is found in 
commerce, is usually a definite chemical combination of one 
equivalent of the so-called anhydrous acid with one equivalent 
°f water (HO, S03). In this state, when pure, it is a color- 
ess, odorless, highly acrid, corrosive, oily liquid, having a 
specific gravity of 1-845, and containing 81-6 per cent, of the 
anhydrous acid; it boils at a temperature of 620°, and freezes 
at F. In certain respects, this hydrated compound is 
*be most powerful acid known. It has a strong attraction for 
Water, which it readily absorbs from the atmosphere; it mixes 
Mlth this liquid in all proportions, with a contraction of volume, 
aud the evolution of much heat. In proportion as it is mixed 
urater, it loses its oily consistency and becomes specific- 
a 7 lighter; when diluted to a density of 1-5 its oily appear- 
ance will have about disappeared, and it will have a less 
energetic, action upon organic substances. The density of the 
uted liquid, when pure, indicates the amount of real acid 
Present. 
The following table, abridged from that first constructed by 
r- Ure, indicates the per cent, by weight of anhydrous (SO3), 
ailcl uionohydrated acid (HO, S03), in pure solutions of different 
specific gravities:— 
strength of aqueous 
SOLUTIONS OF SULPHURIC ACID. 
Percentage of 
Percentage of 
Percentage of 
Specific 
Specific 
Gravity. 
Gravity. 
— 
SOs. 
HO, SO3. 
SOs. 
HO, 8O3. 
80s. 
HO, S03. 
1-848 
I-S37 
81-54 
100 
1-539 
53-00 
65 
1-218 
24-46 
30 
1-811 
17-46 
95 
1-486 
48-92 
60 
1-179 
20-38 
25 
1*767 
73-39 
90 
1-436 
44-85 
55 
1-141 
16-31 
20 
1-712 
69-31 
85 
1-388 
40-77 
50 
1-101 
12-23 
15 
1-652 
65-23 
80 
1-344 
36-69 
45 
1-068 
8-15 
10 
1-697 
61-15 
75 
1-299 
32-61 
40 
1-033 
4-08 
5 
57-08 
70 
1-257 
28-54 
35 
1-007 
0-81 
1 
1 106 
SULPHURIC ACID. 
The acid of commerce has frequently a dark-brown color, 
due to its having «been brought in contact with organic matter. 
Sulphuric acid quickly chars animal and vegetable substances; 
when dropped, even in a much diluted state, on black woolen 
cloth, it causes it to assume a red color, which after a time 
fades to brown. Many substances, such as certain metals, 
charcoal and various organic compounds, when heated with the 
concentrated acid, decompose it with the evolution of sulphur- 
ous acid gas (SO2). In a diluted state, in the presence of 
some of the metals, such as zinc, it decomposes water, at the 
ordinary temperature, with the evolution of hydrogen gas and 
the formation of a salt of the oxide of the metal. 
The salts of sulphuric acid are usually colorless, and for the 
most part readily soluble in water. The sulphates of the fixed 
alkalies and of the alkaline earths are unchanged by a red heat, 
but most other sulphates readily undergo decomposition when 
strongly ignited. When thoroughly mixed and ignited with 
either charcoal or a mixture of carbonate of soda and cyanide 
of potassium, or with ferrocyanide of potassium, all metallic 
sulphates are readily decomposed with the formation of a sul- 
phuret of the metal. This residue when acted upon by hydro- 
chloric acid, evolves sulphuretted hydrogen gas, with the for- 
mation of a chloride of the metal. 
Special Chemical Properties.—When in its concentrated 
state, sulphuric acid may be readily recognised by the proper- 
ties already mentioned, such as its carbonising action on organic 
matter, evolving heat when mixed with water, etc.; but when 
in a diluted state, its presence has to be determined by other 
tests. The acid has the property of reddening veratrine, pip- 
erine, phloridzine, oil of bitter almonds, and several other or- 
ganic compounds. On account of the solubility of most of the 
compounds of sulphuric acid, there are but few reagents that 
precipitate it from solution; however, there is no substance that 
can be detected with greater certainty and ease than this acid. 
The presence of free sulphuric acid in solution with a sul- 
phate may be recognised by adding a little cane sugar and 
evaporating the mixture to dryness at 212° F., when, if the 
free acid be present, the residue has a black color, due to the SPECIAL CHEMICAL PROPERTIES. 
107 
charring action of the acid; if only a trace of it be present, 
*he residue will have a blackish-green color. No other free 
acid behaves in this manner with cane sugar (Runge). 
In the examination of the following tests, aqueous solutions 
°I pure sulphuric acid were chiefly employed. The fractions 
lefer to the amount of monohydrated sulphuric acid (HO, S03) 
piesent in one grain of the solution; and the results, unless 
otherwise stated, to the behavior of one fluid-grain of the 
solution. 
1. Chloride of Barium. 
Chloride of barium, and the Nitrate of baryta, produce in 
solutions of free sulphuric acid, and of its salts, an immediate 
nhite precipitate of sulphate of baryta (BaO, S03), which is 
in free acids and in the caustic alkalies. In applying 
18 test t6 neutral solutions for the detection of combined sul- 
-1 nine acid, the solution should first be acidulated with either 
(h'o chloric or nitric acid. 
Too grain of protohydrated sulphuric acid in solution in one 
grain of water, yields with either of the above reagents, 
an immediate, copious precipitate, which, if the mixture 
be not much agitated, consists of feathery stellate crystals, 
needles, and granules, Plate 11, fig. 4. The same crystal- 
line deposit may be obtained from the acid when in solu- 
tion in the form of a sulphate; at least from the sulphates 
°f potash, soda, magnesia, and copper. If the mixture be 
much agitated on the addition of the reagent, the precip- 
itate is wholly in the form of very small granules. The 
precipitate, whether crystalline or otherwise, remains un- 
changed on the addition of several drops of concentrated 
0 hydrochloric acid. 
TToTi grain, yields a rather copious, principally amorphous 
o partially granular precipitate. 
grain; an immediate amorphous deposit. 
10,000 grain: after a very little time, there is a very good 
precipitate. A drop of the sulphuric acid solution imme- 
-5 reddens litmus-paper. 
grain: an immediate turbidity, and after a little time, 108 
SULPHURIC ACID. 
a very satisfactory deposit. A drop of this solution faintly 
reddens litmus-paper. 
6- TorVoij grain: very soon, the mixture is distinctly turbid, 
and after several minutes it yields a quite distinct precip- 
itate. This solution just perceptibly changes the color of 
normal litmus-paper. | 
7. xitoVjTjT) grain: after some minutes, a distinct deposit, which 
is usually, especially when nitrate of baryta is employed as 
the reagent, granular. 
8. X(To1oij‘o grain: in about one minute there is a perceptible tur- 
bidity, which after several minutes becomes quite distinct. 
9- TooVoo grain, yields after from ten to fifteen minutes, a just 
perceptible cloudiness. This result is equally produced by 
either of the baryta reagents. 
The last-mentioned quantity of sulphuric acid would form 
the 1G B,oooth part of a grain of sulphate of baryta. It is ob- 
vious therefore, especially as there was some fluid added with 
the reagent, that this salt requires more than 168,000 times its 
weight of water for solution. There has been much discrepancy 
among observers in regard to the limit of this test, and the sol- 
ubility of the baryta compound. Thus, Harting placed the limit 
for chloride of barium, at one part of anhydrous sulphuric acid 
in 75,000 parts of water; while Lassaigne placed it, for nitrate 
of baryta, at one part of the acid in 200,000 parts of water, 
after from ten to fifteen minutes (Gmelin’s Handbook, vol. ii; 
pp. 177, 192). Again, Ganelin states (upon the authority of 
Klaproth?) that the sulphate of baryta is soluble in 43,000 
parts of water (Handbook, iii, 152); whereas, Bischof concludes 
from his experiments (Chem. and Phys. Geoh, i, 450), that this 
salt requires something more than 209,424 times its weight of 
water for solution. 
Confirmation of the Test.—lf the sulphate of baryta, precip- 
itated by this reagent, be dried, then thoroughly mixed with 
about twice its weight of powdered charcoal or of a well-dried 
mixture of equal parts of carbonate of soda and cyanide of 
potassium, and the mixture heated to redness, for convenience 
on platinum-foil, the baryta salt yields up its oxygen and be- 
comes reduced to sulphuret of barium (BaS). This same SPECIAL CHEMICAL PROPERTIES. 
109 
conversion may be effected in a similar manner by ferrocyanide 
potassium, as first advised by Dr. E. Davy for the reduction 
°f arsenical compounds, and afterwards applied by Dr. Taylor 
the present purpose; the salt should be previously pulverised 
aad thoroughly dried at 212° in a water-bath. Before using 
cither of these reducing agents for the reduction of the baryta 
precipitate, a portion of the agent should be ignited alone, and 
then tested for a sulphuret, in the manner about to be described; 
this precaution is necessary, since the agent itself might con- 
tain a sulphate. In the absence of platinum-foil or a small 
Platinum or porcelain crucible, the ignition of the sulphate mix- 
ture may be performed in an ordinary reduction-tube. 
The presence of a sulphuret in the ignited sulphate mixture, 
may be shown by moistening the cooled residue with diluted 
hydrochloric acid, when it will evolve sulphuretted hydrogen 
gas. The presence of this gas may be recognised by its pe- 
culiar odor, and by imparting a broAvn color to a slip of bibu- 
°as paper, previously moistened with a solution of acetate of 
cad and exposed to it. Or, the evolved gas may be conducted 
lnto a solution of acetate of lead, when it will produce a black 
Piecipitate of sulphuret of lead, or at least impart a brown 
coloration to the solution. For this purpose, the cooled residue 
placed with a few drops of water, in a small test-tube, 
yurochloric acid, added by means of a small 
miel-tube, a; the evolved gas is conducted 
t rough a delivery-tube, 6, into a few drops of 
16 lead solution, acidulated with acetic acid, 
contained in a second test-tube, B. By blow- 
through the funnel-tube of the apparatus, 
le last traces of the evolved gas will be 
r°nght in contact with the lead solution. 
y this method, the sulphuretted hydrogen 
v°lved from the 100 th part of a grain of sulphuric acid will 
produce a distinct precipitate, and from the I,oooth of a grain, 
c mtinctly brown coloration. 
also, the ignited residue may be placed on a piece of 
leß which has previously been saturated with a lead solution 
Apparatus for detection of 
Sulphuret of Barium. 110 
SULPHURIC ACID. 
and nearly dried, and then touched with a drop of diluted hy- 
drochloric acid, when the moistened paper will assume a brown 
color; or, it may be placed in a watch-glass and moistened 
with the acid, and another similar glass, containing a fragment 
of paper moistened with the lead solution, inverted over this. 
By either of these methods, especially the latter, the most mi- 
nute traces of a sulphuret manifest themselves. 
Fallacies.—Solutions of salts of baryta, also produce white 
precipitates in solutions of Selenic and Hydrofluosilicic acids, 
even in the presence of other free acids. Both these substances 
are very rare, and only possible to be met with in medico-legal 
investigations. The fluorine precipitate, at least from strong 
solutions, is crystalline; but the form of the deposit, Plate 11, 
fig. 4, readily distinguishes it from the sulphate precipitate. 
The seleniate of baryta is amorphous. -This salt is soluble in 
hot hydrochloric acid, with the evolution of free chlorine; but 
the silico-fluoride of barium is almost wholly insoluble in either 
hydrochloric or nitric acid. Solutions of selenic acid, like those 
of sulphuric acid, yield precipitates when treated with soluble 
salts of strontium and of lead; but the fluorine acid forms no 
precipitate with solutions of these metals. The precipitate from 
either of these acids would not, of course, yield a sulphuret 
upon ignition with a reducing agent. 
In applying this test it must also be borne in mind, that 
when relatively large quantities of strong solutions of chloride 
of barium, and of nitrate of baryta, are added to a liquid con- 
taining much free hydrochloric acid or free nitric acid, it may 
yield a white precipitate of the reagent salt, since these salts 
are less soluble in a strong solution of either of these acids 
than in pure water. Under these circumstances, however, the 
precipitate would readily disappear on the addition of waterj 
whereby it would be distinguished from the sulphate of baryta. 
When the reagent is added to neutral or alkaline solutions, 
it produces white precipitates with several acids other than 
those already mentioned, such as carbonic, phosphoric, oxalic, 
etc.; but the precipitate produced from cither of these, unlike 
the sulphate of baryta, is readily soluble in hydrochloric and in 
nitric acids. SPECIAL CHEMICAL PROPERTIES. 
2. Nitrate of Strontia. 
This reagent produces in solutions of free sulphuric acid, 
of its salts, a white precipitate of sulphate of strontia 
S03), which is quite perceptibly soluble in hydrochloric 
and nitric acids, and much more soluble in water than the 
corresponding baryta compound. From dilute solutions, the 
formation of the precipitate is much promoted by warming the 
mixture, and also by agitating it with a glass rod. 
If the precipitate be collected and ignited with charcoal, or 
any other reducing agent, it leaves a residue of sulphuret of 
ontium, which may be recognised as'such in the same man- 
Pcr as the sulphuret of barium. 
* Tor, grain of free sulphuric acid, in one grain of water, yields 
with the reagent a rather copious crystalline precipitate, 
consisting of groups of exceedingly delicate transparent 
needles, and granules, Plate 11, fig. 6. The granules are 
somewhat larger than those produced by the baryta 
reagent. The deposit remains unchanged on the addition 
of a few drops of hydrochloric acid. Similar results are 
obtained from the acid when in solution in the form of a 
sulphate. 
2 1 • • . . 
Toro gram: an immediate cloudiness, and very soon a quite 
good granular deposit. 
ToWo grain: in about one minute there is a perceptible 
cloudiness, and in a few minutes, a good granular precip- 
itate. 
1 
1070T0 gram : after a few minutes a distinct turbidity, and 
after several minutes a quite satisfactory deposit. The 
separation of the precipitate is much hastened by agitating 
g the mixture. 
Tototo grain, yields after several minutes a just perceptible 
cloudiness, which increases but little, even after half an 
hour. 
Wackenroder states that the sulphate of strontia dissolves 
ny Imt completely, in a solution of common salt, in which 
espect it differs from the corresponding salt of baryta. 112 
SULPHURIC ACID. 
The reaction of this test is subject to about the same folia 
cies as the preceding reagent. 
3. Acetate of Lead. 
Solutions of free sulphuric acid and of sulphates, yield with 
this reagent a white amorphous precipitate of sulphate of lead 
(PbO, S03), which is sparingly soluble in dilute hydrochloric 
and nitric acids. It is somewhat soluble in solutions of the 
caustic alkalies, as also in some of the salts of ammonia. 
1. y-o-o grain of the acid, yields a copious amorphous precipi- 
tate, which in a large measure is dissolved on the addition 
of a single drop of concentrated hydrochloric acid. 
2. x.'c Too' grain: a rather copious precipitate, which on the addi- 
tion of a drop of hydrochloric acid, very nearly all dis- 
appears. 
3. 10; 0 0~0 grain, yields an immediate turbidity, and in a few 
minutes a very satisfactory deposit. 
4. xxlixtt grain: after some minutes a just perceptible turbidity, 
which increases but little on standing. 
This test is subject to many more fallacies than either of 
those already mentioned. 
4. Veratrine 
acid, slowly assumes a yellow color and in a little time dissolves 
to a beautiful crimson red solution. This solution is produced 
immediately by warming the mixture. In the diluted acid, the 
Yeratrine, when added to a drop of concentrated sulphuric 
alkaloid dissolves slowly without change of color. 
1. xihr grain: when a small quantity of the alkaloid is introduced 
into one grain of a 100 th solution of the free acid and heat 
applied, it dissolves to a colorless mixture, which when 
evaporated to dryness on a water-bath, leaves a beautiful 
crimson-colored deposit. 
2. Trcroo grain of the acid, when treated in a similar manner, 
leaves a residue, the border of which has a tine crimson 
color. SEPARATION FROM ORGANIC MIXTURES. 
113 
q 1 
r;oiro grain: the residue has a just perceptible red tint, 
which, however, is not well-marked. 
Since this reagent produces no coloration with neutral sul- 
phates, it serves to distinguish the uncombined acid from these 
salts. And for this purpose we recommend it as much superior 
111 every respect to the cane-sugar method of Runge. A drop 
a saturated solution of the neutral sulphate of either of the 
fixed alkalies and of other similar salts, when treated with the 
alkaloid and evaporated to dryness, failed to produce any red 
coloration whatever. 
This reaction is peculiar to the acid in question. 
Other Reactions.—Chloride of Calcium produces in some- 
what concentrated solutions of free sulphuric acid and of its 
salts, a white granular, but sometimes crystalline, precipitate 
°f sulphate of lime, which slowly disappears on the addition of 
Water, it being rather freely soluble in this fluid. One grain of 
a 100 th solution of the free acid, yields only a slight turbidity. 
Metallic copper, when present in strong, boiling solutions of 
sulphuric acid, decomposes it, with the evolution of sulphurous 
acid gas, which may be recognised by its peculiar odor, and its 
teaching properties. This decomposition, however, does not 
occur when the acid is diluted with as much as about ten times 
ds weight of water. So also, when not too dilute, the acid 
ecomposes, at ordinary temperatures, the sulphuret of iron, with 
16 evolution of sulphuretted hydrogen gas, known by its pecu- 
ar odor and action on salts of lead. When the acid contains 
°ut twenty-five times its weight of water, the decomposition 
lukes place very slowly; and when but little more diluted not 
al all. This decomposition, however, is common to several other 
acids. 
Separation from Organic Mixtures. 
Suspected Solutions.—lf the solution presented for examina- 
lon fic some article of drink, food or medicine, having a strong 
a°id reaction, and free from mechanically suspended matter or 
Ws, the tests for sulphuric acid may be applied at once, even 
ollgh the liquid be highly colored. For this purpose, a given 
8 114 
SULPHURIC ACID. 
portion of the solution, after concentration if necessary, is treated 
with a solution of chloride of barium as long as it produces 
a precipitate. The mixture is then warmed and the deposit 
collected on a filter, well washed with water containing pure 
hydrochloric acid, and dried. If the mixture, containing the 
precipitate, be so strongly acid that it perforates the filter, the 
latter is supported on a muslin cloth, or the solution is diluted 
before filtration. 
When an organic mixture thus yields with chloride of barium 
a white precipitate, which is insoluble in hydrochloric acid, there 
is scarcely a doubt of the presence of sulphuric acid, either free 
or otherwise. It is more satisfactory, however, to ignite a portion 
of the dried precipitate with a reducing agent and determine 
the presence of a sulphuret in the residue, in the manner already 
pointed out. When this examination yields positive results, 
there is no longer any doubt whatever of the presence of the 
acid. The reactions of this test may, however, be confirmed by 
examining other portions of the solution by some of the other 
tests for the acid. 
If the mixture presented for examination contain much solid 
organic matter, it should, after dilution if necessary, be kept at 
a boiling temperature for ten or fifteen minutes, then, when 
cooled, filtered, and the solids on the filter well washed with 
warm water. The filtrate thus obtained is properly concentrated 
and examined in the manner just described. 
Although in this manner the presence of sulphuric acid may 
be fully and unequivocally established, yet it does not follow 
that it was present in its free state, even when the liquid had a 
strong acid reaction. For, it may have existed in the form of 
one of the acid sulphates, such as common alum, the solutions 
of which have an acid reaction; or it may have been present 
as a neutral sulphate, such as sulphate of magnesia, and the 
acidity of the mixture have been due to the presence of some 
other acid, as acetic acid in the form of vinegar; or lastly, only 
a portion of it may have been free, the mixture having contained 
both the free acid and a sulphate. 
To determine this point, a portion of the suspected solution 
is evaporated to dryness, when, if it leave no saline residue or SEPARATION FROM ORGANIC MIXTURES. 
115 
Only 
an insignificant one, it is certain that the acid existed in 
ds free state 5 if, however, it leaves a saline deposit, then there 
may have been no free sulphuric acid present. When the 
original mixture contains much organic matter, it may be diffi- 
Cldt at first, by simple inspection, to determine the presence or 
otherwise of saline matter in the evaporated residue. When 
lids is the case, the residue should be moistened with pure nitric 
a°id and the mixture evaporated at a moderate heat to dryness, 
and the operation repeated until the dry residue has a yellow 
color, after which the heat is gradually increased till the organic 
flatter is entirely destroyed, when if a salt be present, it will 
1 emain as a white mass. The nitric acid in this operation facil- 
itates the decomposition of the organic matter, and at the same 
lime prevents the reduction of any sulphate present to the state 
°f sulphuret, which might otherwise take place during the 
oxidation of the organic matter. If the ignited mixture thus 
leaves a saline residue, a portion or the whole of the sulphuric 
acid may have existed in the form of a sulphate. A portion of 
Hie residue may be dissolved in water and the solution tested in 
Hie ordinary manner. It does not follow, however, from thus 
obtaining a sulphate, for reasons pointed out hereafter, that even 
any Part of the acid originally existed in its combined state; yet 
lmder these circumstances, it can never be proved by chemical 
cneans, that the tvhole of the acid was originally present in its 
free state. 
For determining and separating free sulphuric acid from 
Solutions of its salts, various methods have been advised. Thus, 
cl has been proposed to concentrate the mixture to near dryness 
and agitate the residue with absolute alcohol or ether, for the 
Pm pose of dissolving the free acid while its salts would remain 
cccsoluble. But, as remarked by Dr. Christison, alcohol will 
extract a portion of sulphuric acid from acid sulphates, and even 
central sulphates are not wholly insoluble in this menstruum; 
aad again, ether extracts the free acid to only a very limited 
extent, even in the presence of only a very minute quantity 
. evater. It has also been proposed, to add to the warmed 
ccccxture, finely-powdered carbonate of baryta, in small quantity 
a lime, as long as it produces effervescence, by which the 116 
SULPHURIC ACID. 
free acid would be precipitated as sulphate of baryta, while 
the soluble sulphate present would remain unacted upon. The 
precipitate thus obtained would, therefore, represent the amount 
of free acid present. By stopping the addition of the baryta 
carbonate the moment effervescence ceases, this method under 
certain conditions, yields very accurate results; yet, if the sul- 
phate present was a neutral alkaline salt, it would, partially at 
least, be estimated as an acid sulphate, while on the other 
hand, some of the acid sulphates, as common alum, decompose 
carbonate of baryta with effervescence. Should, however, the 
original mixture contain a sulphate and a free acid not sulphuric, 
the operator might be wholly misled by this method. Thus if 
the free acid existed in excess over the salt, the carbonate of 
baryta would precipitate the whole of the sulphuric acid from 
the salt, and still give rise to effervescence: under these circum- 
stances, therefore, the whole of the precipitate would be due 
simply to the presence of a sulphate. 
When the examination has shown the presence of sulphuric 
acid in a solution which contains a saline compound, the safest 
and most accurate method for determining whether or not the 
whole of the acid may have existed in the form of a sulphate, 
is the following: A given volume of the solution, after the 
addition of a little hydrochloric acid, is treated with excess of 
chloride of barium, and the precipitate collected, dried and 
weighed, in the manner described hereafter; an equal volume 
of the solution is then evaporated to dryness, the residue thor- 
oughly dried, but not ignited, then dissolved in acidulated water, 
the filtered solution precipitated as before, and the dried deposit 
weighed. Every 2*38 parts by weight of the former precipitate 
in excess over the latter, correspond to one part of free mono- 
hydrated sulphuric acid. This estimate may however fall short 
of the real amount of the free acid originally present, but it 
could never exceed it. If in determining the amount of com- 
bined acid in the evaporated residue, the latter be ignited, any 
acid sulphate present might give up a portion of its acid, which 
would, therefore, be estimated as free; so also, the ignition might 
reduce some of the sulphate to the state of sulphuret, and thus 
cause an error in the same direction. If the suspected solution SEPARATION FROM ORGANIC MIXTURES. 
117 
contained simply a sulphate and a free acid other than sulphuric, 
the precipitates obtained by both of the above operations, would, 
°f course, be equal in weight. 
Although this method, as just intimated, may under certain 
conditions, fail to show the whole of the acid as free that really 
existed as such, yet in most instances, this would not be likely 
1° seriously affect the results. Nevertheless, cases might occur 
ln which the operator would be led to conclude that little or 
even none of the acid was present in its free state, when the 
whole of it had been added as such. Thus, for example, if free 
sulphuric acid was added to a solution of chloride of sodium, or 
common salt, the mixture on evaporation would leave an acid 
sulphate of soda, the chlorine, in part at least, of the common 
salt being expelled in the form of hydrochloric acid. If under 
these circumstances, the amount of salt present equaled or 
exceeded the acid added, the whole of the latter would be 
estimated as combined. Similar results would be observed in 
regard to solutions of other salts. In a solution containing 
°ne base and two different acids, especially in about equivalent 
proportions, it is impossible by chemistry alone, to determine 
Which acid originally existed in combination with the base, 
bases of this kind, it is true, are not likely to occur in medico- 
legal investigations, especially in the examination of suspected 
articles of food or drink, yet it is well to bear in mind the 
Possibility of their occurrence. In suspected solutions containing 
*his poison, the nature of the mixture and attending circum- 
stances, usually leave no doubt as to its true character. 
Contents of the Stomach.—These, carefully collected in a 
arge porcelain dish, are tested in regard to their chemical 
any solids present cut into small pieces, and the 
fixture, after the addition of water if necessary, kept at about 
a boiling temperature for half an hour or longer; the cooled 
is then strained, the solids washed with hot water, the 
U'uted liquids concentrated, filtered, and the filtrate examined 
j*1 the manner pointed out above. This method would of course 
equally applicable for the examination of the matters ejected 
°m the stomach by vomiting during life. Should an antidote, 
Bllch as an alkaline carbonate, have been administered, the 118 
SULPHURIC ACID. 
contents of the stomach, as well as the matters vomited, may 
contain the acid only in the form of a sulphate and have a 
neutral reaction. Under these circumstances, in the prepara- 
tion of the mixture, it should he strongly acidulated with 
hydrochloric acid ; the amount of combined sulphuric acid is 
then estimated in the manner already described. 
So also, if the person had been actively treated or survived 
the taking of the poison some days, it may have entirely disap- 
peared from the stomach. This result has been observed in 
several instances in which death took place within even short 
periods. Thus in a case mentioned by Mertzdorff, in which the 
poison proved fatal within twelve hours to a child, the contents 
of the stomach had no acid reaction, but on the contrary an 
ammoniacal odor, and contained a soluble sulphate, probably the 
sulphate of ammonia. (Christison On Poisons, p. 126.) This 
conversion, according to Orfila, always takes place with greater 
or less rapidity, when the acid is present in decomposing nitro- 
genised organic mixtures. 
It is well known that the natural secretions of the stomach 
have usually a distinctly acid reaction, due to the presence of 
minute quantities of hydrochloric and lactic acids. Whether 
the acidity of the mixture under examination is due simply to 
these acids or really to the presence of free sulphuric acid, can, 
of course, only be determined by the attending circumstances 
and a chemical analysis. In determining the quantity of free 
sulphuric acid present, it must be borne in mind that the con- 
tents of the stomach usually contain small quantities of alkaline 
salts, particularly chlorides, and that these, on evaporating the 
mixture to dryness, will convert a corresponding portion of the 
free acid into sulphates: the proportion thus converted, however, 
would rarely affect the general results. In this connection it 
must also be remembered that sulphates may be normally present 
in very minute quantity in articles of food and complex organic 
mixtures; and moreover, that some of these salts are used 
medicinally in large doses. 
From the above considerations, it is evident that in poisoning 
by sulphuric acid, cases may readily arise in which the proof 
of the poisoning will rest chiefly or entirely upon the symptoms QUANTITATIVE ANALYSIS. 
119 
and post-mortem appearances. In all such cases, however, we 
should be able to satisfactorily account for the failure of the 
chemical analysis. 
From organic fabrics.—The texture of articles of clothing 
''vith which sulphuric acid comes in contact is usually more or 
less destroyed, and the spots remain moist for a long period, due 
to the affinity of the acid for water; so also, the color of the 
ai'ticle is more or less changed, it in most instances assuming a 
1 eddish or brownish hue. These spots may retain an acid reac- 
tion for many months or even years. 
The presence of the acid in stains of this kind may be 
determined by boiling the stained portion with a small quantity 
pnre water, filtering the solution thus obtained, and examin- 
lng the filtrate in regard to its chemical reaction and with 
chloride of barium, in the usual manner. A portion of the fil- 
trate should also be examined in regard to the presence of 
Saline matter. Should the latter be present with the acid, it 
then becomes necessary to determine, in the manner already 
indicated, whether or not the whole of the acid may have been 
in its combined state. If the examination shows that this may 
ave been the case, it is then necessary to examine an equal 
Portion of the unstained article, after the same process, since in 
the preparation of fabrics of this kind minute quantities of sul- 
phates are sometimes employed. 
Quantitative Analysis.—Sulphuric acid is usually esti- 
mated in the form of sulphate of baryta. For this purpose, the 
Solution is treated with slight excess of chloride of barium, and 
e mixture gently heated until the baryta precipitate has com- 
P etely subsided. The deposit is then collected on a small filter 
of u r 
nnown ash, repeatedly washed with hot water containing 
jUrochloric acid, dried, ignited, and weighed. When only a 
small quantity of the precipitate is present, after being washed 
mid dried it should as far as practicable be removed from the 
er,.and ignited alone; the filter with any adherent sulphate is 
cii ignited, and the weight of the residue, after deducting the 
i °f the filter, added to the weight of the previously ignited 
Sldphate. 120 
NITRIC ACID. 
Every one hundred parts by weight of sulphate of baryta 
thus obtained, correspond to 42‘02 parts of monohydrated sul- 
phuric acid, 105 grains of which measure one fluid drachm. 
Section ll.—Nitric Acid. 
Nitric Acid, or aqua fortis, as found in the shops, is a 
powerfully corrosive acid liquid, having usually a more or less 
yellow or even reddish color. In its action upon organic sub- 
stances, it is about equally active with sulphuric acid. Instances 
of poisoning by it, however, have been of very much less fre- 
quent occurrence than by the latter. 
Symptoms. These in most respects are identical in kind 
with those observed in sulphuric acid poisoning. When the 
acid is swallowed in its concentrated state, the mucous mem- 
brane of the mouth and other parts with which the liquid comes 
in contact, is immediately corroded and assumes a white appear- 
ance, which, however, unlike that produced by sulphuric acid, 
soon changes to yellow, and then in some instances slowly 
becomes more or less brown. All spots produced on the ex- 
ternal skin by the acid, very soon acquire a permanent yellow 
color. 
The usual symptoms are violent pain in the mouth, oesoph- 
agus, and stomach; copious eructations of gaseous matter, hav- 
ing sometimes a reddish color, due to the presence of the 
decomposed acid; excessive vomiting of strongly acid, yellow 
or brownish matters; tenderness and tension of the abdomen; 
general coldness of the body, especially in the extremities; 
difflculty of respiration and of deglutition, from the local action 
of the acid on the internal organs of the mouth and fauces ; a 
small and frequent pulse; extreme thirst, cold sweats, and great 
prostration of strength. The local action of the acid may be 
confined to the mouth and fauces, none of the poison having 
been swallowed. 
In most instances, the more immediate symptoms produced 
by nitric acid are proportionate to the degree of its concentra- 
tion and the quantity taken; but this is by no means always PHYSIOLOGICAL EFFECTS. 
121 
the case. Tims Dr. Beck cites the case of a young man, who 
died in twenty hours, from the effects of the acid, without at 
any time showing signs of acute pain or of agitation; yet after 
death, there was found perforation of the stomach, with great 
effusion of its contents into the abdomen. In another case, a 
lonian swallowed a quantity of the poison, and, at least for 
some hours afterwards, there was neither agitation, pain nor 
vomiting, but a condition rather indicating typhus fever. She 
died the following day, and on examination of the body, there 
Was found most extensive disorganisation of the abdominal 
organs: perforation of the stomach, gangrenous spots, effusion 
into the abdomen, marked erosion, and a general yellow color 
°f all the viscera. 
If the patient survive the primary effects of the poison, 
these may be succeeded by irregular fever, obscure pains in 
the throat and epigastric region, impaired digestion, irritability 
°I the stomach, frequent vomiting, obstinate constipation, dry- 
ness of the skin, disturbed respiration and deglutition, some- 
times profuse salivation, fetid breath, frequent rigors, and great 
muscular emaciation. Sometimes large membranous flakes or 
men masses of the lining membrane of the throat and oesoph- 
a§ns are ejected with the vomited matters. 
The vapor, or fumes, arising from nitric acid, has in several 
caused death. In a recent instance of this kind, a 
chemist, Mr. Stewart, of Edinburgh, and his assistant, inhaled 
|h° fumes while endeavoring to save a portion of the liquid that 
lad escaped from a broken jar. After an hour or two, the 
ormer began to experience difficulty of breathing, and sent for 
medical advice, but he very rapidly became worse, and died 
111 about ten hours after the accident. His assistant was also 
taken ill? and died about fifteen hours later. (Chem. News, Lon- 
-orbrb March, 1863, p. 132.) An instance is also reported by Mr. 
pence, in which the fumes of the acid proved fatal to two 
Poisons; the first of whom died in about forty hours, and the 
°ther some hours afterwards. (Ibid, p. 167.) In at least one of 
ese cases, the symptoms were delayed for some hours. In the 
case of Mr, Haywood, who inhaled the fumes arising 
°m a mixture of nitric and sulphuric acids, the symptoms were 122 
NITRIC ACID. 
delayed for more than three hours, and death occurred in about 
eleven hours. 
Period when Fatal.—Nitric acid has in several instances 
caused death within a very few hours, and in most instances in 
which death occurred .from its primary effects, that event fol- 
lowed within forty-eight hours; but the patient may recover 
from the primary action of the poison and die from secondary 
effects many months afterwards. Thus in a case quoted by Dr. 
Taylor, death occurred in one hour and three-quarters after the 
poison had been swallowed 5 while, on the other hand, Tartra 
mentions an instance in which death did not occur until after a 
period of eight months. Out of fifty-six cases of poisoning by 
nitric acid, collected by Tartra, twenty-one of the patients 
completely recovered, and eight partially. 
Fatal Quantity.—ln most of the instances of poisoning by 
this substance, the quantity taken was not ascertained. Most 
writers on this subject, however, agree in fixing the fatal quan- 
tity, for a healthy adult under ordinary conditions, at about two 
rfrachms of the concentrated acid 5 yet quantities much larger 
than this have in several instances been followed by complete 
recovery. In a case reported by Dr. J. M. Warren, a woman, 
aged thirty-four years, having with suicidal intent taken three 
drachms of the acid into her mouth swallowed a portion, but 
most of it was spit out. She was seized with the usual symp- 
toms, which, however, after several days, under active treat- 
ment, nearly subsided; but secondary symptoms set in and she 
died on the fourteenth day after the poison had been taken 
(Amer. Jour. Med. Sci., July, 1850, p. 36). 
Treatment.—This consists in the speedy administration of 
calcined magnesia, chalk, or a dilute solution of an alkaline 
carbonate, followed by the free exhibition of oily or mucilagin- 
ous drinks. In every respect, the treatment is the same as that 
already mentioned in sulphuric acid poisoning (ante, p. 101). 
Post-mortem Appearances.—These will, of course, depend 
somewhat on the length of time the individual survived after 
taking the poison. In acute cases, the lining membrane of 
the lips, mouth and fauces, has sometimes a white, but more 
generally a deep yellow or even brownish color j often large PATHOLOGICAL EFFECTS. 
123 
patches of this membrane are entirely removed. The mucous 
Membrane of the oesophagus is often much thickened and altered 
structure, of a yellow color, and readily separated. And 
. e appearances may be observed in the larynx and trachea, 
the acid has passed into these organs. In these examin- 
ations, as in sulphuric acid poisoning, it must be borne in 
ttund that the mouth and oesophagus may exhibit but little 
injury, the stomach being the part chiefly affected; and on the 
other hand, that the whole of the local injury may be confined 
!° mouth and air-passages, little or none of the poison hav- 
lng been swallowed. In an instance of poisoning by this acid 
fluoted by Dr. Christison, it left no trace of its passage down- 
ard until it had arrived near the pylorus. 
Tke stomach is usually distended, externally changed in 
c°lor, more or less inflamed, and adherent to the neighboring 
organs. The contents of this organ have frequently a yellow 
due to the action of the acid upon the contained matters. 
16 mucous membrane is often greatly disorganised and much 
anged in color, and the blood-vessels injected with dark coag- 
ated blood. In the case reported by Dr. Warren, the stomach 
externally was of a purple color, and adherent to the neighbor- 
ing parts; internally it was of a greenish-yellow color, and its 
ssues were so softened that it could not be separated from the 
sui rounding parts without being greatly lacerated. When the 
C°ats of the stomach are perforated by the acid, which how- 
o^0r rarely happens, the contents of the organ may escape into 
. e abdomen and cause a yellow coloration and great disorgan- 
-ISati°u of all the neighboring viscera. 
The small intestines, particularly the upper portion, may 
übit appearances similar to those found in the stomach; 
.en, however, they entirely escape the direct action of the 
a°lcl? it not passing below the stomach. The large intestines 
usually filled with hard faeces. The other abdominal organs 
•g 6 °ftcn more or less highly inflamed, even when the stomach 
u°t perforated; the bladder is usually empty, no urine hav- 
been secreted. 
the patient survives the primary effects of the poison 
11 dies from secondary results, the body is greatly emaciated, 124 
NITRIC ACID. 
and the stomach and other portions of the alimentary canal 
more or less contracted, their walls thickened and the cavities 
nearly closed. Stricture of the oesophagus has not unfrequently 
occurred, and the pyloric end of the stomach has been so 
greatly contracted as to nearly obliterate its opening. In some 
few instances, the stomach was so far destroyed that no part of 
its structure could be distinguished. 
Chemical Properties. 
General Chemical Nature.—Anhydrous nitric acid is a 
compound of the elements Nitrogen and Oxygen, in the pro- 
portion of one equivalent of the former to five of the latter 
(NO5). It is a very rare, transparent, colorless, crystalline 
substance; in this state it melts at 85°, and boils at about 
113° P.: it was first obtained, in 1849, by Deville. In com- 
bination with water, it has long been known under the name of 
aqua fortis, which in its most concentrated form, consists of 
one equivalent of the anhydrous acid in combination with one 
of water (HO, N05.) 
In its pure hydrated state, nitric acid is a colorless, intensely 
corrosive acid liquid, which in its most concentrated form, has a 
density of about 1-520, and contains 85-72 per cent, of the an- 
hydrous acid. The density of the acid of the shops, usually 
varies from 1*350 to 1-450. Concentrated nitric acid is one of 
the most powerfully corrosive substances known. It imparts a 
yellow stain to the skin, nails, wool and other organic sub- 
stances. Exposed to the air, it emits white fumes ; when 
mixed with water, it evolves a sensible amount of heat. It 
boils at about 184°, and freezes at —4o° F. When the con- 
centrated acid is boiled, it diminishes in density and its boiling 
point increases, until the liquid acquires a density of 1"424, 
when it distills unchanged in the form of a definite hydrate of 
the acid, consisting of four equivalents of water with one equiv- 
alent of real acid (4 HO; N05). 
The following table, according to Dr. Ure, indicates approx- 
imatively the per cent, by weight, of anhydrous nitric acid 
(NO5) in pure aqueous solutions of different specific gravities: SPECIAL CHEMICAL PROPERTIES. 
125 
STRENGTH OF AQUEOUS SOLUTIONS OF NITRIC ACID. 
sp- OR. 
PEE CENT. 
SP. GR. 
PER CENT. 
SP. GR. 
PER CENT. 
SP. GR. 
PER CENT. 
1-500 
79.7 
1-402 
56-6 
1-258 
35-1 
1-117 
16-7 
1-491 
76-5 
1-383 
53-4 
1-246 
33-5 
1-093 
13-5 
1-479 
73-3 
1-363 
50-2 
1-221 
30-3 
1-071 
10-4 
1-467 
70-1 
1-343 
47-0 
1-196 
27-1 
1-048 
7-2 
1-453 
66-9 
1-322 
43-8 
1-183 
25-5 
1-027 
4-0 
1-439 
63-8 
1-300 
40-4 
1-171 
23.9 
1-016 
2-4 
1-419 
59-8 
1-283 
38-3 
1-146 
20-7 
1.005 
0-8 
Nitric acid as found in commerce, is generally more or less 
colored, the color being due to the presence of some of the 
°wer oxides of nitrogen, and varying from a light yellow to an 
oiange red. In this state, it is even more corrosive than the 
Pure acid. It is not unfrequently contaminated with sulphuric 
and hydrochloric acids, and other impurities. 
The salts of nitric acid are for the most part colorless, and 
d'y freely soluble in water. They are all decomposed by a 
J'cd heat. Their aqueous solutions are also decomposed when 
cated with free sulphuric acid, with the formation of a sul- 
phate, the nitric acid being eliminated in its free state. 
Special Chemical Properties.—Nitric acid very readily 
parts with a portion of its oxygen. When brought in contact 
many of the metals, such as copper, zinc, iron or tin, it is 
lr| Part decomposed with great rapidity, with the formation of a 
titrate and the evolution of one or more of the lower oxides of 
in the form of deep red fumes. The evolution of these 
Ulßes is quite characteristic of the acid. 
. When a nitrate, in its dry state, is brought in contact with 
hinted charcoal, the latter burns vividly at the expense of the 
x}rgen of the nitric acid, the salt, if an alkaline compound, 
e*nS converted into a carbonate. 
Pll account of the free solubility of the compounds of nitric 
acid, it can not be precipitated from solution by reagents; 
°Wever, the presence of very minute traces of the acid, can 
. 6 with great certainty. When not too much diluted, 
may be recognised by the properties already mentioned. In 
e Allowing examination of the behavior of solutions of nitric 126 
NITRIC ACID. 
acid, the fractions employed express the fractional part of a 
grain of the anhydrous acid present in one grain of the solution, 
the menstruum being pure water. 
1. Copper Test. 
When tolerably strong nitric acid is treated in a test-tube 
with a slip of copper-foil, the acid in part is immediately 
decomposed with the evolution of binoxide of nitrogen, which 
in coming in contact with the air is oxidised and escapes in 
the form of deep red fumes of hyponitric acid (N04); at the 
same time, the undecomposed portion of the acid unites with 
the oxide of copper formed to nitrate of copper, which imparts 
to the liquid a more or less greenish color. These reactions 
are expressed by the following formulae: 4N05+3 Cu= 8 CuO, 
N05+N02; then, N02 + 02 = N04. 
When the acid is more dilute, it is not acted upon by 
copper unless the mixture be heated or free sulphuric acid be 
added, and the gas evolved may be colorless; its presence, 
however, may be recognised by its peculiar odor, acid reaction, 
and by rendering blue a piece of starch-paper moistened with 
a solution of iodide of potassium. In the presence of sulphuric 
acid, the whole of the nitric acid, whether in its free state or 
as a nitrate, is evolved finally in the form of hyponitric acid. 
The following results refer to the behavior of five grains of 
the nitric acid solution with a very small slip of copper-foil. 
1. 10th solution, or half a grain of anhydrous nitric acid in five 
grains of water, fails to be acted upon by the copper 
till heat is applied,—then decomposition takes place quite 
briskly, yielding quite perceptible red vapors, which 
quickly redden moistened litmus-paper, and impart a blue 
color to starch-paper prepared as above. The liquid 
assumes a very marked greenish-blue color. 
2. 20th solution, yields only a feeble reaction, even on the 
application of heat; but if a few drops of concentrated 
sulphuric acid be added, there is a brisk reaction and 
ultimately the liquid acquires a very distinct greenish- 
blue color. GOLD TEST. 
127 
°* 50th solution, gives no evidence of decomposition by heat 
alone ; but with sulphuric acid and heat, it yields a brisk 
reaction and a light greenish-blue solution. If this experi- 
ment be performed in a very narrow tube, the evolved 
gas imparts a distinct reddish hue to the contained air. 
lOOth solution, under the influence of a few drops of sul- 
phuric acid and heat, yields a quite good effervescence 
around the surface of the copper, and the liquid acquires 
a faint greenish-blue color. 
500 th solution, under the same influences as 4, yields a 
very distinct effervescence, and after a time the fluid 
acquires a perceptible greenish tint, 
b,oooth solution, yields a perceptible reaction. 
Results similar to the above may be obtained from the acid 
in the form of a nitrate; but then, the addition of sul- 
phuric acid is necessary in all cases. If the nitrate to be 
Rsted is in the solid state, it should be dissolved in the least 
P1 acticable quantity of water; on the other hand, if it is in 
the liquid should be concentrated as far as practicable 
etore the test is applied. In the use of this test, it must be 
vept in mind that sulphuric acid not unfrequently contains 
traces of nitric acid: the presence of this impurity could, of 
c°urse, be determined by the test itself, before it is applied to 
a suspected solution. 
2. Gold Test. 
bf a solution of free nitric acid or of a nitrate, be heated 
excess of pure hydrochloric acid, the two acids react upon 
®ach other and eliminate free chlorine, which has the property 
0 dissolving gold-leaf to the form of chloride of gold. The 
Presence of the gold compound can be recognised, when present 
_llot too minute quantity, by a solution of chloride of tin, 
mix produces a purple precipitate, or at least imparts a 
Prnplish color to the liquid. 
before applying this test to a suspected solution, the hydro- 
-ol'ic acid about to be employed should be tested alone, in 
cl j6l*- determine whether it is entirely free from uncombined 
01 me, which is often present. 128 
NITRIC ACID. 
When one grain of the nitric acid solution is mixed, in a 
small test-tube, with five grains of tolerably strong hydrochloric 
acid and a very small slip of gold-leaf, the mixture on being 
heated to the boiling temperature, yields the following results : 
1. vto' grain of nitric acid: in a very little time, the gold 
dissolves; the cooled solution yields with the tin reagent 
no immediate change, but after a little time, it assumes a 
decided purple color. 
2. rrswo grain: after a little time the gold dissolves, and the 
cooled solution yields with the tin compound a faint purple 
color. 
3. 5- oVo grain, after several minutes, dissolves a very minute 
quantity of gold; but the solution fails to yield satisfactory 
results with the tin reagent. 
These reactions are also common to solutions of chlorates, 
hypochlorites, chromates, iodates, and bromates. The same is 
also true of the sesqui-combinations of iron, as first pointed out 
by Henry Wurtz (Chem. Gazette, xvii, p. 32). This metal is 
readily separated by treating the solution with carbonate of 
soda, and filtration. It need hardly be added that a nitrate 
may be distinguished from all of these fallacious salts, by the 
action of the preceding test. 
3. Iron Test. 
When free nitric acid or a solution of a nitrate, is mixed 
with several times its volume of concentrated sulphuric acid 
and the cooled mixture treated with a crystal of sulphate of 
iron, the latter after a time becomes surrounded by a blackish- 
brown, brownish or purple compound, which is said to consist 
of 4 FeO, S03; H02. Instead of using the iron salt in its solid 
state, it is more satisfactory to employ it in the form of a 
saturated solution. To thus apply the test, a drop of the nitric 
acid solution is thoroughly mixed in a small test-tube with 
eight or ten times its volume of sulphuric acid, the mixture 
gently warmed for a little time, then cooled by immersing the 
tube in cold water; a drop of the iron solution is then allowed 
to flow down the inside of the tube upon the acid mixture, INDIGO TEST. 
129 
'when the stratum where the two liquids are in contact will 
acquire a beautiful purple or brownish-purple color, the tint 
depending on the quantity of nitric acid present; on now 
slowly mixing the liquids by means of a glass rod, taking 
Sieat care that no heat is evolved, the same coloration will be 
°kserved throughout the mixture. 
Tfo' grain of nitric acid, in one grain of water, when treated 
as above, the contact surfaces of the iron and acid liquids 
present a beautiful purple line; on carefully mixing the 
liquids, the mixture assumes a deep purple color, and soon 
begins to effervesce, gives out the odor of hyponitric acid, 
and the color becomes discharged. On the addition of 
another drop of the iron solution, the color is reproduced. 
'* iToWo grain, yields a beautiful purple mixture, which remains 
unchanged for at least several hours. 
* sToTo grain: on mixing the two solutions, they assume a 
very decided purplish tint, which is permanent for some 
hours. 
4. i ..... 
* io.oWo grain: the mixed liquids assume a distinct purplish 
hue, which after some hours becomes pinkish. These 
colors are best seen by inclining the tube over a piece of 
white paper. 
-Much the same results as those just described, may be 
ained by employing the iron compound in the solid state; its 
Solution, however, is preferable. In all cases, before applying 
s test to a suspected solution, the sulphuric acid should be 
. sed alone: in fact, it is somewhat difficult to find that acid 
f the shops entirely free from traces of nitric acid or some of 
le lower oxides of nitrogen. 
4. Indigo Test. 
. Mrhen a solution of nitric acid or of a nitrate, is mixed 
hydrochloric acid, or chloride of sodium as recommended 
y Liebig, and the mixture colored by a solution of indigo, 
ri Suited with sulphuric acid, the chlorine set free through 
ugency of the nitric acid, will discharge the blue color of 
unxture. In applying this test, a small quantity of the 
9 130 
NITRIC ACID. 
nitric acid solution is treated with a few crystals of pure 
common salt or a drop of hydrochloric acid and just enough 
of a strong sulphuric acid solution of indigo to impart a distinct 
blue tint; the mixture is then heated, and while hot a few 
drops of concentrated sulphuric acid cautiously added and mixed 
with the liquid, after which, if necessary, the heat is continued 
until the blue tint of the fluid disappears. 
The following results refer to the behavior of jive grains of 
the nitric acid solution. 
1. 100 th solution, when treated as above, the blue color, on the 
addition of a few drops of sulphuric' acid to the heated 
mixture, is immediately discharged and the liquid assumes 
a yellow color. 
2. I,oooth solution, yields much the same results as 1. 
3. 10,000 th solution: the blue color is not discharged until the 
mixture is heated some minutes with several drops of sul- 
phuric acid; the liquid then acquires a faint yellow tint. 
4. 20,000 th solution, behaves much the same as 3. 
5. 50,000 th solution, requires to be boiled several minutes with 
several drops of sulphuric acid, before the blue tint dis- 
appears. For the success of this reaction, it is necessary 
to employ the merest trace of indigo, the tint of which is 
best seen by inclining the tube containing the mixture, 
over white paper. 
It is well known that chlorates, chromates, iodates, binoxide 
of manganese, and several other similar compounds, have, like 
nitric acid, the property of evolving chlorine from hydrochloric 
acid, and therefore of bleaching a solution of indigo; and 
Wurtz, in his valuable paper already referred to, has shown 
that the chlorides of gold, platinum and tin, bleach an indigo 
solution, even without the presence of hydrochloric acid, and 
that in the presence of this acid, arsenic acid has a similar 
property. It is not likely, however, that either of these falla- 
cious substances |fbuld be present in a medico-legal investiga- 
tion for nitric acid. 
Much more probable sources of error than either of those 
just mentioned, to be guarded against, are the presence of free 
chlorine in the hydrochloric acid, and of traces of nitric acid BRUCINE TEST. 
131 
0r some of the lower oxides of nitrogen, in the sulphuric acid 
employed. No reliance whatever could be placed in this test 
''vhen applied to organic mixtures. 
5. Brucine Test. 
This test, which was first suggested by Berthemont, is based 
the production of a blood-red color, when nitric acid or a 
titrate is mixed with a sulphuric acid solution of brucine. Pure 
brucine, when added to pure sulphuric acid, assumes a pale 
pink color and slowly dissolves to a colorless or nearly colorless 
solution, unless the proportion of alkaloid he comparatively 
large, when the solution has a pinkish hue. 
When one grain of the free nitric acid solution or of a 
titrate is mixed, for convenience in a white porcelain dish, 
!th about five fluid grains of concentrated sulphuric acid, and 
a few crystals of brucine added, if the solution contains : 
1* Ton grain of anhydrous nitric acid, the brucine immediately 
to a solution of the same hue, which very slowly fades to 
bright yellow. 
*" TTcroo grain: the alkaloid acquires a red color, and yields a 
dull orange solution, which slowly becomes yellow. 
sTToo grain: the brucine assumes a rose pink color, and 
assumes a red-orange color, and on being stirred, dissolves 
dissolves to a solution having a decided reddish-pink hue, 
which changes to faint orange, then fades to yellow. 
Torero grain: the crystals acquire a pink color and dissolve 
to a solution of the same tint, which becoming amber 
changes to yellow. 
’ arrows grain: the brucine assumes a reddish color, and when 
stirred in the mixture, imparts to it a decided amber color, 
which soon changes to light yellow. 
s'oToro grain: the alkaloid becomes slightly colored, and 
yields a solution of a faint amber color, which quickly 
changes to very light yellow. These colors are quite 
feeble, yet when the reaction is compared with that 
obtained from the alkaloid and sulphuric acid alone, the 
difference is very well marked. 132 
NITRIC ACID. 
When the nitric acid is in the solid state in the form of a 
nitrate, the reaction of this test is even more delicate than 
when applied to solutions. Under these circumstances, a very 
small portion of the salt, or the residue left on evaporating its 
solution to dryness, is dissolved in a few drops of sulphuric 
acid, and then a crystal or two of the alkaloid added. The 
residue obtained from a solution of nitrate of potash containing 
only the 100,000 th part of a grain of nitric acid, when moist- 
ened with a very small drop of sulphuric acid containing a little 
brucine, immediately assumes a distinct orange color, and dis- 
solves to a brick-dust pink solution, the tint of which-soon 
fades to faint yellow. 
This test furnishes the most ready and delicate means of 
determining the purity of sulphuric acid in regard to the pres- 
ence of traces of nitric acid. 
A sulphuric acid solution of brucine also produces a some- 
what similar coloration with chloric acid and its salts. But, the 
most minute quantity of a salt of this kind, imparts a strong 
yellow, and a very small quantity an orange color, to sulphuric 
acid alone, and evolves fumes of hypochloric acid, having a 
greenish color and peculiar odor. To guard against this fallacy, 
therefore, it is only necessary to observe the action of the sul- 
phuric acid alone. 
6. Narcotine. 
When a small quantity of narcotine is added to a few drops 
of pure concentrated sulphuric acid, the alkaloid dissolves to a 
light-yellow solution, which when heated assumes a purplish 
color; but if free nitric acid or a nitrate be present, the narco- 
tine dissolves to a reddish-brown solution, which on the appli- 
cation of a gentle heat acquires a deep blood-red color. Mialhe 
was the first to employ this reaction as a test for nitric acid. 
When one grain of the nitric acid solution is mixed with 
five fluid grains of sulphuric acid, and the mixture allowed to 
cool, the addition of a few crystals of narcotine produces the 
following results : 
1. wow grain of nitric acid: the alkaloid assumes a deep-brown 
color, and imparts to the liquid a decided brownish-yelloW lODINE AND OTHER TESTS. 
133 
color, which by heat is changed to a permanent deep 
blood-red. 
9 i 
row grain: the narcotine dissolves to a decided reddish 
solution, which when heated assumes a fine blood-red 
color. 
O 
row grain, yields a distinct reddish color, which is changed 
to reddish-brown by heat, 
nyow grain: the solution of the alkaloid has a faint red- 
dish tint, which by heat is changed to a purple-red. This 
last color might be readily confounded with that from nar- 
cotine alone; but this alkaloid singly would not impart the 
primary reddish tint. 
When the nitric acid is in solution in the form of a nitrate, 
liquid should be evaporated, and the dry residue dissolved 
111 a few drops of colorless sulphuric acid, then tested by a few 
Crystals of narcotine. Under these conditions, given quantities 
the acid yield even stronger colors than described above. 
lodine Test.—This method, first proposed by J. Higgin 
Whem. Gaz., viii, p. 249), takes advantage of the property 
Possessed by nitric acid of decomposing hydriodic acid with the 
of free iodine, and the ready detection of the latter 
. y of starch. To apply this test, the suspected solution 
18 mixed with about one-sixth of its volume of concentrated 
Sldphuric acid and heated to near the boiling temperature for 
Several minutes, then allowed to cool; the mixture is then 
heated with a drop of starch mucilage and a few drops of a 
. Gly dilute solution of iodide of potassium, when, if nitric acid 
ls present, the liquid acquires a more or less blue color. The 
aTthor of this method states that a 20,000 th solution of the 
acid yields in a few minutes, a decided blue coloration. It 
niUst be remembered, however, that sulphuric acid alone, will 
. a time, liberate iodine, even from very dilute solutions of 
0 "de of potassium. 
, /Wher Tests.—Mr. J. C. Schaeffer has suggested a test, 
.ICa depends on the conversion of nitric acid into nitrous 
Cld by the action of metallic lead, and the production of 
Uch yellow color when the liquid is treated with yellow 134 
NITRIC ACID. 
prussiate of potash and acetic acid (Chem. Gaz., ix, p. 289). 
In somewhat strong solutions of the acid, this reaction is well 
marked; but as the reagent alone yields a yellow coloration, it is 
not applicable for the detection of the acid when much diluted. 
Mr. J. Horsley has proposed a test, which is applied as 
follows: A small quantity of water, acidulated with a few drops 
of sulphuric acid, is placed in a small test-tube, and a small 
portion of pyrogallic acid added, after which a little concen- 
trated sulphuric acid is allowed to flow down the inside of the 
tube and subside to the bottom of the mixture; a few crystals 
of chloride of sodium are then added, and after the efferves- 
cence has ceased, a small quantity of the solid nitrate to be 
examined dropped into the mixture, when the subsided acid, in 
a very little time, assumes an intense purple or deep orange- 
brown color, which may ultimately extend throughout the entire 
mixture (London Chem. News, Jipae, 18G3, p. 268). We can 
confirm the statement of Mr. Horsley in regard to the extreme 
delicacy of this reaction, the smallest particle of a nitrate 
yielding a very satisfactory coloration. 
Separation from Organic Mixtures. 
Suspected Solutions.—lf the suspected liquid has a strong 
acid reaction and is free from suspended solid matters, even 
though it is somewhat colored, a portion of it may be examined 
at once, by being placed in a small test-tube with a slip of 
copper, when if the fluid contains one-third or more of its vol- 
ume of the ordinary nitric acid of the shops, it will immediately 
be acted upon by the metal, give off red fumes and yield a 
greenish-blue solution. If this reaction fail, the mixture, after 
the addition of sulphuric acid if necessary, is gradually heated, 
and any evolved gas examined in regard to its color, odor, and 
with wet litmus-paper and starch-paper moistened with a solu- 
tion of iodide of potassium, in the manner already directed. 
A very good method of applying this test, when the quantity 
of liquid is limited, is to warm a few drops of the suspected 
solution with several drops of sulphuric acid and a slip of cop- 
per, in a watch-glass covered by an inverted glass containing SEPARATION FROM ORGANIC MIXTURES. 
135 
separate slips of the moistened litmus and starch papers. In 
applying this method, it must be remembered that when a sul- 
phuric acid solution of a chloride is heated, it will evolve 
hydrochloric acid gas, which also reddens litmus-paper; and if 
aily oxidising substance is present, a portion of the evolved acid 
niay undergo decomposition with the elimination of free chlo- 
line, which will blue moistened iodised starch-paper. If there 
he any uncertainty in regard to the true nature of these results, 
a portion of the original solution is treated with a saturated 
solution of acetate of silver, when, if a chloride is present, it 
yield a white precipitate of chloride of silver. If a pre- 
Clpitate be thus obtained, the solution is treated with slight 
°xcess of the silver reagent, filtered, and then examined by the 
c°pper test. Should the liquid under examination be free, or 
nearly so, from organic matter, some of the other tests for the 
acid may be applied. 
. When these examinations show the presence of nitric acid, 
d may become necessary to prove that it was not in the form 
a nitrate and the acidity of the solution due to the presence 
pf some other acid. For this purpose, a portion of the solution 
evaporated to dryness, when if it leave no saline residue it 
j F>ws that the acid existed in its free state. If however it 
ave a saline residue, the examination must be conducted on 
+1 ' 
i® same principles as pointed out for the determination of sul- 
I uric acid under like circumstances {ante, p. 116). 
Should the suspected solution be mixed with solid organic 
atters, the mixture, after the addition of pure water if neces- 
filt'^? boiled for about twenty minutes, allowed to cool, 
ered, the solids on the filter washed, and the concentrated 
ate tested. In thus preparing an organic mixture contain- 
free nitric acid, it is well to bear in mind that a portion of 
e acid may undergo decomposition: for this reason, it is some- 
nes est to neutralise the acid by an alkali, before subjecting 
e mixture to the action of heat. When the prepared liquid 
°ntains even only a limited quantity of organic matter, the 
°Pper test is the only one that can be reliably applied. 
Citric acid may be separated and purified from organic mat- 
rs? by neutralising the solution, if this has not already been 136 
NITRIC ACID. 
done, with pure carbonate of potash or of soda, whereby the 
acid will be converted into nitrate of potash or of soda, as the 
case may be; the liquid is then, after filtration if necessary, 
concentrated at a moderate heat until a small portion removed 
to a watch-glass deposits crystals on cooling, when the mass of 
liquid is allowed to stand in a cool place until the crystals have 
separated. If the crystals consist of the nitrate of potash, they 
will usually be in the form of long striated six-sided prisms : 
if of the nitrate of soda, they usually appear in the form of 
small obtuse rhombohcdra. As both of these salts are freely 
soluble in water, much of the salt may fail to separate from 
the liquid. The crystals are now removed from the liquid, 
drained and dried. By again concentrating the decanted liquid, 
a second crop of crystals may be obtained. If the crystals be 
highly colored, as will usually be the case when obtained from 
very complex organic mixtures, they are coarsely powdered and 
washed with absolute alcohol, which will remove much of the 
foreign matter without dissolving more than a mere trace of the 
salt. They are then dissolved, by the aid of a gentle heat, 
in a small quantity of pure water and again separated by 
recrystallisation, when they will generally be sufficiently pure 
for the application of any of the tests. A small crystal may 
now be examined by the brucine test, and the result confirmed 
by some of the other tests, especially the copper method. 
Although the copper reaction is the least delicate of the several 
tests for nitric acid, yet for medico-legal purposes its results are 
the most satisfactory. 
Contents of the Stomach.—These are carefully collected, their 
reaction noted, and then gently boiled for some time with a 
proper proportion of water, the solution filtered, and the con- 
centrated filtrate examined in the manner above described. 
Should an alkaline carbonate or a carbonate of lime or mag- 
nesia, have been administered as an antidote, the whole of the 
acid may be in the form of a nitrate of one of these bases, and 
the mixture have a neutral reaction. In case the potash or 
soda antidote was employed, the examination is conducted as 
before for the separation of the alkaline nitrate; but, when the 
lime or magnesia antidote was administered, the concentrated QUANTITATIVE ANALYSIS. 
137 
filtered solution is treated with carbonate of potash or of soda 
as l°ng as it produces a precipitate, whereby the base of the 
earthy nitrate will be converted into an insoluble carbonate, 
the acid will be changed into an alkaline nitrate. This 
nnxture is then heated for some minutes to cause the complete 
snbsidence of the insoluble carbonate, and the solution filtered, 
after which the filtrate is concentrated and the nitrate separated 
111 its crystalline state. 
From organic fabrics.—Stains produced by this acid on arti- 
oles of clothing and like substances, have usually at first a more 
0r loss yellow color, then become reddish, and after a time 
yellowish-brown. The presence of the acid may be determined 
fiy boiling the stained portion of the article in a very small 
Quantity of pure water, filtering, and concentrating the filtrate, 
if even only a minute quantity of the acid is present, the 
Lquid will have an acid reaction. The solution is then tested in 
Ifie usual manner. Instead of boiling the stained substance with 
Pare water, it may be boiled with a very dilute solution of car- 
°nate of potash or of soda, the acid being thus at once con- 
certed into the form of a nitrate. As nitric acid is volatile and 
IXlol’e readily decomposed than sulphuric acid, it much more 
Readily disappears from stained articles of clothing. Neverthe- 
Cssj Br. Christison detected it in stains on cloth after the lapse 
°f seven weeks; and Dr. Guy quotes an instance in which it 
Vas recovered under similar circumstances, after an interval of 
s°me months. 
The yellow stains produced by nitric acid on the skin, after 
a tune assume a brownish-yellow color. When these spots are 
Moistened with a solution of caustic potash, they immediately 
acquire a bright orange hue, wherein they differ from some- 
at similar stains occasioned by iodine and bromine, which, at 
ast when recent, on the application of the alkali immediately 
disappear. 
Quantitative Analysis. There is no ready method of 
'■’bmating the amount of nitric acid when in solution with 
tfilei .SU^s^ances* If the liquid be simply a diluted solution of 
e acid, the quantity of the latter may be estimated sufficiently 138 
HYDROCHLORIC ACID. 
near for most purposes, from the specific gravity of the fluid. 
When the acid exists in its free state and the solution contains 
no other acid (except sulphuric), its exact • quantity may be 
determined as follows; The solution is treated with very slight 
excess of baryta water, and slowly evaporated to dryness: 
during the evaporation the excess of baryta added will absorb 
carbonic acid from the atmosphere and become changed into 
carbonate of baryta, which is insoluble in water. The dry 
residue is then treated with a sufficient quantity of pure water, 
and the solution filtered. The filtrate, which now contains the 
whole of the nitric acid in the form of nitrate of baryta, is 
treated with diluted sulphuric acid as long as a precipitate is 
produced; the sulphate of baryta thus thrown down, is col- 
lected on a filter, washed, dried, and weighed. Every one 
hundred parts by weight of sulphate of baryta thus obtained, 
correspond to 54 parts of monohydrated nitric acid or 77-2 
parts of acid of specific gravity 1-424, every 81 grains of the 
latter of which measure about one fluid drachm. 
If during the investigation the acid has been converted 
into nitrate of potash, this is transformed into the sulphate by 
treating the concentrated solution with sufficient sulphuric acid. 
The mixture is then cautiously evaporated to dryness, and the 
residue heated to dull redness, when the nitric acid will be 
entirely expelled and leave for each equivalent, one equivalent 
of neutral sulphate of potash. If the residue on cooling be 
not entirely neutral in its reaction, it is moistened with a little 
bicarbonate of ammonia solution and again heated. Every one 
hundred parts by weight of this salt correspond to 72-4 parts 
of monohydrated nitric acid. 
Section lll.—Hydrochloric Acid. 
Hydrochloric, or muriatic acid, formerly called spirit of salt, 
as found in commerce, is a more or less yellow, powerfully acid 
liquid, which evolves irritating fumes when exposed to the air. 
Very few cases of poisoning by this substance are reported, and 
among these, only perhaps in two instances, was it criminally PHYSIOLOGICAL EFFECTS. 
139 
_ ministered. In its action, it is somewhat less corrosive than 
either of the acids already considered. 
Symptoms.—The symptoms produced by hydrochloric acid 
are very similar to those observed in poisoning by sulphuric 
acid. When the acid is swallowed in its concentrated state, the 
patient immediately experiences an intense burning sensation 
throughout the parts with which the liquid comes in contact, 
with a sense of suffocation and the eructation of gaseous 
Matters. These effects are usually sooner or later succeeded by 
Vlolent vomiting, great restlessness, intense pain in the stomach, 
c°ldness of the extremities, and a small, frequent pulse. At 
l'st the tongue and throat usually present a white appearance; 
111 a few instances, white fumes were observed to escape from 
le mouth soon after the poison had been taken. In some 
mstances, on account of the great soreness of the throat and 
swollen condition of the neighboring parts, there is great diffi- 
culty of swallowing. The bowels usually become obstinately 
c°nstipated, and the urine scanty or entirely suppressed. 
In a case cited by Orfila (Toxicologie, 1852, i, 195), in 
which a man who had administered to him by mistake about 
°ac ounce and a half of hydrochloric acid, there was extreme 
station, with a hot and dry skin, small and hard pulse, fiery- 
led tongue, blackness of the lips, hiccough, repeated efforts to 
°niit, and intense pain in the stomach. These symptoms were 
. loWed by vomiting of yellow matters, cold and clammy skin, 
pleased pain, extremely frequent pulse, and continuous delir- 
!Unb and death within about twenty hours after the poison had 
ee:a taken. 
In a singular case quoted by Dr. Christison (On Poisons, 
P* 148), a man, with suicidal intent, swallowed a quantity of 
acid, and exhibited no signs of uneasiness for some time 
ciwards; he then, however, suddenly became faint and fell 
AVri’ In about three hours after the acid had been taken, 
llagnesia and milk were administered; but without relief. He 
cied intense thirst, complained of excessive pain in the 
°at and stomach, and died in about fifteen hours. 
eri°d when Fatal.—Most of the recorded cases of poisoning 
•I A drochloric acid were followed by death. The most rapidly 140 
HYDROCHLORIC ACID. 
fatal case yet recorded, is, perhaps, that mentioned by Dr. 
Christison, in which two ounces of an equal mixture of strong 
hydrochloric acid and tincture of steel (muriated tincture of 
iron?), caused death in five hours and a half. Vomiting occurred 
soon after the mixture was taken, but subsequently ceased. 
Although the patient retained her consciousness until the time 
of death, she made no complaint either of heat or pain any 
where, or of thirst; but the pulse was imperceptible, and the 
muscles of the extremities contracted. In three other instances, 
two of which have already been cited, death took place in 
fifteen, eighteen, and about twenty hours, respectively. But 
Dr. Beck cites a case in which a dose of two ounces did not 
prove fatal until after a period of eight days (Med. Jur., ii, 495). 
And two instances are recorded in which death did not occur 
until eight iveeks had elapsed (Orfila, Toxicol., i, 221; and Taylor 
on Poisons, p. 291). 
Fatal Quantity.—ln a case reported by Dr. Budd, half a 
fluid ounce of the acid, taken with suicidal intent, proved fatal 
in eighteen hours to a woman aged sixty-three years. (Wharton 
and Stille’s Med. Jur,, p. 494.) This seems to be the smallest 
fatal dose yet recorded. In this case the following symptoms 
were observed: vomiting, collapse, whitening and abrasion of 
the lips, mouth, and fauces; also, swelling of the throat and 
inability to swallow, with stridulous breathing and thick inar- 
ticulate voice, and intense epigastric pain. Death, without loss 
of consciousness until near the last, took place by exhaustion. 
On the other hand, Dr. Toothaker reports a case in which 
a man recovered after having taken, by mistake, one ounce of 
official muriatic acid. It was immediately succeeded by violent 
burning of the mouth and fauces, a sense of suffocation, and 
spasms. After the administration of olive oil, followed by a 
mixture of milk and calcined magnesia, copious vomiting ensued. 
The strength of the patient became greatly reduced, and the 
extremities so cold as to require the application of sinapisms. 
The next day there was pain and costiveness, but these were 
relieved by a dose of castor oil. After this, the patient very 
gradually recovered. (Boston Med. and Surg. Journal, vol. 
xv, p. 270.) CHEMICAL PROPERTIES. 
141 
Treatment.—The proper chemical antidote is either chalk, 
0r calcined magnesia, or a dilute solution of an alkaline 
carbonate. If neither of these substances be at hand, milk, 
of egg, oil, or demulcents of any kind, should be freely 
administered. In every respect, the treatment is the same as 
ln sulphuric acid poisoning (ante p. 101). 
Post-mortem Appearances.—ln acute cases, the mucous 
Membrane of the mouth, throat, and oesophagus, is usually more 
°r less softened, and of a whitish or brownish color. The lining 
Membrane of the stomach is generally highly inflamed, softened, 
and readily separated. In the case cited above which proved 
fatal in five hours and a half, the lower portion of the oesoph- 
aSUS had the appearance of being charred. The mucous mem- 
brane of the stomach presented black elevated ridges, as if 
charred, while the intervening furrows were of a scarlet-red 
color | similar appearances were observed in the duodenum and 
Jejunum. In Dr. Budd’s case, the mucous membrane of the 
rri°uth, fauces, and larynx, was whitened and softened, the soft 
Palate and tonsils swollen, and a portion of the lining membrane 
°f the larynx was entirely removed. In this case, the local 
actiou of the poison was chiefly confined to the parts just 
Mentioned. 
In the case cited by Orfila which did not prove fatal until 
aftcr a period of eight weeks, the lining membrane of the throat 
oesophagus was thickened, and in a state of suppuration. 
16 stomach was entirely disorganised, softened, and presented 
Several round perforations, having thickened and inflamed 
edges; the pyloric orifice was thickened and contracted. In 
e small intestines, the mucous membrane throughout its ex- 
t Was thickened, injected in patches and of an arborescent 
aPpearancej the large intestines were healthy, and contained a 
brownish, fetid liquid. 
Chemical Properties. 
is Chemical Nature.—Anhydrous hydrochloric acid 
a Saseous compound of hydrogen and chlorine (HCI). It is 
c°lorless, powerfully suffocating gas, having a density of 1-26; 142 
HYDROCHLORIC ACID. 
when it conies in contact with the air, it produces white fumes, 
due to its strong affinity for water. 
Hydrochloric, or muriatic acid of the shops, is an aqueous 
solution of the gaseous compound, of which, according to Davy, 
water at a temperature of 40°, will absorb 480 times its volume, 
increasing both in volume and density. Such a solution has a 
specific gravity of I*2l, and contains nearly 43 per cent, of an- 
hydrous acid. The solution is colorless, has a highly irritating 
odor, and yields dense white fumes when a rod moistened with 
ammonia is presented to it. If the solution be heated, a portion 
of the anhydrous acid is readily expelled in the form of vapor. 
The following table, according to E. Davy, exhibits the per 
cent, by weight, of the anhydrous acid in pure aqueous solutions 
of different specific gravities:— 
STRENGTH OF AQUEOUS SOLUTIONS OF HYDROCHLORIC 
ACID; 
SP. GR. 
PER CENT. 
SP. GR. 
PER CENT. 
SP. GR. 
PER CENT. 
1-21 
4243 
1-14 
28-28 
1-07 
14-14 
1-20 
40-80 
1-13 
26-26 
1-06 
12-12 
1-19 
38-38 
1-12 
24-24 
1-05 
10-10 
1-18 
36-36 
1-11 
22-22 
1-04 
8-08 
1.17 
34-34 
1-10 
20-20 
1-03 
6-06 
1-16 
32-32 
1-09 
18-18 
1-02 
4-04 
1-15 
30-30 
1-08 
16-16 
1-01 
2-02 
Hydrochloric acid as found in the shops, has usually a 
density of about 1-15; and a more or less yellow color, due to 
the presence of free chlorine gas or chloride of iron, or both. 
It is also liable to be contaminated with sulphuric and sulphur- 
ous acids, arsenic, nitric acid and some of the lower oxides of 
nitrogen, and common salt; occasionally, other impurities are 
jiresent. 
Liquid hydrochloric acid is readily decomposed by iron, 
zinc, and the stronger electro-positive metals, with the forma- 
tion of a chloride of the metal and the evolution of hydrogen 
gas. But it is unacted upon by metallic copper, even at the 
boiling temperature; in this respect it differs from nitric and 
sulphuric acids. It is readily decomposed by the basic metallic 
oxides and their carbonates, with the formation of a chloride SPECIAL CHEMICAL PROPERTIES. 
143 
and water, and, in the case of a carbonate, the evolution of 
carbonic acid. 
The salts resulting from this acid, or chlorides as they are 
termed, are mostly colorless, and with the exceptions of the 
chlorides of silver and lead and the sub-chloride of mercury, 
are freely soluble in water. When heated with diluted sulphuric 
acid, the soluble chlorides, together with water, are readily de- 
composed, giving rise to a sulphate and evolving hydrochloric 
acid gas, thus: NaCl + HO, S03 = NaO, S03 + HCI. 
Special Chemical Properties.—When hydrochloric acid is 
heated with black oxide of manganese, both compounds undergo 
decomposition with the formation of the chloride of the metal 
and the evolution of free chlorine, thus: Mn02 + 2 HCI =2 HO -f- 
MnCl + Cl. The presence of the eliminated chlorine may be 
recognised by its pecidiar odor, its bleaching properties, and, if 
in too minute quantity, its greenish-yellow color. Its bleach- 
lxig property is readily determined by exposing to it a slip of 
moistened litmus-paper, or a slip of paper moistened with a 
Solution of indigo; if a slip of starch-paper be moistened with 
a solution of iodide of potassium and exposed to the gas, it im- 
mediately acquires an intense blue color, which after a time, 
nnder continued action of the gas, is partially or wholly 
discharged. If the evolved gas be brought in contact with a 
IOP °f a solution of nitrate of silver, or be conducted into a 
Ration of this salt, it produces, in the first instance a white 
j ln_ and in the second a white precipitate, of chloride of silver, 
a\mg the properties to be presently described. 
When a soluble chloride is mixed with black oxide of man- 
ganese, and heated with sulphuric acid, previously diluted with 
°ut an equal volume of water, the whole of the chlorine is 
minated in its free state. The reactions in this case, taking 
o loride of sodium as the type, are as follows: NaCl+Mn02 + 
S03 + NaO, S03 + Cl. The presence of the evolved 
_ °une may be determined by the methods just indicated. If 
lB decomposition be conducted in a thin watch-glass covered 
} an inverted glass containing slips of the moistened test 
Papers, the fractional part of a grain of the salt will yield sat- 
mfactory results. 144 
HYDROCHLORIC ACID. 
Since tlie compounds resulting from hydrochloric acid are, 
with very few exceptions, freely soluble in water, there are hut 
few reagents that precipitate it from solution. In the following 
investigations in regard to the behavior of solutions of hydro- 
chloric acid, pure aqueous solutions of the free acid were chiefly 
employed. The fractions indicate the amount of the anhydrous 
acid in solution in one grain of liquid, and the results, the 
behavior of one gram of the solution. 
1. Nitrate of Silver. 
Nitrate of silver throws down from solutions of hydrochloric 
acid, of chlorides, and of free chlorine, a white amorphous pre-. 
cipitate of chloride of silver (Ag Cl), which is readily soluble 
in ammonia, but insoluble in nitric and sulphuric acids; it is 
also readily soluble in cyanide of potassium, but insoluble in 
the fixed caustic alkalies. When exposed to light, chloride ot 
silver soon acquires a purple color; on the application of heat, 
it readily fuses without decomposition, to a yellowish liquid, 
which on cooling solidifies to a hard, compact, nearly colorless 
mass. 
1. yoo" grain of anhydrous hydrochloric acid, in one grain of 
water, yields a very copious, curdy precipitate. 
2. xtwol} grain: much the same results as 1. 
3. totWo grain, yields a very good flocculent precipitate. The 
solution strongly reddens litmus-paper. 
4. s-oTinro grain: a very satisfactory deposit. The solution, 
5. xooTo'oo grain: in a few moments, a distinct cloudiness, which 
after a time, slightly reddens litmus-paper. 
soon becomes well-marked. 
6. T(ToVoU grain, yields after a little time, a slight opalescence. 
Nitrate of silver also produces in solutions of hydrocyanic acid, 
even when strongly acidulated, a white precipitate of cyanide 
of silver, which, like the corresponding chlorine compound, is 
soluble in ammonia (although less freely), and insoluble in nitric 
acid. But the cyanide of' silver, when dried and heated in a 
reduction tube, readily undergoes decomposition, with the evolu- 
tion of an inflammable gas, in which respects it differs from the SPECIAL CHEMICAL PROPERTIES. 
145 
cMorine salt. A more ready method of distinguishing between 
these acids, is to treat a portion of the suspected solution with 
the mercury reagent described below. 
In neutral solutions, nitrate of silver produces precipitates 
Wlth several other acids or elements. All of these precipitates, 
however, except that from hydrocyanic acid, unlike the chloride 
°f silver, are readily soluble in nitric acid, at least in its con- 
centrated state. So again, the reagent is readily decomposed, 
Wlth the production of a white precipitate, by a great variety 
cf organic substances; these precipitates, however, like those 
Just mentioned, are soluble in nitric acid. 
The chlorine may be recovered in a soluble form from the 
chloride of silver, by fusing the latter with a mixture of car- 
bonate of soda and potash, when the chlorine will be transformed 
mto an alkaline chloride, readily soluble in water. 
2. Nitrate of Suboxide of Mercury. 
This reagent produces in solutions of free hydrochloric acid 
und of chlorides, a white amorphous precipitate of subchloride 
°f mercury, or calomel (Hg2CI), which is insoluble in concen- 
trated nitric acid. The precipitate is readily decomposed by 
*he caustic alkalies, with the formation of a black compound 
°f mercury. 
Tro grain of the anhydrous acid, yields a very copious 
precipitate. 
’ Trloo grain, yields much the same results as 1. 
* grain: a quite good precipitate. 
sTJTcToo grain: a very satisfactory deposit. 
* TiroToo-o grain, yields after a little time, a very distinct 
turbidity. 
. titrate of suboxide of mercury, also produces white pre- 
Clpitates in solutions of several other substances. When the 
leagent is added to a solution of free hydrocyanic acid, as well 
8 °f a cyanide, one half of the mercury is thrown down in its 
y divided state as a dark grey precipitate, while the other 
Potion remains in solution in the form of cyanide of mercury. 
18 reaction, as intimated above, readily serves to distinguish 
10 146 
HYDROCHLORIC ACID. 
between hydrochloric and hydrocyanic acids, as well as between 
their salts. 
3, Acetate of Lead. 
Acetate of lead produces in solutions of hydrochloric acid 
and of its salts, when not too dilute, a white precipitate of 
chloride of lead (Pb Cl), which is somewhat less soluble in 
diluted nitric acid than in pure water. The precipitate is 
rather freely soluble in boiling water, from which on cooling 
it separates in its crystalline state. 
1. y-jCj- grain of hydrochloric acid, when treated with the re- 
agent, crystals immediately begin to separate, and in a 
little time there is a quite good crystalline deposit, Plate 
111, fig. 1. 
2. 2iro grain: on agitating the mixture with a glass rod, it 
yields after a few minutes, some few crystals of chloride 
of lead, which are chiefly confined to the margin of the 
drop. 
Acetate of lead also produces white precipitate—usually, 
however, amorphous—in solutions of several other acids, espe- 
cially if the mixture be neutral. Moreover, the reagent is 
readily decomposed by various organic substances, with the 
production of a white amorphous precipitate. 
Separation from Organic Mixtures 
Suspected Solutions.—lf the solution has a strong acid reac- 
tion, and is tolerably free from organic matter, a small portion 
of the liquid may be treated with a few drops of a strong 
solution of nitrate of silver. If this produces a white precip- 
itate, which when washed in diluted nitric acid is insoluble 
in the stronger acid, there is little doubt of the presence of 
chlorine. If this examination indicates the presence of chlorine, 
it then becomes necessary, even should the solution have a 
strong acid reaction, to determine whether it existed in the 
form of free hydrochloric acid or as a chloride. For this 
purpose, a portion of the solution is evaporated to dryness, and 
gently ignited, when if it leaves no saline residue, it is quite SEPARATION FROM ORGANIC MIXTURES. 
147 
certain that the acid was uncomhined. Should, however, it 
leave such a residue, this is dissolved in water and tested for 
chlorine. If this element be absent, it is most probable that 
the acid was free; however, a mixture of a chloride, as com- 
flien salt, and excess of sulphuric acid, would, as heretofore 
pointed out in the consideration of the recovery of sulphuric 
acid, yield upon evaporation a residue entirely free from chlo- 
rine. Whether these conditions really existed, could be readily 
determined by treating a portion of the suspected solution with 
chloride of barium, when if it failed to yield a precipitate or 
gave one readily soluble in nitric acid, the absence of sulphuric 
acid would be fully established. 
Should the suspected liquid on evaporation leave a residue 
containing a chloride, it then becomes necessary to ascertain 
yhether the whole of the hydrochloric acid may have existed 
ln that form. To effect this, a given portion of the liquid is 
Neutralised by pure carbonate of soda, evaporated to dryness, 
incinerated residue dissolved in water containing a little 
Nitric acid, the chlorine precipitated by nitrate of silver, and 
the precipitate collected, washed, dried, and weighed: an equal 
yolume of the liquid, without the addition of carbonate of soda, 
18 then evaporated to dryness, the residue incinerated, and the 
chlorine precipitated, as in the previous operation, by nitrate 
°f silver. If the weight of the precipitate obtained by the 
°i'Nier of these methods exceed that obtained by the latter, 
then a portion of the acid existed in its free state: the exact 
Tiantity of the acid thus present, may of course, be readily 
educed from the difference thus observed. 
For the separation of free hydrochloric acid from complex 
fixtures containing organic solids, it has been proposed to heat 
le Niixture, after the addition of water if necessary, to near 
le boiling temperature, then filter, and distill the filtrate at a 
gentle heat to the consistency of a thin syrup, the distillate 
. GlNg collected in a proper receiver. The liquid thus collected 
18 then examined by the silver test. As, however, hydrochloric 
a°id strongly adheres to organic matter, none of the acid, unless 
1 resont in comparatively large quantity, may pass over into the 
eceiver. Under these circumstances, Orfila recommended to 148 
HYDROCHLORIC ACID. 
treat the residue in the retort with a solution of tannin, filter, 
and then distill the filtrate, as before, to near dryness. From 
what has already been stated, it is obvious that if the mixture 
thus distilled contained a chloride and free sulphuric acid, it 
would give rise to hydrochloric acid, which would appear in the 
distillate. This objection could of course be answered by test- 
ing a portion of the residue with chloride of barium. 
Contents of the Stomach.—Any solids present are cut into 
small pieces and the mass, after dilution with distilled water if 
necessary, kept at near the boiling temperature for half an hour 
or longer, then strained, the strained liquid filtered, and then 
submitted to the process of distillation described above. If, 
however, an alkaline or earthy antidote has been administered 
and the mixture has a neutral reaction, then a given portion of 
the filtered liquid is evaporated to dryness, the incinerated 
residue dissolved in water, and any chlorine present estimated 
in the form of chloride of silver. In these investigations, it 
must be borne in mind that the gastric juice contains not only 
alkaline chlorides, but also free hydrochloric acid; and more- 
over, that common salt, or chloride of sodium, is almost uni- 
versally present, at least in minute quantity, in articles of food. 
The gastric juice, however, according to most observers, nor- 
mally contains only the merest trace of the free acid; but the 
chlorides exist in very notable quantity. 
From the facts just stated, it is obvious that the detection of 
a mere trace of free hydrochloric acid or of a chloride in minute 
quantity, would not in itself be any evidence of poisoning by 
this acid. If it be shown that the base of the chloride present 
corresponds to that of the antidote alleged to have been admin- 
istered, this fact may materially assist in forming an opinion as 
to the true nature of the case. When the whole of the acid 
has been converted into a chloride, by the administration of an 
antidote, it may be recovered in its free state by first evapora- 
ting the mixture to dryness, then distilling the incinerated resi- 
due with strong sulphuric acid, and collecting the evolved acid 
in a small quantity of water contained in a well-cooled receiver. 
From organic fabrics. Stains produced by this acid on 
articles of clothing, and like substances, may be examined by QUANTITATIVE ANALYSIS. 
149 
gently boiling the stained portion with pure water for some 
minutes, and testing the filtered liquid in regard to its reaction 
uP°n litmus-paper, and with a solution of nitrate of silver. 
When chlorine is thus discovered, it should be determined, in 
the manner already pointed out, whether it exists in the form of 
the free acid or simply as a chloride. As hydrochloric acid is 
volatile, it sooner or later entirely disappears from stains of 
this kind. 
Quantitative Analysis.—The quantity of free hydrochloric 
acid, or its equivalent in the form of a soluble chloride, is most 
readily determined by precipitating it as chloride of silver. 
The solution is treated with a solution of nitrate of silver as 
long as it yields a precipitate, and the mixture gently heated 
Until the whole of the precipitate has deposited; the precipitate 
18 then collected on a small filter, thoroughly washed, dried, and 
Weighed. Every one hundred parts, by weight, of chloride of 
silver thus obtained, correspond to 25‘43 parts of anhydrous 
hydrochloric acid, or about 81 parts of liquid acid of specific 
gravity 1*15; one fluid drachm of the latter acid weighs about 
sixty-five and a half grains. 150 
OXALIC ACID. 
CHAPTER 111. 
OXALIC ACID, HYDROCYANIC ACID, PHOSPHORUS. 
Section I.—Oxalic Acid. 
History.—Oxalic acid, in its crystalline state, is an organic 
compound of the elements carbon and oxygen with water. It 
is found in the common rhubarb-plant, wood-sorrel, and several 
other plants, and is occasionally met with in the human urine, 
only, however, as an abnormal product. For commercial pur- 
poses, it is usually obtained by the action of nitric acid upon 
starch or sugar. In its uncombined state, it is a white crystal- 
line solid, having an intensely acid taste. From its close resem- 
blance to sulphate of magnesia, or Epsom salt, it has on several 
occasions been fatally mistaken for that substance. Either alone, 
or in combination in a soluble form, it is a powerful poison, and 
has in several instances been administered as such; but it has 
much more frequently been taken for the purpose of self- 
destruction. 
Symptoms.—The symptoms produced by oxalic acid, depend 
not only on the quantity taken, but also, somewhat, on the de- 
gree of concentration under which it exists. When swallowed 
in large quantity and in a concentrated state, it produces an 
immediate burning pain in the mouth and throat, succeeded by 
vomiting and intense pain in the stomach; and as the case 
advances, great muscular prostration, with hurried respiration, 
pale and anxious countenance, cold and clammy skin, small and 
feeble pulse, and in some instances, delirium and convulsions. 
The vomited matters have not unfrequently contained blood. 
When the dose is not large or is much diluted, nothing more 
than a strongly acid taste may be experienced in the mouth 
and throat, and the pain in the stomach, as well as the vomit- 
ing, may be much delayed. Although early and continuous PHYSIOLOGICAL EFFECTS. 
151 
vomiting is a common symptom, yet it has in some cases been 
entirely absent. In a case quoted by Dr. Christison, a man 
swallowed half an ounce of the poison, dissolved in ten parts of 
Water, without experiencing any pain in the abdomen for six 
hours, and there was no vomiting for seven hours, except when 
emetics were administered. In most of the instances in which 
no vomiting occurred, the dose was either small or greatly 
diluted ; but this symptom has been absent, when the poison 
vras taken in large quantity, and in a concentrated state. 
In a protracted case reported by Dr. C. T. Jackson (Boston 
and Surg. Journal, vol. xxx, p. 17), the following symp- 
toms were observed. A man, aged thirty years, took in solution 
about one ounce of crystallised oxalic acid, mistaking it for 
Epsom salt. He immediately perceived, by the strong acid 
taste and burning sensation in the throat, that he had made a 
mistake, and he drank a large quantity of warm water to excite 
omiting, which produced the desired effect. He also took, by 
the advice of a physician, ipecacuanha and antimony in emetic 
doses, and castor oil. The matter first vomited, was of a dark 
chocolate color. In twelve hours after the occurrence, the 
patient was in a state of complete prostration: face, lips, throat, 
aild tongue, swollen and livid; pulse almost extinct, fluttering, 
and irregular ; heart, in a continual fluttering palpitation ; great 
Jactitation and distress; with incessant vomiting. The matter 
vomited, was a thick, grumous, and jelly-like fluid, of a yellow 
color, mixed with white flocculi. He complained of no pain at 
le epigastrium, or over the bowels, on pressure. Carbonate of 
116 "was now administered, but rejected. On the second day, 
m face was tumid, and of a livid color; tongue swollen and 
..5 pulse 130; and the urine entirely suppressed. The vom- 
lting continued for two or three days, with great distress and 
anxiety; the tongue became covered with a brown coating, the 
*P of the organ being red and dry; and there was great thirst, 
no pain. On the sixth day, his mind began to wander, and 
Pctechise appeared on the face, chest, and other parts of the 
Y? which appeared as if sprinkled with blood. He con- 
md to fail, and died on the tenth day after the poison had 
oen taken. In several of the reported cases, there was great 152 
OXALIC ACID. 
irritability of the boAvels, with frequent purging, and the dis- 
charged matters in some instances contained blood. 
Period ivhen fatal. Much the larger proportion of the 
recorded cases of poisoning by oxalic acid proved fatal; and 
among these, death in most instances, perhaps, occurred in less 
than an hour after the poison had been taken. In a case quoted 
by Dr. Taylor, an unknown quantity of the poison caused death 
in about three minutes (On Poisons, p. 312). And Dr. Christi- 
son refers to two cases which proved fatal in about ten minutes; 
and in another, death ensued in from fifteen to twenty minutes. 
In a case mentioned by Dr. Pereira, death occurred in twenty 
minutes. Death also occurred within a similar period, in an 
instance in which the patient vomited almost immediately after 
the poison had been taken. 
The fatal period has however been delayed for many hours, 
and even days. Two instances are reported in which death did 
not occur until thirteen hours had elapsed; and another, in 
which it was delayed until the fifth day. In Dr. Jackson’s case, 
already mentioned, life was prolonged until the tenth day. The 
most protracted case yet recorded, is, perhaps, that mentioned 
by Dr. Beck (Med. Jur., ii, p. 499), in which a woman died 
from the secondary effects of the poison, after a period of some 
months. 
Fatal Quantity.—The effects of given quantities of oxalic 
acid, like those of most other poisons, have been far from uni- 
form. In one of the cases just referred to, that proved fatal in 
thirteen hours, half an ounce of the poison, largely diluted with 
water, had been taken. Dr. Taylor quotes a case in which a 
boy, aged sixteen years, ate about one drachm of the solid acid, 
and it proved fatal within nine hours; and another, in which a 
woman, aged twenty-eight years, swallowed three drachms of 
the crystallised acid and was found dead in one hour afterwards. 
These are the smallest fatal doses yet reported. Serious symp- 
toms, however, have followed the taking of much smaller quan- 
tities of the poison. In a case reported by Dr. Babington, two 
scruples of the acid, taken in combination with carbonate of 
soda, caused severe symptoms, from which the patient did not 
entirely recover until some weeks afterwards. ANTIDOTES. 
153 
On the other hand, complete recovery has taken place after 
VeiT large quantities of oxalic acid had been 'taken. Not less 
than six instances of this kind are reported, in each of which 
half an ounce of the acid had been swallowed: in most of these, 
1 # 7 
However, early treatment was employed. A like result has also 
heen observed in several instances in which an ounce of the 
Poison had been taken. In a singular case quoted by Wharton 
aild Stilld (Med. Jur., p. 496), a woman dissolved two large 
tablespoonfuls of oxalic acid, by mistake for Epsom salt, in a 
sKiall quantity of water, and took it on an empty stomach. 
S°ine twenty minutes afterwards she vomited, at first the solu- 
tion she had taken, and then a dark-colored, bloody fluid, in 
which were numerous white flakes. Ipecacuanha and after- 
wards prepared chalk were administered, and in about an hour 
she was found quiet and nearly free from the intense burning 
pain in her stomach and throat. She subsequently vomited 
again, and matters similar to those vomited were discharged 
T* ° 
10111 the bowels by purging. Soon after this she entirely recov- 
er®d- If this case is correctly reported, the quantity of the 
poison taken, was about one ounce and a quarter. 
Treatment.—Powdered chalk, magnesia, or its carbonate, 
Sllspended in water or milk, or a solution of the bicarbonate 
magnesia, should be administered as speedily as possible. 
. er of these substances will completely neutralise oxalic acid, 
the production of an insoluble compound. After thus neu- 
a ising the poison, if there is not free vomiting, an emetic 
°uld be administered. Large draughts of warm water may 
e given to aid the vomiting. One or other of these chemical 
aatidotes has in several instances been employed with great 
Vantage. When however the symptoms have once fully man- 
s °d themselves, they usually terminate fatally in spite of any 
trGatment. 
If neither of these earthy compounds is at hand, an emetic 
be given, and its exhibition followed by large quantities 
tepid water. The stomach-pump may sometimes be em- 
} Gcl with advantage. As the alkaline carbonates form with 
in'3 So^ul)lg poisonous salts, they will not serve as antidotes 
t us kind of poisoning. 154 
OXALIC ACID. 
Post-mortem Appearances.—These are subject to consid- 
erable variation. In rapidly fatal cases, the mucous membrane 
of the mouth and throat is generally more or less disorganised, 
and of a white appearance. The lining membrane of the oesoph- 
agus is sometimes much softened, and easily detached, and the 
blood-vessels congested with dark blood. The stomach has been 
found much contracted in size, and its external coat highly 
inflamed. The contents of this organ are usually thick, highly 
acid, and of a dark color, due to the presence of altered blood. 
The mucous membrane is pale or of a brownish color, injected, 
softened, and sometimes corrugated. In a few instances, the 
coats of the stomach presented a dark or nearly black appear- 
ance ; and they have been so much softened, as to be lacerated 
by the slightest pressure. In a case mentioned by Dr. Christi- 
son, the coats of the stomach were perforated. The small intes- 
tines have in several instances shown signs of irritation; and 
the liver and spleen have been found in a highly congested 
state. In this connection, it is important to bear in mind, that 
oxalic acid, even when taken in large quantity, has in some 
few instances destroyed life, without leaving any well-marked 
morbid changes, or in fact any abnormal appearance whatever, 
in the dead body. 
In a case which proved fatal in thirteen hours, the lining 
membrane of the throat and oesophagus presented an appearance 
similar to that of having been scalded, and could be easily sep- 
arated. The stomach contained a pint of thick, dark-colored 
fluid; and its mucous coat was pulpy, in many points black, 
and in others highly inflamed; its outer coat was also inflamed. 
Similar appearances, but in a less degree, were observed both 
externally and internally in the small intestines. The lining 
membrane of the trachea was also very red. 
In the protracted case reported by Dr. Jackson, the stomach 
contained a yellow fluid, and was remarkably corrugated; its 
mucous membrane was much thickened, soft, of a bright-red 
color, and contained numerous small ulcers. The lining mem- 
brane of the duodenum was also thickened, red, and studded 
with ulcers ; and that of the other portions of the small intes- 
tines congested. The large intestines, and other abdominal GENERAL CHEMICAL NATURE. 
155 
°rgans, were healthy. The heart was empty, except a small 
quantity of blood in the right side. In a case that proved fatal 
011 the twenty-third day, the lining membrane of the oesophagus 
and stomach was completely destroyed, and in places entirely 
Amoved; and the muscular coat, throughout the gullet and 
stomach, was much thickened, highly injected, and presented a 
dark appearance. 
Chemical Properties. 
General Chemical Nature.—Oxalic acid, when pure, forms 
colorless, transparent, odorless, four-sided crystalline prisms, 
contain two equivalents of water of crystallisation (HO, 
2G3, 2 Aq). It is the strongest of the vegetable acids. The 
Clystals are permanent, at ordinary temperatures; but when 
exposed to warm air, they part with their water of crystallisa- 
lolb and become opake. 
Oxalic acid is readily soluble in water at ordinary tempera- 
The extent to which the acid dissolves in this fluid has 
een variously stated, at from eight to fifteen times its weight 
0 the liquid. And in fact, either of these extremes will equally 
its solubility, unless some exact temperature be specified. 
s the mean result of three very closely accordant experiments, 
?e have found, that when excess of the pure crystallised acid 
|s hept in contact with pure water for five hours at a tempera- 
le of 60°, and the solution then filtered, the filtrate contains 
part of the acid in 9*5 parts of water. It is more freely 
Qlp.l "I 1 JL J 
. ehl warm water; and boiling water, it is said, will take 
P its own weight of the acid. Berzelius met with a sample of 
crystallised acid, which was so strongly impregnated with 
c acid, used in its preparation, that it required only two 
sof cold waf-er for solution. The pure acid is also freely 
s 1 1 6 111 a^c°hol, but insoluble in ether, and very sparingly 
®ln chloroform. When one grain of the pure crystallised 
bou sso^ in one hundred grains of water, and the solu- 
0£ Vl°lently agitated, for a few moments, with an equal volume 
0 P-e chloroform, this liquid extracts one-twentieth of a grain 
the acid. 156 
OXALIC ACID. 
The oxalates, or salts of this acid, are usually colorless and 
crystallisable, and for the most part, except those of the alkalies, 
insoluble in water. They are all decomposed by heat, the acid 
being resolved into carbonic acid and carbonic oxide. 
Special Chemical Properties.—Oxalic acid, when pure, 
is entirely dissipated at a temperature of about 350° F. In 
this respect, it differs from the sulphate of magnesia, which it 
closely resembles in appearance, and which leaves a fixed resi- 
due, even at high temperatures. When the acid is heated 
with strong sulphuric acid, it is resolved, without charring, into 
carbonic acid and carbonic oxide gases, which escape: tartaric 
and other organic acids when thus heated, are speedily charred. 
Solutions of the acid have a strongly acid taste and reaction, 
even when much diluted, and fail to be precipitated by the 
alkaline carbonates: a solution of Epsom salt has a bitter taste, 
is neutral in its reaction, and yields a white precipitate when 
treated with carbonate of soda. 
Pure aqueous solutions of oxalic acid, when slowly evapo- 
rated to dryness, leave the acid in the form of long crystalline 
prisms. When one grain of a 100 th solution of the acid is 
allowed to evaporate spontaneously, it leaves a comparatively 
large mass of crystals; when the solution contains the I,oooth 
part of a grain of the acid, it yields a quite good deposit, the 
crystals having the forms represented in Plate 111, fig. 2; the 
10,000 th part of a grain of the acid, under similar circum- 
stances, yields a very satisfactory deposit of small prisms and 
crosslets. 
In the following details in regard to the behavior of solu- 
tions of oxalic acid, the fractions indicate the fractional part 
of a grain of the pure crystallised acid in solution in one grain 
of water; and the results refer to the reactions of one grain of 
the solution. 
1. Nitrate of Silver. 
Solutions of free oxalic acid, and of its alkaline salts, yield 
with nitrate of silver, a white amorphous precipitate of oxalate 
of silver (AgO, C 2 03), which is slowly soluble in cold nitric acid? 
but readily soluble in the heated acid; it is also readily soluble SPECIAL CHEMICAL PROPERTIES. 
157 
111 solutions of ammonia, but insoluble in concentrated solutions 
acetic, tartaric, and oxalic acids. When the dried precipitate 
18 heated on platinum foil, it is decomposed and dissipated in 
slightly detonating puffs, being resolved into metallic silver and 
carbonic acid gas, thus: AgO, C 203= Ag + 2 C02. 
!• TFo grain of oxalic acid, in one grain of water, yields a 
very copious precipitate, which, in the mixture, requires 
about three drops of strong nitric acid for complete solution. 
When dried and heated, it is dissipated in the manner 
peculiar to this salt. 
“• TTTou grain, yields a rather copious precipitate, which, when 
dried and heated, is rapidly dissipated, but not in distinct 
puffs. 
Eo7<nro grain: a very good deposit. 
VoTrcTo grain, yields an immediate turbidity, and in a very 
short time, a quite satisfactory deposit. 
* rroroou grain: an immediate opalescence, and after a little 
time, a quite distinct deposit. 
* siToToTo grain, yields after some minutes, a distinct cloudiness. 
Fallacies.—Nitrate of silver is also readily decomposed with 
e production of a white precipitate, by a great variety of 
organic principles. And it also produces similar precipitates 
)Vlth several other acids, especially from neutral solutions. Thus 
occasions precipitates in neutral solutions of the carbonates, 
rt*'ates, phosphates, borates, citrates, chlorides, and cyanides, 
also, in most instances, with the free acids of these salts, 
these precipitates, however, except those from the chlorides, 
Cyanides, and their free acids, are soluble in acetic acid, in which 
fospect they differ from the oxalate of silver. So, also, the 
°nd.e and cyanide of silver—produced by the reagent from 
uions of chlorides and cyanides or their free acids—are 
t®a(% distinguished from the oxalic acid precipitate, in that 
gij6y are insoluble in nitric acid. Moreover, the chloride of 
tio er’ wben dried and heated, quietly fuses without decomposi- 
-5 and the cyanide, under similar circumstances, is decom- 
0£ e<a 'vvith the production of a fixed residue and the evolution 
c^ail gas. The precipitates produced from the 
°uates, tartrates, phosphates, borates, and citrates, when 158 
OXALIC ACID. 
dried and heated, also, unlike the oxalic acid deposit, leave a 
fixed residue. 
2. Sulphate of Lime. 
Sulphate of lime throws down from solutions of free oxalic 
acid, and of soluble oxalates, a white granular precipitate of 
oxalate of lime (CaO, C 203, 2 Aq), which is readily soluble in 
nitric and hydrochloric acids, but insoluble, or very nearly so, 
in acetic and other vegetable acids. As sulphate of lime is 
soluble only to a limited extent in water, its solution does not 
precipitate the whole of the oxalic acid from somewhat con- 
centrated solutions, unless the reagent solution be added in very 
large quantity. From such solutions, the whole of the acid 
may be readily precipitated, as oxalate of lime, by employing 
as the reagent, a solution of chloride of calcium or any of the 
other more soluble salts of lime. 
1. -jinr grain of free oxalic acid, yields with a drop of sulphate 
of lime solution, a very good, granular precipitate. A 
small drop of chloride of calcium solution produces a much 
more copious deposit, and which is in the form of small 
rectangular and notched plates, somewhat larger than the 
granules produced by the sulphate of lime. 
2. yttoo grain: an immediate cloudiness, and soon a quite good 
granular deposit. Chloride of calcium produces much the 
same reactions, but the precipitate consists chiefly of small 
plates and octahedral crystals, which vary in size from 
the B,oooth to the 7,000 th part of an inch, Plate 111, fig. B. 
The precipitate occasioned by the sulphate of lime is in 
the form of oval granules, which uniformly measure about 
the 10,000 th part of an inch in their longest diameter. 
3. roToiro grain: very soon, a perceptible cloudiness, and in a 
little time, a quite satisfactory deposit. 
4- sTToiro grain, yields after a little time, a quite distinct 
5. yoA»tto grain: after some minutes, a just perceptible opa- 
lescence. 
turbidity. 
Fallacies.—The reaction of this reagent is much less open to 
fallacy than that of nitrate of silver. From neutral solutions? SPECIAL CHEMICAL PROPERTIES. 
159 
however, sulphate of lime produces somewhat similar precipi- 
tates with the alkaline carbonates, phosphates, and borates; but 
s’om the last-mentioned, only when the solution is extremely con- 
centrated. Chloride of calcium also occasions white precipitates 
111 solutions of these salts, and in addition, in strong solutions of 
the alkaline citrates. But these precipitates are all readily 
soluble in acetic acid, and may thus be distinguished from the 
°xalate of lime. In this connection, it may be remarked that 
even concentrated solutions of free tartaric, citric, hydrochloric, 
hydrocyanic acids, and of their salts, fail to yield a pre- 
Clpitate with sulphate of lime. When, therefore, this reagent 
arid nitrate of silver, produce in a suspected solution, white 
Pl©cipitates, which in both instanced are insoluble in acetic 
acid, the results are not then open to any of the objections 
thus far mentioned under both these tests. 
_ Sulphate of lime also produces white precipitates, even in 
acid solutions of lead, baryta, and strontia, the sulphates of 
lese metals being thrown down. These precipitates, however, 
llldike the oxalate of lime, are insoluble in nitric and hydro- 
Chl°ric acids; they are also insoluble in acetic acid. Chloride 
calcium fails to precipitate solutions of baryta and strontia; 
, \ it causes in strong solutions of salts of lead, a white pre- 
ClPitate of chloride of lead, which slowly disappears on the 
ac dition of water. 
3. Chloride of Barium 
This reagent occasions in solutions of free oxalic acid, when 
too dilute, a white precipitate of oxalate of baryta, which 
b !cadily soluble in nitric and hydrochloric acid, but soluble 
difficulty in oxalic acid, and still less soluble in acetic acid. 
f *he oxalate of baryta is soluble in hydrochloric acid, even 
0£ Gn highly diluted, the reagent fails to precipitate the whole 
tfi le °Xa^c a°id from strong solutions of the free acid: since 
e hydrochloric acid set free by the decomposition, prevents the 
str iGr ac^on the reagent. The precipitate produced from 
0£ solutions of the acid, is usually in the form of groups 
oid, sharp-pointed crystalline needles. Neutral solutions of 160 
OXALIC ACID. 
the alkaline oxalates, yield with the reagent, a white amorph- 
ous precipitate, which soon becomes crystalline. This reaction 
is very much more delicate than when the acid exists in its 
free state. 
1. ywo grain of free oxalic acid, yields a quite good amorphous 
precipitate, which soon becomes granular, and in a little 
time crystalline, forming in most instances bold dumb- 
bells, and needles, Plate 111, fig. 4. If nitrate of baryta 
be employed as the reagent, the precipitate is usually in 
the form of small octahedral crystals. 
2. rroVo grain: after a few moments, the mixture becomes 
turbid, and in a little time, yields a good deposit of 
crystalline needles, and granules. 
3. stctoo grain: on stirring the mixture with a glass rod, it yields, 
after some time, a quite distinct deposit of granules and 
needles, which under the microscope are quite satisfactory. 
Fallacies.—Chloride of barium also produces in solutions of 
free sulphuric acid and of sulphates, a white precipitate of 
sulphate of baryta, which, however, differs from the oxalic acid 
precipitate, in regard to its form, and in being insoluble in 
strong nitric acid. In neutral solutions, the reagent also pro- 
duces white precipitates with the alkaline carbonates and several 
other salts; but all these deposits, except that from sulphates, 
are readily soluble in acetic acid. 
4. Nitrate of Strontia. 
Nitrate of strontia throws down from solutions of free oxalic 
acid a white precipitate of oxalate of strontia, which is very 
sparingly soluble in acetic and oxalic acids, but freely in nitric 
and hydrochloric acids. When the acid exists in the form of 
an alkaline oxalate, the delicacy of the reaction of this reagent 
is much increased. 
1. grain of the free acid, yields an immediate precipitate. 
and in a little time there is a very good deposit of octa- 
hedral crystals, plates, and small granules, Plate 111, fig. 5- 
2. rrcroo grain: in a little time, granules, prisms, and octahe- 
dral crystals. SPECIAL CHEMICAL PROPERTIES. 
161 
570V0 grain: in a little time, a distinct turbidity, and soon 
a rather good granular precipitate. 
To.Voi) grain: after a few minutes, a very distinct granular 
deposit. 
The objections to the reactions of this test, and the methods 
°f answering them, are the same as pointed out under the pre- 
ceding reagent. 
5. Acetate of Lead. 
Solutions of free oxalic acid, and of its soluble salts, yield 
Vlth this reagent, a white precipitate of oxalate of lead, which 
18 insoluble in acetic acid, but readily, soluble in nitric acid. 
TcTo grain of the free acid, yields a very copious precipitate, 
consisting of a mass of crystalline needles, Plate 111, tig. 6. 
Trowo grain: a copious precipitate, which immediately begins 
to crystallise. 
°* 570V0 grain: a good deposit, which soon becomes changed 
into stellate crystalline groups. 
TotWo grain, yields an immediate turbidity, and soon, stel- 
late crystals. 
a’oTsiro grain: very soon the mixture becomes opalescent, and 
in a little time, yields a satisfactory granular deposit. 
* ToTtTo'o grain: after some time, the mixture becomes slightly 
turbid. 
Fallacies.—Solutions of sulphuric acid and of sulphates, and 
stiong solutions of hydrochloric acid and of chlorides, also yield, 
treated by the reagent, white precipitates, which, how- 
-oVer? are insoluble in strong nitric acid. The reagent also 
pi educes white precipitates in neutral solutions of carbonates, 
P losphates, and several other salts, and also with a great vari- 
of organic substances. These deposits, however, at least 
01 the most part, are readily soluble in acetic acid. 
The oxalic acid may be recovered in its free state from the 
palate of lead, by suspending the latter in water and passing- 
trough the mixture a stream of sulphuretted hydrogen gas, as 
th‘b causes any blackening of the acid compound. By 
s means the oxalate of lead will be entirely decomposed, the 
lx°tal being precipitated as black sulphuret of lead, while the 
11 162 
OXALIC ACID. 
eliminated acid will remain in solution: PbO, C 203+ HS = PbS + 
HO, C 203. On now warming the mixture, to facilitate the de- 
position of the precipitate and expel the excess of gas added, 
filtering, and concentrating the filtrate at a moderate tempera- 
ture, the solution on cooling, if sufficiently concentrated, will 
deposit the acid in its crystalline form. 
The precipitate produced by the reagent from ten grains of 
a I,oooth solution of the free acid, when washed and suspended 
in ten grains of water, then treated with sulphuretted hydrogen, 
and the solution filtered, will furnish ten grains of liquid, which 
when examined in separate drops by all the preceding reagents 
will yield results not to be distinguished from those obtained 
from a I,oooth solution of the pure acid. In other words, the 
100 th part of a grain of the acid, when in solution in ten grains 
of water, may be precipitated by acetate of lead and the acid 
recovered in its free state, without any appreciable loss. The 
presence of organic matter may however considerably modify 
these results. 
6. Sulphate of Copper. 
Sulphate of copper produces in solutions of free oxalic acid, 
when not too dilute, a precipitate of oxalate of copper, having 
a very light bluish or greenish color, the tint depending on the 
strength of the solution. The precipitate is insoluble in acetic 
and oxalic acids, and dissolves to a very limited extent in even 
large excess of strong nitric acid; it is also insoluble in salts of 
ammonia, but dissolves readily in the pure alkali. 
1. ywo grain, yields a very copious flocculent precipitate. 
2. 5-oir grain: after a little time, a granular precipitate, which 
for the most part floats on the surface of the mixture ; the 
addition of a few drops of strong nitric acid does not cause 
the granules to disappear. 
3. rpnnr grain, yields after some time, a slight precipitate, which 
is dissolved on the addition of a drop of nitric acid. 
Fallacies.—Sulphate of copper also produces precipitates in 
neutral solutions of carbonates and of phosphates, and is also 
decomposed by certain kinds of organic matter with the produc- 
tion of a precipitate; but all these deposits are distinguished SEPARATION FROM ORGANIC MIXTURES. 
163 
from the oxalate of copper, in being readily soluble in nitric and 
hydrochloric acids. Solutions of free sulphuric, hydrochloric, 
tartaric, and citric acids, and of their salts, fail to be precip- 
itated by this reagent. 
Separation from Organic Mixtures 
Suspected Solutions.—When the solution contains much or- 
ganic matter, none of the preceding tests should be applied 
directly to the mixture, since under these conditions they are 
ail liable to produce a precipitate, even in the absence of oxalic 
acid. If the solution is strongly acid in its reaction and con- 
tains mechanically suspended solids, the mixture, properly diluted 
water if necessary, is digested at a moderate heat for fifteen 
nilnutes or longer, then filtered, the filtrate concentrated to a 
small volume, and if necessary, again filtered. 
As a preliminary step, a drop of the liquid may now be 
examined by the sulphate of copper test. If this produces a 
faintly bluish precipitate, insoluble or nearly so, in nitric or 
hydrochloric acid, there is little doubt of the presence of oxalic 
acid. If the precipitate thus produced is quite copious, and the 
Ucfmd under examination nearly colorless, then the remaining 
portion, after further concentration if thought best, is allowed to 
stand in a cool place for some hours, in order that the acid, in 
Part at least, may crystallise out. Any crystals thus obtained 
aie separated from the liquid, gently washed, then dissolved in 
a small quantity of pure water, and the solution tested in the 
01 dinary manner. On further concentrating the liquid from 
the crystals separated, a second crop may be obtained, 
th 1G ClAs^afr deposited in these operations are highly colored, 
ey should be re-dissolved in a little warm water and purified 
} recrystallisation before being tested. 
Should, however, the preliminary examination by the copper- 
* mdicate the presence of only a minute quantity of the acid, 
1 should the liquid be highly colored, then the remaining por- 
k 1 18 treated with slight excess of a solution of acetate of lead, 
dich the whole of the acid will be precipitated as oxalate of 
’ together with more or less organic matter. The precipitate 164 
OXALIC ACID. 
thus produced is collected on a filter and thoroughly washed, first 
with water acidulated with acetic acid, then with pure water. 
The moist precipitate is then diffused in an appropriate quantity 
of water and exposed to a stream of sulphuretted hydrogen gas 
until the whole of the white compound is thoroughly blackened, 
which may require an hour or longer. By this treatment, as 
already pointed out, any oxalate of lead present will be decom- 
posed, the acid entering into complete solution, and the metal 
being thrown down as sulphuret. The liquid is now separated 
from the precipitate by filtration, and kept at a moderate temper- 
ature until the odor of the sulphuretted gas has entirely disap- 
peared. It is then, if colorless, examined by the usual tests; if, 
however, it is highly colored, any oxalic acid present, is purified 
by crystallisation, in the manner above described, and then tested. 
The methods now described, would yield equal results, 
whether the acid existed in its uncombined state or in the 
form of a soluble oxalate, in the original liquid; and, therefore, 
do not serve to distinguish the state in which it was present. 
This, however, in medico-legal investigations, is rarely a matter 
of any importance. Should it be desired to determine this point, 
it may be approximatively done, by evaporating the prepared 
filtered liquid to dryness on a Avater-bath, and extracting the 
residue with very strong alcohol, which Avill dissolve the free 
acid if present as such, together with more or less foreign mat- 
ter, but only a trace of an alkaline oxalate, nearly the whole of 
the latter, unless present in only ATery minute quantity, remain- 
ing undissolved. The filtered alcoholic solution may now be 
evaporated to dryness on a water-bath, the residue digested with 
a small quantity of AArater, and the filtered liquid examined by 
either of the above-mentioned methods. The residue remaining 
undissolved by the alcohol, supposed to contain an alkaline oxa- 
late, is stirred with distilled water, the solution filtered, and then 
examined in the usual manner. 
Contents of the Stomach.—lf no chemical antidote has been 
administered, the contents of the stomach are .collected in a 
porcelain dish, tested in regard to their reaction, and the inside 
of the organ well Avashed with distilled Avater, the washingß 
being collected with the contents in the dish. The mixture, SEPARATION FROM ORGANIC MIXTURES. 
165 
after the addition of more water if necessary, is gently boiled 
for about half an hour, the cooled liquid strained, the solids on 
the strainer washed, and the united liquids filtered, then concen- 
trated and again filtered. The liquid may now, either be evap- 
orated to dryness, and the residue thoroughly extracted by strong 
alcohol, as described above for suspected solutions; or, it may 
be treated with slight excess of acetate of lead, the precipitate 
collected on a filter, washed with Avater acidulated with acetic 
acid, and any oxalate of lead present, subsequently decomposed 
by sulphuretted hydrogen gas. 
Instead of decomposing the oxalate of lead by sulphuretted 
hydrogen, it has been proposed to boil it for about half an hour 
ln an appropriate quantity of highly diluted sulphuric acid, by 
which it will be resolved into insoluble sulphate of lead and free 
oxalic acid. The liquid is then filtered, exactly neutralised by 
ammonia, and tested. Under these circumstances, the poison 
would exist as oxalate of ammonia, mixed Avith more or less 
sulphate of ammonia 5 the latter being formed from the excess 
°f sulphuric acid employed in the decomposition of the oxalate 
°f lead. The presence of this sulphate Avould not interfere with 
the reactions of the silver, sulphate of lime, and copper tests 5 
but it AArould yield with the barium, strontia, and lead reagents, 
white precipitates of the sulphates of these metals. Of these 
two methods of effecting the decomposition of the oxalate of 
ead, the former is much to be preferred. 
Should lime or magnesia have been administered as an 
autidote, the contents of the stomach, as Avell as any matters 
v°mited prior to death, may have a neutral reaction, and con- 
tam the poison in the form of an insoluble oxalate of one or 
°tlier of these bases. . Under these circumstances, the suspected 
Matters, especially all earthy solids, are collected in a dish, the 
ttiass made quite liquid by the addition of warm water, and 
thoroughly stirred; any organic solids present, are then washed 
111 the liquid and removed, and the remaining solids allowed to 
subside. When this has taken place, the liquid is 
ecanted, and the solids again washed Avith fresh water; they 
aie then diffused in a small quantity of pure water, a quantity 
pure carbonate of potash, somewhat exceeding that of the 166 
OXALIC ACID. 
earthy matter present, added, and the mixture boiled for about 
half an hour, the liquid evaporated during the operation being 
replaced by distilled water. The earthy oxalate will now be 
changed into an insoluble carbonate, while the oxalic acid will 
be in solution in the form of oxalate of potash. This solution, 
after filtration, is treated with decided excess of acetic acid, and 
the oxalic acid precipitated by a solution of acetate of lead. 
The precipitate thus produced, is collected, washed, and de- 
composed by sulphuretted hydrogen, in the manner already 
described. 
In case of the discovery of oxalic acid in vomited matters 
or the contents of the stomach, it might be objected, in a medico- 
legal investigation, that the acid was a normal constituent of 
certain vegetable structures, some of which are sometimes used 
as articles of food or administered medicinally. Thus, it is 
present in common sorrel, in culinary rhubarb, or pie-plant, and 
in the rhubarb of the shops. In these substances, however, it 
exists only in minute quantity, and in its combined state, either 
as oxalate of potash, or of lime. But should even only a minute 
quantity of the poison be discovered, the symptoms and other 
circumstances attending a case of poisoning by the acid, would 
rarely leave any doubt whatever as to its true nature. 
The Urine.—Oxalic acid, when taken either in its free or 
combined state into the stomach, soon appears in the urine, usu- 
ally in the form of octahedral crystals of oxalate of lime. The 
forms of these crystals readily distinguish them from all other 
urinary deposits; they are very similar in form to those of the 
oxalate of strontia, as figured in Plate 111, fig. 5. These crys- 
tals are often present in the urine at the time it is voided, but 
more frequently they do not separate until after some hours. 
For the purpose of making this examination, a small portion 
of the liquid is gently rotated in a watch-glass, until the sedi- 
ment collects at the bottom of the fluid, when the clear liquid 
is decanted ; the sediment is then washed in a similar manner 
with pure water, which in its turn is decanted, and the deposit 
examined by the microscope, under an amplification of about 
one hundred and twenty-five diameters. If none of the crystals 
are thus found, and the urine is fresh, some ounces of it may be QUANTITATIVE ANALYSIS. 
167 
allowed to stand quietly for several hours, the clear liquid de- 
canted, the sediment collected, washed, and examined as before. 
In this connection, it must be borne in mind that these crys- 
tals also thus occur, not only after the ingestion of certain articles 
°f food, but not unfrequently as the result of disease, and some- 
times even without any apparent cause. In fact, we have found 
tlie latter to be the case much more frequently than seems to be 
generally supposed. 
If it be desired to examine the urine for the presence of the 
free acid or of a soluble oxalate, the liquid, after the addition of 
a little acetic acid, may be evaporated to about one-fourth its 
volume, filtered if necessary, the filtrate treated with slight 
excess of acetate of lead, any precipitate thus produced decom- 
posed by sulphuretted hydrogen, and the filtered solution tested 
fry the usual reagents. 
Quantitative Analysis.—From pure solutions, oxalic acid 
may be estimated with considerable accuracy, in the form of 
oxalate of lead. The solution is treated with a little pure acetic 
acid, and a solution of acetate of lead added as long as a pre- 
Clpdate is produced; when the precipitate has completely sub- 
sided, it is collected on a filter of known weight, well washed 
Vuth pure water, dried at 212°, and weighed. Every one hund- 
red parts by weight of oxalate of lead thus obtained, corre- 
spond to 42-5 parts of crystallised oxalic acid. 
If the acid has been precipitated as oxalate of lime, this is 
thoroughly washed and dried, then exposed for a few minutes to 
a very dull-red heat. In this last operation, the oxalate wall be 
c‘°nverted into the carbonate of lime, every one hundred parts 
°I which correspond to one hundred and twenty-six parts of the 
crystallised acid. 
Section ll.—Hydrocyanic Acid. 
History and Composition. This substance, also known as 
Prussic acid, is a compound of the organic radical cyanogen 
V with the element hydrogen; and is usually represented by 168 
HYDROCYANIC ACID. 
the symbols HCy. In its pure state, it is a colorless, volatile 
liquid, having a peculiar odor, somewhat resembling that of 
bitter almonds. It is one of the most powerful and rapidly 
fatal poisons yet known; and many of its compounds are about 
equally poisonous. It may be obtained from various vegetable 
substances, as bitter almonds, the kernels of peaches, plums, 
apricots, and cherries, apple-pips, the flowers of the peach, and 
cherry-laurel, the bark of wild cherry, and the root of mountain 
ash. In many of these substances, however, the acid does not 
exist as such, but is the result of the decomposition to which 
they are subjected in its preparation. 
For ordinary purposes, hydrocyanic acid is usually obtained 
by distilling one of its salts with dilute sulphuric or hydrochloric 
acid. The acid of the shops, is a solution of the anhydrous 
acid, usually in water but sometimes in alcohol, and varies in 
strength from one to twenty-five per cent., according to the 
directions of the pharmacopoeia followed for its preparation. 
The United States Pharmacopoeia directs a strength of two per 
cent, of the pure acid ; and about the same proportion is directed 
by the British Colleges. The preparation known as Scheele’s 
acid, sometimes contains as much as five per cent, of real acid, 
but usually its strength falls very far short of this. Of several 
specimens of commercial acid examined, wTe found none to con- 
tain over 1-5 per cent, of anhydrous acid. And one of the 
samples, which had not before been opened after having left 
the hands of the manufacturer, did not contain even a trace of 
the acid. 
An aqueous solution of hydrocyanic acid, especially when 
exposed to the light, is prone to undergo spontaneous decom- 
position, with the formation of a brown deposit. This fact, in 
a measure at least, accounts for the difference observed in the 
strength of samples of the acid prepared after the same formula. 
This decomposition is much retarded by the presence of a 
minute quantity of a mineral acid, and for that pmqiose a trace 
of sulphuric acid is frequently added to the solution. An aque- 
ous solution of the acid, when pure, is perfectly colorless. In 
regard to its physiological effects, hydrocyanic acid belongs to 
the class of narcotic poisons. PHYSIOLOGICAL EFFECTS. 
169 
Symptoms.—These, both in respect to the time within which 
they appear and their character, depend upon the quantity of 
the acid taken. When taken in large quantity, it not unfre- 
Juently proves so rapidly fatal that no well-marked symptoms 
are observed. During the act of swallowing a large dose, the 
patient experiences a hot bitter taste, and is either immediately 
0r at most within a very few minutes, seized with complete loss 
°f muscular power and of consciousness. The respiration be- 
comes hurried, but often convulsive, and sometimes stertorous, 
the pulse imperceptible, the extremities cold, eyes prominent, 
the pupils dilated, and in many instances there are convulsions. 
In a case reported by Hufeland, in which a man sAvallowed 
ah°nt forty grains of the pure acid, in the form of an alcoholic 
solution, the patient immediately staggered a few steps, and 
then fell, 
apparently lifeless. When seen, almost instantly 
afterwards, by a physician, the pulse was imperceptible and 
the respiration entirely suspended. After a short interval, the 
man made a very forcible expiration; the extremities became 
c°hl, the eyes prominent, glistening, and insensible to light, and 
after a few convulsive expirations he died, within five minutes 
after the poison had been taken. 
It was formerly believed that when prussic acid was taken 
m rapidly fatal quantity, it always produced immediate insensi- 
.l 1v 5 but this is by no means always the case. When taken 
11 SUch quantity, the symptoms usually appear within a very 
n seconds, yet they have in several instances been delayed 
Sufficiently long for the patient to perform a series of voluntary 
acts. In a case re]ated by Dr, Sewell, a man swallowed seven 
. Cams of Scheele’s preparation of the acid, believed to con- 
cln about twenty-one grains of the anhydrous poison, after 
Uch he walked to the door of his room, unlocked it, called for 
assistance, then walked to a sofa, and stretched himself upon 
’ 111 a very little time after this, he was found in an insensible 
e, with stertorous breathing, and soon died. (Boston Med. 
Surg. Jour., xxxvii, p. 822.) 
following remarkable instance is quoted by Dr. Taylor 
11 Poisons, p. 646). A gentleman, aged forty-four years, 
owed, it was supposed, half an ounce of prussic acid 170 
HYDROCYANIC ACID. 
(strength not stated). He then walked ten paces to the top of 
a flight of stairs, descended the stairs, seventeen in number, 
and went to a druggist’s shop at forty-five paces’ distance, where 
he had previously bought the poison, entered the shop, and 
said, in his usual tone of voice, u I want some more of that 
prussic acid !” He then became insensible, and died in from 
five to ten minutes after taking the poison. 
When the dose is not sufficiently large to produce rapid 
insensibility, the first symptoms usually experienced are giddi- 
ness and a sense of great weakness; these effects are soon suc- 
ceeded by irritation in the throat, an increased flow of saliva, 
nausea, difficult and spasmodic respiration, and loss of voluntary 
motion; the pulse becomes small or imperceptible, the face livid, 
and the eyes glaring, the pupils generally being dilated. These 
cases are frequently attended with tetanic convulsions. 
The following case of recovery is quoted in detail by Dr. 
Stifle (Mat. Med., ii, p. 210). A French physician swallowed 
a dessert-spoonful of the medicinal acid, prepared by a chemist 
of Paris. He almost immediately afterwards fell down as if 
struck by lightning. Among the symptoms observed, were loss 
of consciousness and sensibility ; trismus; a constantly increas- 
ing dyspnoea ; cold extremities *, a noisy and rattling respiration; 
the characteristic odor of the acid upon the breath; distortion 
of the mouth; and a thready pulse. The face was swollen and 
dusky, and the pupils fixed and dilated. The trismus increased, 
and was soon accompanied by opisthotonos. At the end of an 
hour, a violent convulsion occurred, the whole trunk grew stiff? 
and the arms were twisted outwards. After two hours passed 
in this condition, the patient began to regain his consciousness, 
and in several hours afterwards, he was able to walk without 
assistance; but it was a fortnight before he entirely recovered. 
In a non-fatal case reported by Mr. W. H. Burnam, iu 
which a dose containing 2*4 grains of the anhydrous acid was 
taken by mistake, insensibility did not occur until two minutes 
after the poison had been swallowed. In the mean time, how- 
ever, the patient, having almost immediately discovered his 
mistake, took as an antidote half an ounce of aromatic spirits 
of ammonia, with a little water; and he told what had occurred : PHYSIOLOGICAL EFFECTS. 
171 
lie spoke hurriedly, and breathed deeply. A solution of sul- 
phate of iron was then administered. The respiration became 
deeper and slower. In four minutes after the poison was taken, 
the cold douche was freely employed, and an additional quan- 
tity of the iron solution with spirits of ammonia administered. 
Vomiting took place ,* and there was a slight convulsive shudder. 
In twenty minutes, the patient began to exhibit signs of return- 
mg consciousness; and in about fifteen minutes later, he was 
ahle to walk up stairs to bed. (Brit, and For. Med.-Chir. Rev., 
April, 1854.) In a case of recovery reported by Mr. Garson, 
m which a teaspoonful of the acid of unknown strength had 
heen taken, the symptoms were delayed for about fifteen minutes. 
Vhe individual was then found in a state of insensibility, and 
this continued for about four hours, although active remedies 
ivere employed. This is the most protracted case, in regard to 
the appearance of the symptoms, yet recorded. 
Several instances are reported, in which the inhalation of 
the diluted vapor of hydrocyanic acid caused most alarming 
symptoms ; and Dr. Christison quotes a case in which the liquid 
acid applied to a Avound in the hand, caused death in an hour 
afterwards. 
Hydrocyanic acid is also equally poisonous, with the pro- 
duction of similar symptoms, when taken into the system in the 
toriu of an alkaline cyanide. Since the introduction of cyanide 
°f potassium into the arts for photographic and other purposes, 
Numerous instances of poisoning by it have occurred. In a 
case of poisoning by this salt related by Dr. Schauenstein, of 
. leilna, occurring in a young man, death took place almost 
lllstantly; AArithout any striking symptoms. In another case, 
by the same Avriter, strong tetanic spasms came on 
Meetly after the poison had been taken, and death ensued in 
jGss than an hour. (Amer. Jour. Med. Sci., Jan., 1860, p. 279.) 
r| a case in which we Avere consulted in 1864, a man took, 
suicidal intent, about sixteen grains of the salt in solution; 
after SAvalloAving the poison, he Avalked about six 
steps, then fell insensible, and death ensued in about five minutes. 
Period when Fatal.—The fatal period, in poisoning by hy- 
°cyanic acid, is subject to considerable variation; yet it is 172 
HYDROCYANIC ACID. 
extremely limited when compared with that of the action of 
most other poisons. Several instances are recorded in which 
death took place in from five to ten minutes, and it has occurred 
in two minutes, and, perhaps, even within a shorter period. 
On the other hand, death has been delayed for nearly an hour, 
even when the quantity of poison taken was sufficiently great 
to produce almost immediate insensibility. In fatal cases, how- 
ever, life is rarely prolonged beyond half an hour: those who 
survive this period usually entirely recover. In an accident 
that occurred in one of the hospitals of Paris, by which seven 
epileptic patients were fatally poisoned, by equal quantities of 
hydrocyanic acid, the fatal period varied from fifteen to forty- 
five minutes. 
Fatal Quantity.—That similar quantities of prussic acid do 
not always produce the same result, is Avell illustrated in the 
instance of the Parisian epileptics just mentioned. The quan- 
tity of the poison taken by each of these patients is stated by 
most toxicological writers, on the authority of Orfila, to have 
been equivalent to about two-thirds of a grain of the anhydrous 
acid; but it appears from more recent statements (Braithwaite’s 
Retrospect, xii, p. 125), that the quantity actually taken by 
each, was equivalent to five grains and a half of the real acid. 
In a case reported by Mr. Hicks, a solution containing nine- 
tenths of a grain of the pure acid, proved fatal to a healthy 
woman, aged twenty-two years, in from fifteen to twenty min- 
utes. This seems to be the smallest fatal quantity yet recorded. 
Smaller quantities have, however, in several instances produced 
most dangerous symptoms. 
On the other hand, Mr. Bishop has related a case in which 
a man entirely recovered, after having taken a dose, in the 
form of forty minims of a solution, containing one grain and a 
third of anhydrous prussic acid (London Lancet, Sept., 1845; 
p. 315). In this case, the patient, according to his own ac- 
count, remained sensible for at least two minutes after taking 
the poison. When first seen by Mr. Bishop, about ten minutes 
after the occurrence, he was senseless, the countenance ghastly 
pale, face swollen and covered with perspiration, the respiration 
slow and labored, the eyes fixed and glazed, the pupils dilated; ANTIDOTES. 
173 
and the whole body in a rigid state. The treatment consisted 
m cold affusion, ammonia, emetics, and bleeding. So also, Dr. 
Christison has recently reported a case, in which a gentleman 
recovered after having taken a solution equivalent to between 
a grain and a half and two grains of the anhydrous acid. And 
in a case already cited, that reported by Mr. Burnam, recovery 
folloAved even after 2-4 grains of the pure acid, in solution, had 
been swallowed. In this case, however, as well as in that 
reported by Dr. Christison, active remedies were almost imme- 
diately employed. 
Treatment.—On account of the rapid action of hydrocy- 
anic acid, when taken in poisonous quantity, it rarely happens 
that treatment can be resorted to in time to be of much service. 
The remedies consist chiefly in the exhibition of stimulants; 
bat certain chemical antidotes have also been advised. 
The exhibition of the vapor of ammonia has been highly 
recommended, and several instances are reported in which its 
use was attended with great advantage. It has also been pro- 
posed to administer a solution of ammonia, diluted with water; 
but in this form, according to Orfila, it is of no service. Chlo- 
administered either in the form of vapor or taken inter- 
nally, has also been strongly advised. It may be used in the 
form of a weak solution of hypochlorite of lime or of the cor- 
responding salt of soda. The gas is readily obtained by acting 
°a either of these salts with diluted hydrochloric or acetic acid. 
From experiments on inferior animals, Orflla was led to believe 
Ibat chlorine was the most efficient antidote yet proposed. It 
need hardly be added, that great caution should be exercised 
111 its administration. 
Cold affusion, first recommended by Herbst, has perhaps on 
the whole been found the most efficient remedy hitherto em- 
ployed in the human subject. Its use should be accompanied 
by the exhibition of the vajjor of chlorine or ammonia. In 
Several instances of recovery, in which this treatment was em- 
ployed, it was aj)parently the means of averting death. Arti- 
fieial respiration was strongly insisted on by the late Dr. 
Fereira. He successfully employed it in experiments on ani- 
frials. Stimulating injections, as well as blood-letting, have also 174 
HYDROCYANIC ACID. 
been advised. The latter should be resorted to with great 
caution. 
As a chemical antidote, it has been suggested, by Messrs. 
Smith, of Edinburgh, to administer a solution of a mixture of 
the sulphates of the protoxide and sesquioxide of iron, quickly 
followed by a solution of carbonate of potash. A mixture of 
this kind produces with hydrocyanic acid, Prussian-blue, which 
is inert, being insoluble. In experiments on animals, this treat- 
ment was quite successful. Even if this antidote be at hand, 
it should never be relied on to the exclusion of stimulants and 
cold affusion. 
Post-mortem Appearances. These will, of course, de- 
pend somewdiat on the length of time the individual survived 
after taking the poison, and also the period that has elapsed 
since death. The face is usually pale, but often livid, the 
eyes glistening and staring, the lips blue, the jaws closed, 
and the extremities soon become rigid. The blood through- 
out the body is fluid, and generally of a dark or bluish color; 
the venous system turgid; the arteries nearly empty; the 
liver, and in some instances the lungs, much congested. The 
stomach, other than so far as cadaveric changes have taken 
place, is generally natural. It need hardly be observed, that 
neither of these appearances is peculiar to death from hydro- 
cyanic acid. 
One of the most striking characters in death from this 
poison, is the exhalation of the peculiar odor of the acid. This 
is sometimes emitted from the corpse, even before any dissec- 
tions are made, and, at least in recent cases, is nearly always 
exhaled when the stomach or thoracic cavity is opened; and it 
is often detected in the blood throughout the body. As, how- 
ever, hydrocyanic acid is very volatile, and also readily under- 
goes decomposition, it may in a little time, so far disappear 
from the body, that its odor can no longer be recognised. 
Moreover, the odor of the acid is liable to be masked by the 
presence of other odors. In a singular case related by Proh 
Casper, however, in which a woman had poisoned herself with 
a mixture of prussic acid and a variety of essential oils, and 
the body diffused a sweet odor, on opening the stomach such a CHEMICAL PROPERTIES. 
175 
powerful aroma of bitter almonds came forth as almost to stupefy 
every one present. In several reported instances in which this 
character was not observed in the stomach, a subsequent chem- 
ical analysis revealed the presence of very notable quantities 
°f the poison, in one case even so much as one grain of the 
anhydrous acid. In Dr. Sewell’s case, in which seven drachms 
°f the medicinal acid had been taken, he failed to detect the 
odor of the poison upon applying his nose to the mouth of the 
deceased, very soon after death. 
In the case reported by Hufeland, already mentioned, the 
hody exhaled the odor of the acid on the day following death. 
The countenance was pale and composed, the eyes glistening, 
spine and neck stiff, and the back livid. The blood was fluid, 
hluish in color, and throughout the body emitted a very strong 
°dor of the poison. The vessels of the brain, as well as the 
hver and lungs, were gorged with blood; the arteries empty, 
the veins distended, and the mucous membrane of the stomach 
aiid intestines reddened. 
In the cases of the seven Parisian epileptics, no odor of the 
poison was perceived in any part of the body, twenty-four 
hours after death. The lips, face, and head were bloated and 
°f a violet color; the back livid; frothy blood escaped from 
the mouth and nostrils; the eyes were closed, and the body 
rigid. The stomach was highly injected; the liver, spleen, and 
hidneys much gorged with black blood; the arteries empty, 
ar*d the veins turgid. In Mr. Hicks’ case, in which only nine- 
tenths of a grain of the acid was taken, the odor of the poison 
Was plainly perceived on opening the chest, and was also 
strongly emitted from the contents of the stomach, although the 
Examination was not made until ninety hours after death. 
Chemical Properties. 
GtEneral Chemical Nature.—Anhydrous hydrocyanic acid 
t-'j), is a colorless, very volatile, inflammable liquid, of a 
Peculiar odor. It readily mixes in all proportions with alcohol 
11(i Water. The pure acid has a specific gravity of 0*706, and 
°ils at 80° F., yielding a combustible vapor. 176 
HYDROCYANIC ACID. 
The medicinal acid is usually obtained by distilling, at a mod- 
erate heat, a solution of ferrocyanide of potassium (K2FeCy3)7 
with dilute sulphuric acid, and collecting the product in water, 
contained in a cooled receiver. The reaction is as follows: 
2 K2Fe Cy3+ 6 HO, S03= K Cy, 2FeCy + 3 KO, 2 S03+ 3HO + 
3 H Cy. The commercial acid, when pure, has a very feeble 
acid reaction, and a density varying with its strength; when it 
contains about three per cent, of the acid, its specific gravity 
is about 0998. 
When hydrocyanic acid is brought in contact with a solu- 
tion of an alkaline oxide, both the acid and alkaline compound 
undergo decomposition, with the formation of a salt, or cyanide, 
of the metal, and the production of water, thus KO +HCy = 
KCy + HO. These salts are freely soluble in water; they are 
readily decomposed by acids, with the evolution of free hydro- 
cyanic acid. When exposed to the air, either in their solid 
state or in solution, they slowly absorb carbonic acid, and thus 
become changed into carbonates, the eliminated prussic acid 
being dissipated in the form of vapor. The cyanides of the 
metals proper, unlike those of the alkalies, are for the most 
part insoluble in water; but many of them are freely soluble 
in a solution of an alkaline cyanide, with the formation of & 
double salt. 
Special Chemical Properties.—lt has been claimed by 
several toxicological writers, that the odor of hydrocyanic acid 
serves to detect the presence of smaller quantities of the poison 
than can be recognised by any of the chemical tests; but this 
is an error, even in regard to the vapor from perfectly pure 
solutions of the acid. Nevertheless, under certain conditions, 
extremely minute quantities of the acid may thus be recog- 
nised. We have found in repeated experiments, that when ten 
grains of a 50,000 th solution of the pure acid grain 
H €j) are enclosed for some time in a small test-tube, and the 
tube then opened, the peculiar odor of the poison is sufficiently 
marked to be described by persons entirely ignorant of the true 
nature of the solution. With a similar quantity of a 100,000 th 
solution, an odor is perceptible, but its peculiar character is 
lost. It need hardly be repeated, that the odor from even SILVER TEST. 
177 
strong solutions of the poison, may be entirely disguised by the 
presence of other odors. 
There are but few chemical tests to which we resort for the 
detection of hydrocyanic acid, but these are so characteristic 
and delicate in their reactions, as to leave nothing more to be 
desired in this respect. Moreover, they are equally applicable 
for the detection of the vapor of the poison. In the following 
eXainination of these tests, the fractions employed indicate the 
Quantity of anhydrous prussic acid in solution in one grain of 
pure water. The results, unless otherwise stated, refer to the 
behavior of one grain of the solution. 
1. Nitrate of Silver. 
Nitrate of silver throws down from solutions of free hydro- 
cyanic acid, and of soluble cyanides, a white amorphous pre- 
Clpitate of cyanide of silver (Ag Cy), which is insoluble in the 
dxed caustic alkalies, and only sparingly soluble in ammonia, 
but readily soluble in the alkaline cyanides. Cold nitric acid 
fidls to dissolve it, but it is soluble in the hot concentrated acid; 
hydrochloric acid decomposes it with the formation of chloride 
°f silver and the evolution of hydrocyanic acid. 
To'o' grain of hydrocyanic acid, in one grain of water, yields 
a very copious precipitate, which does not entirely disap- 
pear when the mixture is heated with several drops of 
strong nitric acid. 
TTVoij grain, yields a copious precipitate, which readily dis- 
solves on the addition of a drop of strong ammonia; but 
dissolves with difficulty, in the mixture, in several drops 
°f warm nitric acid. 
' iVToiro grain: a quite good flocculent precipitate. 
2Toro grain, yields no immediate precipitate, but in a very 
little time the mixture becomes turbid, and soon there is a 
w very satisfactory deposit. 
STTo'oo grain: after a little time, a very distinct opalescence, 
g an(i soon a very perceptible deposit. 
1 grain: in a few minutes, the mixture becomes very 
distinctly turbid. 
12 178 
HYDROCYANIC ACID. 
Fallacies.—Nitrate of silver also produces white precipitates 
in solutions of free hydrochloric acid, of chlorides, carbonates, 
phosphates, tartrates, and some other salts, and also with various 
kinds of organic matter. These precipitates, however, except 
that from chloi’ine, are readily soluble in strong nitric acid, in 
which they differ from the cyanide compound. The chloride 
of silver readily darkens when exposed to light, whereas the 
cyanide remains unchanged in color; again, the former salt is 
readily soluble in ammonia, whilst the latter is not, unless pres- 
ent only in very minute quantity. Tolerably strong solutions 
of iodides and bromides, and of their free acids, yield with 
nitrate of silver yellowish-white precipitates; from dilute solu- 
tions, however, these precipitates, in regard to color, might 
readily be mistaken for the cyanide compound, especially when 
they are obtained from organic mixtures: like the cyanide 
deposit, they are nearly insoluble, or dissolve with difficulty, m 
cold nitric acid. 
The cyanide of silver is readily distinguished from all other 
precipitates produced by this reagent, in that when thoroughly 
dried and heated in a narrow reduction-tube, it undergoes de- 
composition with the evolution of cyanogen gas, which, when 
ignited, burns with a rose-colored flame. If this decomposition 
be effected in a small tube, which after the introduction of the 
dried cyanide has been drawn out into a very narrow capillary 
neck, beginning something less than an inch above the cyanide 
compound, the 100 th part of a grain of the salt will yield sat- 
isfactory results. For the success of this experiment, it Is 
essential that the cyanide be thoroughly dried before being 
introduced into the tube. 
Vapor of Hydrocyanic Acid.—When the vapor of prussic 
acid is received on a drop of nitrate of silver solution, the latter 
becomes coated with a white film of cyanide of silver, which, 
especially from dilute solutions of the acid, is crystalline, and 
most abundant along the margin of the drop. In its behavior 
with reagents, this deposit has the properties already de- 
scribed. This test may be applied by placing a drop of the 
acid solution in a watch-glass, and covering the latter with 
a similar, inverted glass, containing a small drop of the silver SILVER TEST. 
179 
solution. By this method, one grain of the acid solution yields 
as follows: 
Tro grain of hydrocyanic acid, in one grain of water: an 
immediate cloudiness is observed in the silver solution, 
and in a very little time there is a quite copious white 
deposit. Under the microscope, the deposit has the ap- 
pearance of an amorphous mass, but if broken up, with 
the point of a needle, it will be found to consist of very 
small but distinct crystals. If the watch-glass containing 
the poison be first placed on the stage of the microscope 
and then covered by the glass containing the silver solu- 
tion, the formation of the crystals may, at least for a time, 
be observed. 
9 i . 
“• TToiro grain: an immediate cloudiness appears in the reagent 
solution, and soon there is a quite good, white film. If its 
formation be observed under the microscope, the crystals 
will be found to form more slowly and become somewhat 
larger than in 1. 
°* ToTFoi) grain: in a little time a cloudiness appears, and after 
a few minutes there is a quite good deposit, which con- 
sists principally of irregular crystals, varying from the 
IjOOOth to the 2,000 th part of an inch in length, of 
the forms illustrated in Plate IV, fig. 1. Usually, small 
granules, prisms, and needles form along the margin of 
the drop. 
4. ___ -) 1. 
ssroou grain: after a little time the margin of the silver solu- 
tion becomes white, and soon there is a good crystalline 
g deposit. 
s'oTo'oo grain: when a very small drop of the reagent solu- 
tion is employed, crystals appear in less than two minutes, 
g and before long there is a very satisfactory deposit. 
1 u'oTo'ro grain: after a few minutes crystals can be seen with 
the microscope, and after some minutes they are quite 
evident to the naked eye. The deposit is confined to the 
margin of the drop, and chiefly consists of granules, small 
prisms and needles, Plate IV, fig. 2. So far as the evi- 
dence of the presence of hydrocyanic acid is concerned, 
this quantity furnishes as unequivocal results as any larger 180 
HYDROCYANIC ACID. 
amount. The formation of the deposit is much facilitated 
by applying the warmth of the hand to the watch-glass 
It need hardly be observed that if the silver solution be- 
comes nearly dry from evaporation, crystals of nitrate of silver 
may separate; but these have a very different form from those 
of the cyanide, and moreover they immediately disappear on 
the addition of a very small drop of water, whilst the cyanide 
crystals are almost wholly insoluble in this liquid. 
containing the acid solution. 
The vapors of chlorine, bromine, and iodine, and of their 
hydrogen acids, also yield white or nearly white films with a 
solution of nitrate of silver. The deposits from all these sub- 
stances, however, are amorphous; whereas the cyanide com- 
pound is always crystalline, even when obtained from complex 
organic mixtures of the acid, provided sulphuretted hydrogen 
or some other gaseous substance which also produces a deposit, 
is not present. The odor of these substances, as well as that 
of hydrocyanic acid, would generally suffice to determine the 
true nature of the film produced by these various vapors, even 
without the aid of the microscope. The deposits produced by 
the vapors of bromine and iodine, have a faint yellowish-white 
color. It may be remarked that the vapors of chlorine and of 
hydrochloric acid, generally cause the dispersion of the silver 
solution, so that it trickles down the inside of the inverted 
watch-glass; and the films produced by them are quite thin, 
even when occasioned by the pure gases. 
2. Iron Test. 
When a solution of free hydrocyanic acid is treated with & 
solution of caustic potash or soda, and then with a solution of 
sulphate of iron which has been exposed to the air and contains 
some persulphate of the sesquioxide of iron, it yields a precipi' 
tate of Prussian-blue (Fe43FeCy3), mixed with more or less 
protoxide and sesquioxide of iron: this mixture may have either 
a yellowish-brown, greenish, or bluish color, the hue depending 
upon the relative quantities of the iron compounds present- 
On treating this mixture with a few drops of hydrochloric or IRON TEST. 
181 
sulphuric acid, the oxides of iron dissolve, while the Prussian- 
blue remains in the form of a deep blue deposit, it being- insolu- 
ble in the acid. Should the hydrocyanic acid already exist in 
the form of an alkaline cyanide, the addition of the potash or 
soda solution should be omitted. In a solution of free prussic 
acid, the iron compounds alone produce no change. 
The object of the addition of the free alkali in the above 
process, is to convert the free hydrocyanic acid into an alkaline 
cyanide. When this salt is then treated with the sulphates of 
the prot- and sesqui-oxides of iron, a double decomposition takes 
place, in which the alkaline cyanide becomes changed into sul- 
phate of potash, and the iron sulphates into proto- and sesqui- 
cyanides of iron, thus: 9KCy + 3 FeO, S03+ 2 Fe203*, 3 S03 = 
9 KO, SO 3+B Fe Cy + 2 Fe2Cy3; the elements of the iron cyan- 
-1(les then coalesce to form Prussian-blue (3 Fe Cy + 2 Fe2Cy3 = 
Fe43FeCy3). It is thus obvious that the presence of both the 
11 on oxides are necessary for the production of the blue com- 
pound. The oxides of iron precipitated by any excess of 
Potash employed, are dissolved by the hydrochloric or sul- 
phuric acid added, as chlorides or sulphates of iron. 
In very dilute solutions of hydrocyanic acid, the test fails 
produce an immediate precipitate; but the liquid, after the 
Edition of the mineral acid, immediately acquires a greenish 
and after a time deposits flakes of the blue compound. 
cu solutions also require a proper adjustment of the potash 
j*jUd *r°n solutions. A large excess of potash will decompose 
e Prussian-blue, while a similar excess of the iron mixture, 
Pr°duces with hydrochloric acid, a yellow liquid which may 
unr solution a small quantity of the blue compound. When, 
retore, the addition of the chlorine acid produces a yellow 
1 ion from which no Prussian-blue separates, even after a 
ah U°n So^u^0Ib before pronouncing hydrocyanic acid entirely 
sent. There is no difficulty in the application of the test, 
Xcept in very dilute solutions of the poison. In no case, 
any inference be drawn from the color of the precipitate 
.r Ibe addition of the mineral acid, since it may have a 
Ulsh color, even in the absence of prussic acid. 182 
HYDROCYANIC ACID. 
One grain of a hydrocyanic acid solution, when treated as 
above, yields the following results : 
1. two grain of the pure acid, yields a very copious deposit of 
Prussian-blue. 
2. tto'o‘o grain: a very good deposit.' 
3. stoVo grain: a greenish-blue, flocculent precipitate, and a 
greenish solution; after a time, the deposit increases in 
quantity and acquires a deeper blue color. Solutions 
dilute as this, especially when only a single drop is op- 
erated upon, require a proper adjustment of the reagent 
solutions : when these are very strong, only a very small 
drop of each should be employed. 
4. Torero's grain: with a very small quantity of the potash and iron 
solutions, yields a quite perceptible greenish-blue, flocculent 
precipitate, with a greenish solution; after the mixture has 
stood some little time, the result is perfectly satisfactory. 
5. 25700Ti grain, yields just perceptible greenish flakes, and 
after a few hours, a quite distinct deposit, which when 
examined by a hand-lens, has a well-marked blue color. 
The production of a blue precipitate, insoluble in hydro- 
chloric acid, by this test, is perfectly characteristic of hydro- 
cyanic acid, or at least of a cyanide. At the same time, the 
reaction is not interfered with by any substance at all likely to 
be mot with in medico-legal investigations. 
Vapor of Hydrocyanic Acid.—ln the application of this test 
for the detection of the vapor of the poison, the vapor is 
received for some minutes on a drop of potash solution, by 
which it will be absorbed as cyanide of potassium, without how- 
ever any visible change ; the solution is then treated with the 
iron mixture and hydrochloric acid, in the manner above de- 
scribed. The vapor from one grain of a 5,000 th solution of the 
poison, will, when the manipulations are conducted with great 
care, yield quite satisfactory results. This, however, is about 
the limit of the vapor reaction. 
This method may be employed to confirm the nature of the 
cyanide of silver, produced by the preceding reagent. F°r 
this purpose the washed deposit, placed in a watch-glass, is 
treated with a drop of hydrochloric acid, and the vapor of the SULPHUR TEST. 
183 
hydrocyanic acid thus eliminated, absorbed by a drop of potash 
s°hition, in the manner just pointed out. By this process, the 
B'ue nature of a much less quantity of the silver precipitate may 
he fully established than by the method of reduction, heretofore 
described. 
3. Sulphur Test. 
When a solution of free hydrocyanic acid or of an alkaline 
cyanide is treated with a solution of yellow sulphuret of ammo- 
niUllb and the mixture gently heated, it gives rise to sulpho- 
oyanide of ammonium, which when treated with a persalt of 
iron, yields a deep blood-red solution of sulphocyanide of iron. 
ais reaction was first pointed out in 1847, by Prof. Liebig. 
In applying this test, a few drops of the prussic acid solu- 
lon, placed in a small white dish or watch-glass, are treated 
a drop of the sulphuret of ammonium, and the mixture 
®vaporated at a moderate temperature, on a water-bath, to near 
yness. Should the residue have a yellow color, it is moist- 
ened with a drop of water and again evaporated. The cooled 
residue—consisting of sulphocyanide of ammonium, often in its 
Crystalline state, and a white film of sulphur—is then treated 
a drop of a colorless solution of persulphate of iron or 
Sesquichloride of iron, when the mixture will immediately 
assnnie, unless very dilute, a very deep blood-red color. If the 
Excess of sulphuret of ammonium added has not been entirely 
Ecomposed or volatilised, the iron reagent will produce a black 
Plecipitate of sulphuret of iron; this however is readily dis- 
ved by a drop of dilute hydrochloric acid, without interfering 
red color of the mixture, unless it is very feeble. 
i 0~0 grain of hydrocyanic acid, when treated as above, yields 
9 a beautiful blood-red solution, 
g’ Togo grain, yields an orange-colored mixture. 
1 °.ooT) grain: the final solution has a very satisfactory light- 
orange hue. 
2 STou'o grain, yields a mixture having a distinct reddish tint. 
The color of this mixture is quite well marked when com- 
- pared with that of the reagents alone. 
5 o.owo grain, yields a just perceptible coloration. 184 
HYDROCYANIC ACID. 
The red color produced by this test is immediately dis- 
charged by corrosive sublimate, and by nitric acid; but it is 
unaffected by even very large excess of strong hydrochloric 
acid, except from very dilute solutions, when it is readily 
destroyed by an excess of this acid. It is also discharged, 
to a faint reddish hue, by an alkaline acetate, but immedi- 
ately restored upon the addition of hydrochloric acid; ammonia 
causes it to disappear, with the precipitation of sesquioxide 
of iron. 
Fallacies.—Persalts of iron also strike a deep blood-red color 
with solutions of meconic acid. This color, however, is not 
discharged by corrosive sublimate, nor is it affected by an alka- 
line acetate, and it is readily changed to yellow or reddish- 
yellow, by an excess of hydrochloric acid. The reagent also 
changes very strong solutions of the alkaline acetates to a deep 
dark-red color, due to the formation of acetate of sesquioxide 
of iron 5 this color, however, is immediately discharged to a 
faint yellow tint, by even a very small quantity of hydrochloric 
acid. In this connection, it may be remarked that both meconic 
acid and the alkaline acetates are destitute of odor. 
The objections just mentioned are the only ones that can 
reasonably be urged against the sulphur test, and they are 
readily answered. When, therefore, a suspected solution yields 
with the test a strong red color, unaffected by large excess of 
hydrochloric acid, there is no doubt of the presence of a sul- 
phocyanide ; yet, should the color be only faint, its disappear- 
ance, on the addition of the acid, would not prove the entire 
absence of the poison. 
Vapor of Hydrocyanic Acid.—The sulphur test may also 
be apjDlied for the detection of the vapor of the acid, as first 
suggested by Dr. A. Taylor. For this purpose, a drop of the 
sulphuret of ammonium solution, contained in an inverted watch- 
glass, is exposed to the evolved vapor for some minutes, and 
then examined in the manner above described. 
The vapor evolved from the 10,000 th part of a grain of 
prussic acid, in one grain of water, will after this method, pro- 
viding the ammonium solution has been exposed to the vapor 
from ten to fifteen minutes, yield a very distinct coloration ] RELATIVE VALUE OF TESTS. 
185 
but the result could hardly be claimed to be satisfactory. It 
need hardly be added, that when the sulphur test is applied in 
Hds manner, it is free from the fallacies that hold in its direct 
aPplication to a suspected liquid. 
The sulphur test may also be employed to confirm the pre- 
cipitate produced by the silver reagent. For this purpose, the 
hashed precipitate is treated with a few drops of sulphuret of 
ammonium, and the mixture evaporated, at a gentle tempera- 
lai’e, to dryness. In this operation, the cyanide of silver will 
de decomposed by the ammonium compound, with the formation 
°f sulphuret of silver and sulphocyanide of ammonium. On 
110 treating the dry residue with a little water, the ammonium 
salt will dissolve, and the solution, after filtration and concen- 
tration, yield the usual blood-red color when treated with a 
persalt of iron. 
So also, this test may be applied to the vapor evolved, when 
le cyanide of silver is decomposed by a drop of strong hydro- 
chloric acid. 
Relative Delicacy of the foregoing Tests.—ln regard 
the relative value, in this respect, of the Silver and Iron 
tests, it may be observed, that when they are applied to the 
Vapor of the poison, the former is much the most delicate, while 
solutions, the latter is much the most susceptible. It is 
true, that the silver test will produce a precipitate with a much 
ess quantity of the poison than the iron test will reveal; yet 
. e silver deposit cannot in itself be regarded as peculiar, until 
T yields an inflammable gas when heated in a reduction-tube, 
fa’ which purpose it requires, with the greatest care, the pre- 
Clphate corresponding to the 500 th part of a grain of the poison, 
even the deposit from this single quantity could by no 
Cleans be collected and confirmed: but the iron test produces a 
aracteristic reaction with one grain of a 10,000 th solution of 
tfle poison. 
*511 the other hand, when applied to the vapor of hydro- 
V* anic acid, the iron reaction has its limit with about the 
>sooth part of a grain of the acid, whilst the silver test yields 
Satisfactory result with the 100,000 th part of a grain, in one 186 
HYDROCYANIC ACID. 
grain of water. In other words, for solutions, the iron test is 
about twenty times more delicate than the silver test, while for 
the vapor of the jioison, the silver reaction is about twenty 
times more delicate than the iron test. 
In regard to the Sulphur test, when applied to solutions of 
the acid, it is somewhat more delicate than the iron reaction, 
and so also in regard to the detection of the vapor, but in the 
latter respect very much inferior to the silver method. From a 
review of these tests, it is obvious that should a suspected solu- 
tion fail to yield a precipitate with nitrate of silver, it would 
be useless to apply either of the other tests; yet it should be 
remembered that a solution which only yields a faint reaction 
with the silver reagent, may evolve a vapor that will yield with 
it very satisfactory results. 
The comparative value of these tests may be approxima 
tively exhibited as follows: 
Silver test, with Solutions, grain; with Yapor, xurr,WiT grain. 
Iron test, “ “ TTTjoTnj grain; “ “ totW grain. 
Sulphur test, “ “ TSihuu grain; “ “ xmoury grain. 
It need hardly be observed that these results are based upon 
the assumption that the poison is in solution in one grain of puV6 
water, and it may be added, manipulated with care by experi- 
enced hands. 
Other Tests.—For the detection of hydrocyanic acid, Las- 
saigne advised to precipitate it by a solution of Sulphate of 
Copper, as cyanide of copper; but in every respect, this test 
is inferior to those already mentioned. 
Nitrate of Suboxide of Mercury, produces in solutions of free 
hydrocyanic acid, and of alkaline cyanides, a dark grey or 
nearly black precipitate of finely divided metallic mercury- 
This reaction serves to distinguish hydrocyanic acid, and its 
simple salts, from hydrochloric acid and its compounds, which 
yield with the reagent a white precipitate of subchloride of 
mercury, or calomel. The application of this test, for this 
purpose, would of course be unnecessary if the iron or sulphur 
test has been applied. SEPARATION FROM ORGANIC MIXTURES. 
187 
Separation from Organic Mixtures. 
As hydrocyanic acid is liable to be rapidly dissipated in the 
form of vapor, and even to undergo spontaneous decomposition, 
examination of a mixture in which its presence is suspected, 
should not be delayed. The same method of research will apply 
eqnally to suspected articles of food or medicine, the matters 
Vomited, and the contents of the stomach. Before resorting to 
the application of any chemical test, the suspected mixture 
should be carefully examined in regard to its odor; but it must 
he borne in mind, that mixtures of this kind may contain a 
ery notable quantity of the poison, without emitting its pecu- 
har odor. 
Examination for the Vapor.—For this purpose, the suspected 
fixture is placed in a glass jar or any similar vessel, and the 
Sleuth of the vessel then covered by an inverted watch-glass in 
has been previously placed a drop of nitrate of silver 
solution. Sooner or later, even if only a minute trace of the 
VaP0r is being evolved from the mixture, the silver solution 
'vhl acquire a white incrustation of cyanide of silver. Any 
eP°sit thus produced is then examined under the microscope: 
the same time, the mouth of the bottle should be closed by a 
Col'k, or by another watch-glass containing a drop of the silver 
Should the microscope reveal the presence of crystals, 
0 the forms already described, these will fully establish the 
Presence of the poison, since there is no other substance that 
yield similar results. Should, however, the deposit be 
aißorphous, it may still, in part at least, be due to the cyanide; 
it might be due to the presence of chlorine, or jmssibly to 
vapor of bromine or of iodine. Under these circumstances, 
e true nature of the deposit, if cyanide of silver, may be 
either by the iron or sulphur test in the manner 
1 eady indicated. One or both ihese latter tests should also 
.. aPplied directly to the suspected mixture, even in case the 
Ver faction is satisfactory, 
ut ie silver solution, after an exposure of several min- 
eb fail to indicate the presence of the poison, the suspected 188 
HYDROCYANIC ACID. 
mixture should be occasionally agitated, by shaking the bottle, 
and the application of the reagent be continued for half an hour 
or longer. If there is still no evidence of the presence of the 
poison, it is not likely that it would be detected by this method, 
even if applied for several hours; yet it must not be concluded 
that the poison is entirely absent, even in its free state, since 
it may be strongly retained by organic substances. In case the 
silver reagent should fail to receive a deposit, it would of course 
be useless to apply either of the other tests for the vapor. 
Method hy simple Distillation.—After testing the suspected 
liquid in regard to its reaction and setting apart a small portion, 
for future examination if necessary, the remaining portion is 
placed in a retort having its neck slightly inclined upwards and 
connected, by means of a bent tube and corks, with a Liebig’s 
condenser, the lower end of which opens into an ordinary 
receiver. In the absence of Liebig’s condenser, the retort may 
be connected directly with a well-cooled receiver. The liquid 
is then distilled at a moderate heat, by means of a water-bath, 
until about one-eighth of the fluid has passed over into the 
receiver. On account of its volatile nature, any free hydro- 
cyanic acid originally present in the liquid, will now be found 
in the distillate, which may be examined in the usual manner. 
If prussic acid is thus obtained and the original liquid was 
destitute of a strongly acid reaction, then there is little doubt 
but the poison was present in its free state, yet it may have 
existed as an alkaline cyanide; but it could not have been in 
the form either of a ferro- or sulpho-cyanide. To determine 
whether it existed in its uncombined state or as an alkaline 
cyanide, a portion of the reserved fluid is treated with a mix- 
ture of proto- and per-sidphate of iron: if this yields no change? 
the hydrocyanic acid is free; but if it yields Prussian-blne, 
either at once or after the addition of hydrochloric acid, then 
the poison exists in the form of a cyanide. If the liquid under 
examination has an alkaline reaction, the poison, if present, 
will of course be in the form of a cyanide, even though origi*l' 
ally added in its free state. 
Should the mixture in the retort evolve either hydrochloric 
acid or sulphuretted hydrogen, this will collect with the distillate, SEPARATION FROM ORGANIC MIXTURES. 
189 
ari(i interfere with the reaction of the silver test; neither of 
these substances, however, would prevent the normal reaction 
°f either the iron or sulphur test. Hydrochloric and hydrocy- 
aillc acids may be separated, by redistilling a portion of the 
distillate with powdered borax or carbonate of lime, which will 
letaiu the chlorine compound, but not hydrocyanic acid. 
-Distillation with an acid.—lf the above method fail to 
reveal the presence of the poison, the contents of the retort, 
after the addition of water if they have become thick, are 
acidulated with sulphuric acid, and distilled as before. Any 
Sllnple cyanide present, would now evolve the whole of its 
cyanogen in the form of hydrocyanic acid. Should it at first 
e suspected that the poison existed as an alkaline cyanide, 
this method of distillation may at once be adopted. It must 
e remembered, however, that by this process a ferrocyanide, 
Such as ferrocyanide of potassium, or yellow prussiate of potash, 
]v°uld also evolve prussic acid; and the same may also be true, 
1 the distillation is continued for some time, in regard to the 
Sulphocyanide of potassium, which exists in small proportion in 
human saliva. 
# source of the poison obtained in the distillate when an 
acul has been employed, may be determined by treating a por- 
°u of the reserved liquid, after filtration if necessary, with a 
drops of hydrochloric acid, and stirring the mixture for 
f°rrie rninutes, and then adding a solution of sesquichloride of 
!r°n. If the liquid thus treated contained a simple cyanide, the 
lr°u reagent will produce no visible change, since the cyanide 
v°uld have been converted by the hydrochloric acid added, 
a chloride, and the whole of the prussic acid evolved; 
1 rf it contained a feiTocyanide or a sulphocyanide, this will 
req1^11’ 
c solution, as the case may be. As commercial cyanide of 
+c ssium is liable to be contaminated with ferrocyanide of 
Lt ssium, traces of the latter might be present in poisoning by 
ae former. 
lere reason to suspect that free hydrocyanic acid or 
tfi 1C ° potassium, is present with ferrocyanide of potassium, 
ey may be separated, according to Otto, in the following 190 
HYDROCYANIC ACID. 
manner. The mixture is treated with a solution of sesquichlo- 
ricle of iron as long as a precipitate is produced, by which the 
ferrocyanide compound will be converted into Prussian-blue; 
carbonate of soda is then added, until the mixture exhibits an 
alkaline reaction, then tartaric acid, until it shows a feebly acid 
reaction; it is then distilled in the ordinary manner. By this 
method, ferrocyanide of potassium yields a distillate entirely free 
from hydrocyanic acid, since it is retained as Prussian-blue, 
which is unaffected by the distillation; but when hydrocyanic 
acid or an alkaline cyanide is present, the distillate will contain 
the poison in its free state. 
This process is admirably adapted for the separation of free 
hydrocyanic acid from a ferrocyanide; but when the poison is 
present in the form of an alkaline cyanide, much or even 
the whole of it, if only in small quantity, may be retained as 
Prussian-blue. It is true, that sesquichloride of iron produces 
with cyanide of potassium, at first only free hydrocyanic acid, 
sesquioxide of iron, and chloride of potassium; but this mixture 
will after a little time form more or less Prussian-blue. This 
conversion will, of course, take place at once, if the iron reagent 
contains a proto-salt of the metal. 
For the separation of free hydrocyanic acid, cyanide of 
potassium, and ferrocyanide of potassium, it has also been pro- 
posed to distill the mixture without the addition of an acid, 
when the free prussic acid would pass over with the distillate; 
the residue in the retort is then filtered, the filtrate concentrated 
to a small volume and treated with strong hot alcohol, which 
will dissolve the cyanide, whilst the ferrocyanide would be pre- 
cipitated in yellowish-white scales, it being insoluble in this 
liquid. 
From the Flood and Tissues.—The methods already described 
are equally applicable for the examination of any of the fluids 
or soft solids of the body, in poisoning by prussic acid. Experi- 
ments upon animals have shown that the poison, when intro- 
duced into the stomach, may be diffused throughout the blood; 
within a few seconds. In the case already cited from Casper? 
in which a mixture of prussic acid and some essential oils 
proved fatal to a woman, the distillate obtained from about an FAILURE TO DETECT. 
191 
°unce of blcfod from the body, gave with the iron and sulphur 
tests, very distinct evidence of the presence of the poison: the 
silver test was not applied. The blood was treated with a 
small quantity of spirits of wine and phosphoric acid, and dis- 
tilled until about two drachms of fluid, smelling slightly of bitter 
abnonds, had passed over. In this case, death apparently must 
have taken place with great rapidity, since the deceased was 
found lying on the floor, with half a cucumber in one hand and 
a water jug in the other. The same writer relates another 
in which an apothecary took, with suicidal intent, an 
Unknown quantity of hydrocyanic acid, and the poison was also 
iecovered from the blood, by being distilled, in this case, with 
a few drops of sulphuric acid. It was also found in the con- 
tents of the stomach; but not in the urine contained in the 
bladder. 
Failure to detect the poison.—On account of its rapidly 
fatal effects, there is no ordinary poison more likely than hydro- 
cyanic acid to remain in the body at the time of death; yet on 
account of its ready decomposition and great volatility, there is 
Perhaps none that may more rapidly disappear from the dead 
cv. The time in which a given quantity of the poison may 
Us entirely disappear from the body, or any organic mixture, 
;vbl of course depend upon a variety of circumstances. In a 
°f suicidal poisoning by hydrocyanic acid mentioned by 
iQb Casper, twenty-six hours after death, no trace of the poi- 
-8011 urns found in the stomach, but there was present a consid- 
erable quantity of formic acid, as a result of the decomposition 
the prussic acid. 
Ou the other hand, cases are recorded in which the poison 
recovered after comparatively long periods. Thus Dr. 
quotes a case in which it was detected in a body 
P Cn days after death, although the corpse had never been 
and had been for some time lying in a drain. And in 
g lnstauce cited by Dr. Taylor, in which a dose equivalent to 
fat 1 . *= over three grains of anhydrous prussic acid proved 
111 about fifty minutes, it was detected both before and 
ei distillation, in the contents of the stomach, seventeen days 
after death. 192 
PHOSPHORUS. 
Quantitative Analysis.—The quantity of hydrocyanic acid 
present in a pure solution of the poison, may be readily determ- 
ined by precipitating it as cyanide of silver. For this purpose, 
the solution is treated with a solution of nitrate of silver as long 
as a precipitate is produced ; the mixture is then slightly acid- 
ulated with a few drops of nitric acid, and the precipitate col- 
lected on a filter of known weight, thoroughly washed, dried at 
212°, and weighed. Every one hundred parts by weight of 
cyanide of silver thus obtained, correspond to 2015 parts of 
anhydrous hydrocyanic acid. 
Section lll.—Phosphorus. 
History.—This remarkable elementary substance was first 
discovered by Brandt, in 1669, and received its name from ifg 
ready inflammability and from being luminous in the dark. 
Phosphorus is found in the three kingdoms of nature, but most 
abundantly as a constituent of bones, in which it exists as 
phosphoric acid, and this in combination with lime. In its un- 
combined state, it is a most powerful poison; and numerous 
instances of poisoning by it have occurred, especially since the 
introduction of friction-matches, and of phosphorus-pastes for 
the purpose of destroying rats. 
Symptoms. The more usual effects produced by phos- 
phorus, when taken in poisonous quantity, are a feeling of 
lassitude; gaseous eructations, which have a garlic-like odor, 
and are sometimes luminous in the dark; burning pain in 
the stomach and bowels ; nausea ; violent vomiting; sometimes 
purging; great thirst; cold perspirations; great anxiety; and 
a feeble, irregular pulse. The matters first vomited have gen- 
erally an alliaceous odor, and evolve white fumes, which shine 
in the dark 5 similar appearances have also been observed 
in the faeces, which have even contained solid particles 
the poison. The abdomen becomes tender to the touch; the 
extremities cold; the pulse almost imperceptible; the pupds 
dilated and insensible ; and frequently death is preceded by 
convulsions. PHYSIOLOGICAL EFFECTS. 
193 
In a case of poisoning by this substance related by Dr. 
mwinsky, in which a girl, aged twenty-two years, swallowed a 
Portion of phosphorus scraped from a small packet of lucifer- 
ftiatches, the following symptoms were observed. Soon after 
taking the poison, the patient experienced a sharp burning pain 
111 the abdomen, followed by vomiting of matters which were 
°hserved to be luminous while being ejected from the stomach. 
k°me hours afterwards, she was suffering from vomiting and 
purging ; but no odor of phosphorus was perceptible in the 
excretions. The abdomen was swollen and sensitive on press- 
*Uef the tongue white, and moist; the pulse normal, and the 
Illtellect clear. Vomiting, alternating with diiccough, continued 
Unceasingly until the third day ; but the purging ceased on the 
See°nd day. On the third day, there were signs of jaundice; 
® Urme was scanty and of a dark color; and the pupils were 
dilated, and nearly insensible to light. On the fourth 
a} ? the jaundiced appearance of the face was much increased, 
there was collapse, and great restlessness, with extreme 
11 and a weak, quick pulse; but the vomiting had abated, 
Sl*all quantity of blood only being thrown up; convulsions, 
impaired consciousness then supervened, and death occurred 
?!' le sixth day after the taking of the poison. (Brit, and For. 
V e(f--Chir. Rev., Oct., 1859.) 
COntrast with the above case, may be cited the following, 
e ated by Prof. Casper (Forensic Medicine, vol. ii, p. 100). A 
J oUng iady, aged twenty years, took at six o’clock in the even- 
off” t least three grains of phosphorus, in the form of the 
eul‘ electuar7- Those around her remarked nothing pe- 
thear ’ c^urinS tDe evening she wrote a letter. Later in 
(ey' eVening she seemed to her family to exhale “sulphur” 
ph confounding the vapor of sulphur with that of phos- 
-s|,ad,ad US~niatches), and complained that the light blinded her, but 
gJ 110 complaint whatever of pain. During the night, which 
full sleeplessly, she vomited once, and. died quite peace- 
j J six o’clock in the morning, just twelve hours after 
poison. 
llsUa]i° W^len belted.—ln fatal poisoning by phosphorus, death 
y takes place in from one to three days. The most 
13 194 
PHOSPHORUS. 
rapidly fatal case yet recorded, is perhaps that related by Prof 
Casper, just mentioned, in which death occurred in twelve 
hours. In a case quoted by Dr. Christison, the taking of a 
portion of lucifer-match composition, was followed by vomiting? 
pain in the abdomen, anxiety, restlessness, excessive thirst, and 
death in fifteen hours (Op. cit., p. 151). In an instance reported 
by Dr. Flachsland, a young man, aged twenty-four years, took 
an unknown quantity of the poison, spread on bread with butter. 
He soon experienced violent pain in the stomach and bowels? 
and intense vomiting, which continued the following day : after 
the use of clysters, he passed small fragments of phosphorus? 
which were luminous in the dark and burned spots in the bed- 
linen. Death ensued in forty hours after the poison had been 
taken. (Medizinisch-Chirurgische Zeitung, 1826, iv, p. 183.) 
Orfila, in quoting this case (Toxicologie, 1852, i, 84), errone- 
ously states that death took place in u four ” hours. 
Among the more protracted cases, may be mentioned the 
following. M. Diffenbach, an apothecary of Biel, as a matter 
of experiment, took one grain of phosphorus, on the 2d of July? 
1828. On the 21st of the same month he took two grains, and 
on the following day increased the dose to three grains. During 
the evening of the last day, he experienced uneasiness and a 
sense of pressure in the abdomen. These symptoms were suc- 
ceeded by violent and incessant vomiting, convulsions, delixlnin? 
and partial paralysis, and death ensued on the 29th of the 
month, or the seventh day after the last dose of poison had been 
taken. (Revue Medicale, 1829, iii, 429.)# In a case quoted by 
Dr. Beck, in which a young man took one grain and a half 
phosphorus, death did not occur until the twelfth day, after the 
taking of the poison. (Med. Jur., vol. ii, p. 511.) This seem8 
to be the most protracted case yet recorded. 
Fatal Quantity.—The effects of a given quantity of phos- 
phorus will depend much upon the state in which it is taken- 
A child, two years and a half old, died after swallowing the 
phosphorus contained on eight friction-matches; and a child? 
* For the examination of the original publication of this case, as well aS 0 
that reported by Dr. Flachsland, I am indebted to the kindness of Dr. Schiin® ’ 
of Wurzburg, Bavaria. ANTIDOTES. 
195 
tiv° months old, is said to have died from the effects of two such 
batches. (Wharton and Stille, Med. Jnr., p. 505.) The quantity 
the poison taken in the last-mentioned instance, could not 
have much exceeded the fiftieth part of a grain. In a case 
looted by Dr. Taylor, one-eighth of a grain destroyed the life 
a lunatic. In another instance, the composition from thirty 
01 forty lucifer-matches, administered with milk, proved fatal to 
a Woman, in less than forty-eight hours. (London Chem. News, 
April, 1860, p. 207.) Again, Dr. Christison quotes the case of 
a patient, affected with lead-palsy, who died in about two days 
10111 fke effects of considerably less than a grain of the poison, 
faken in the form of an emulsion. 
On the other hand, a case is related in which a child swal- 
k Wed. nearly a teaspoonful of phosphorus-paste, prepared for 
dling rats, and, under the free administration’ of magnesia, 
Entirely recovered. (U. S. Dispen., 1865, p. 644.) The quan- 
°f phosphorus taken in this case, probably exceeded one 
Aam. In 
a case quoted by Dr. Taylor, a young woman 
allowed the phosphorus obtained from about three hundred 
Clutches—equal to rather less than five grains of the poison— 
aild recovered without any very severe symptoms. (On Pois- 
lls> p. 345.) These are the most remarkable instances of 
recovery, after the taking of this poison, yet recorded; in fact, 
Veiy few cases of recovery have as yet been reported. 
Treatment.—No chemical antidote is known to the action 
lls poison. If there is not already free vomiting, it should 
mduced by the exhibition of an emetic. Calcined man- 
la> suspended in large draughts of any demulcent liquid, 
W fhen be freely administered: this may serve to neutralise 
°Xl(^e °f phosphorus remaining in the stomach. Instances 
1 elated in which this treatment was employed with great 
GSS’ as heen proposed to administer the magnesia in 
pension in chlorine water; but more recent experiments on 
v af§? have indicated that this mixture has no special ad- 
sta d^e' ®lnce phosphorus is somewhat soluble in fatty sub- 
, Ces, the administration of these should be avoided. If the 
V+r.oll as Passe<f inf° the intestines, purgatives may be used 
advantage. 196 
PHOSPHORUS. 
Post-mortem Appearances.—The contents of the stomach 
have in some instances evolved white fumes, having an allia- 
ceous odor, and being luminous in the dark. The lining mem- 
brane of the stomach is generally much inflamed, and has even 
presented a gangrenous appearance; these appearances may 
extend throughout the intestines, which are often much con- 
tracted. The liver, spleen, and kidneys are often highly red- 
dened, the lungs gorged with blood, the heart empty, and the 
brain congested. The blood throughout the body is usually 
dark colored and remarkably fluid. 
In the case fatal in twelve hours, related by Prof. Casper? 
forty-eight hours after death, luminous vapors were observed 
to issue from the vagina, and a greyish-white vapor smelling 
strongly of phosphorus continuously streamed from the anus ! 
A very distinct odor of phosphorus also came from the mouth? 
but without any visible vapor. The stomach itself diffused no 
odor of phosphorus; and no part of its mucous membrane was 
either softened or corroded. It contained about six to eight 
ounces of a bright, bloody-like fluid, mingled with coagulated 
milk ; no particles of phosphorus could be detected in the 
stomach, even with a magnifying glass. The intestines were 
pale, and presented nothing abnormal. The blood was dirty- 
red, of a syrupy consistency, and the blood-corpuscules were 
transparent and deprived of their coloring-matter. The liver? 
spleen, and kidneys were congested. The bladder was of a 
livid color, and contained about a tablespoonful of milky urine* 
The lungs contained but little blood, and the heart was almost 
completely empty ; but the large blood-vessels contained much 
blood. The meninges were moderately congested, and the brain 
contained more blood than usual. 
In Dr. Lewinsky’s case, in which death occur red on the 
sixth day, the stomach was filled Avith gas and a blackish- 
brown fluid; its mucous coat was raised from beneath, and 
covered with a thick mucus, streaked Avith dark-brown lines* 
The intestines contained a blackish-broAvn, thin frothy liquid* 
The bladder Avas contracted and empty. The cavity of the 
throat contained a bloody, frothy mucus, which extended into 
the bronchial tubes. The lungs Avere covered Avith a flaky CHEMICAL PROPERTIES. 
197 
exudation. The heart was contracted, and its cavities con- 
tained fluid blood with a little coagulated fibrin. The structure 
°f the brain was free from blood, but the ventricles contained 
a drachm of serum. A chemical examination of the stomach 
and its contents, by Dr. Schauenstein, showed no indication of 
the presence of phosphorus. 
In the case reported by Dr. Flachsland, which proved fatal 
111 forty hours, watery blood flowed in large quantity from the 
Nostrils; and also from the first incisions made into the skin 
and muscles of the abdomen. The stomach and bowels exter- 
nally were inflamed; the mucous membrane of the stomach pre- 
dated a gangrenous inflammation, which extended into the 
nodenurn; the large intestines were contracted to the size of 
le little finger. The mesenteric glands were hardened; and 
le spleen and kidneys inflamed. 
Chemical Properties. 
Qereral Chemical Nature.—Phosphorus, at ordinary tem- 
Pmatures, is a soft, colorless, transparent solid, having a waxy 
appearance, and a specific gravity, according to Schrotter, of 
,^’J* It fuses at a temperature of about 110°, and boils at 
000 hh When exposed to the air, it slowly absorbs oxygen, 
fll emits white fumes of phosphorous acid; at the same time 
exhales a peculiar garlic-like odor, and the fumes arejumin- 
lliS in the dark. Berzelius believed that this luminosity was 
G to the volatilisation of free phosphorus, but Schrotter has 
°Wrx that it is due to the combination of the phosphorus with 
Nfgen. (Chem. Gaz., vol. xi, p. 312.) This oxidation, and 
Gfrequently the luminosity, is prevented by the presence of the 
0r °f ether, alcohol, turpentine, and of certain other liquids, 
11 when these are present only in minute quantity. 
0£ eated in the open air, phosphorus takes fire at a temperature 
ab°ut 140°, and burns with a brilliant white light, evolving 
rise white fumes of phosphoric acid. The presence of certain 
ISlng agents causes it to inflame at much lower temperatures. 
t0 —Phosphorus is insoluble in water, but it dissolves 
a limited extent in fixed and volatile oils, especially by the 198 
PHOSPHORUS. 
aid of heat. It also dissolves to a limited extent in ether, and 
somewhat more freely in hot naphtha, from which, however, it 
partially separates on cooling in rhombic dodecahedral crystals. 
It is freely soluble in chloride of sulphur, and in bisulphuret of 
carbon ; five parts of the latter liquid dissolve one of phos- 
phorus (Graham). It is insoluble in hydrochloric acid, but 
warm nitric acid readily oxidises and dissolves it, in the form 
of phosphoric acid. 
When phosphorus is immersed in water and exposed to the 
action of light, it slowly becomes covered with a white opake 
coating, which, according to H. Rose, is nothing more than 
pure phosphorus, the change being simply due to a change in its 
state of aggregation. At the same time, however, a little of the 
phosphorus undergoes oxidation, and is dissolved by the liquid- 
Varieties.—Of the several allotropic forms of phosphorus, 
the Bed or amorphous variety is the only one that need be 
mentioned. This form is obtained by heating ordinary phos- 
phorus in an atmosphere of carbonic acid or of any gas that 
does not act upon it chemically, when after a time it will be- 
come converted into a dark-red amorphous mass, from which 
any unchanged phosphorus may be dissolved by treating the 
mixture with bisulphuret of carbon. 
This variety of phosphorus differs, not only in respect to if® 
physical properties, but also in regard to its physiological effects 
and chemical properties, from ordinary phosphorus, although 
its ultimate composition is precisely the same. Thus, it is des- 
titute of odor, and does not become luminous in the dark until 
heated to about 400°. Its fusing point is about 480°; at a 
temperature of about 500° it is reconverted into ordinary phos- 
phorus. It is insoluble in bisulphuret of carbon, terchloride of 
sulphur, ether, alcohol, and in naphtha; but it is sparingly sonl' 
ble in oil of turpentine. Moreover, from experiments on apl' 
mals, it appears to be entirely destitute of poisonous properties- 
Special Chemical Properties.—The physical appearance 
of phosphorus, together with its odor, the production of whdc 
fumes when exposed to the air, its ready inflammability, and 
its phosphorescence in the dark, readily serve to distinguish d 
in its solid state, even in very minute quantity. SPECIAL CHEMICAL PROPERTIES. 
199 
When a mixture containing free phosphorus is gently heated, 
best by means of a water-bath, in a test-tube, in the neck of 
which is suspended a slip of filtering-paper moistened with a 
solution of nitrate of silver, the vaporised phosphorus on coming 
111 contact with the silver compound decomposes it, with the 
production of phosphoric acid and the elimination of metallic 
silver, which imparts to the paper a brown or black coloration. 
A very minute trace of the poison will thus manifest itself. 
Since, however, there are several other vapors that will 
Slacken a solution of nitrate of silver, this change taken alone 
not prove the presence of phosphorus. That the result 
18 really due to the presence of phosphorus, may be determined 
digesting the blackened paper with a small quantity of hot 
precipitating any undecomposed nitrate of silver present 
- hydrochloric acid, filtering, and examining the concentrated 
hhrate for phosphoric acid, in the manner hereafter indicated. 
When phosphorus in its free state is mixed with diluted sul- 
phuric acid and zinc in a test-tube, or any convenient vessel, a 
Portion of the hydrogen gas evolved, by the action of the acid 
aild zinc, unites with the phosphorus with the production of 
Phosphuretted hydrogen gas, which is luminous in the dark, 
and sometimes spontaneously inflammable. A very small quan- 
y °f phosphorus will in this manner evolve a phosphorescent 
Sas for |lajf 
an hour or longer| and when the experiment is 
Pei formed in a small, narrow test-tube and in a perfectly dark- 
eilod room, or better at night, the least visible quantity of the 
poison will yield very satisfactory flashes of light, which con- 
Ue to be produced for some time. 
lf the phosphuretted hydrogen thus evolved, together with 
•leIIre hydrogen, be conducted through a drawn-out tube, and 
Snked, they burn with a greenish flame surrounded by a deli- 
ate .blue mantle. A paper moistened with nitrate of silver 
ion and exposed to the unignited gas, is immediately black- 
1 ' If the gas be conducted into water, it gives rise to white 
of^?S as A escapes from the liquid. With a solution of nitrate 
soi> if gives rise to phosphoric acid, which remains in 
lolb and a black precipitate, consisting of a mixture of 
athc silver and phosphide of silver. When conducted into 200 
PHOSPHORUS. 
a solution of corrosive sublimate, it produces a yellow or 
yellowish-white precipitate, which, according to H. Rose, con- 
sists of phosphide and chloride of mercury. 
1. Mitscherlich's Method. 
The most delicate method yet proposed for the detection of 
uncombined phosphorus, is that first pointed out by E. Mitscher- 
lich. It consists in distilling the substance containing the phos- 
phorus with diluted sulphuric acid, and conducting the evolved 
vapors through a glass tube surrounded by a condenser. The 
vapor of phosphorus is thus condensed, and gives rise to a con- 
tinuous luminosity, when observed in the dark. 
Mitscherlich’s Apparatus for the detection of Phosphorus. 
For the application of this method, the phosphorus mixture, 
after the addition of water if necessary, is acidulated with sul- 
phuric acid and placed in a glass flask, A, Fig. 2. The flask MITSCHERLICH’S TEST. 
201 
18 connected by means of an exit-tube, a, with a delivery tube, 
which is bent at a right angle, and after passing through a 
glass cylinder, B, filled with cold water, terminates in a drawn- 
°ut point within a small bottle, which serves as a receiver. 
The condenser may be readily constructed by taking a glass 
tube, about twenty inches in length and one inch and a half in 
diameter, and closing the ends with good corks, the upper of 
which has three perforations, while the lower has one for the 
passage of the delivery tube : the condenser is supplied with 
cold water from the reservoir C, the liquid being conducted by 
a fennel-tube, c, to the bottom of the condenser; the warmed 
Water is carried off from the surface of the liquid by a syphon, 
d- Having thus adjusted the apparatus, a dark screen is placed 
between the flask and the condenser. 
On now gently boiling the contents of the flask, while a 
stream of cold water flows through the condenser, a very dis- 
tinct and continuous luminosity, usually some inches in length, 
AOfl be observed in the dark to play up and down the cooled 
Portion of the delivery tube. The phosphorus thus distilled, 
Collects with the condensed aqueous vapor in the receiver, and 
iinparts to the liquid a strong alliaceous odor. When the quan- 
tity 0f phosphorus is not too minute, a portion of it collects in 
receiver in the form of small globules; a portion of it, how- 
er, always undergoes oxidation and remains in solution in the 
Clfkillate, in the form of phosphorous acid, and also, sometimes, 
a's_ phosphoric acid. The true nature of any globules thus ob- 
a^ned may bo determined even by their physical properties. 
The presence of phosphorous acid in the distillate may be 
own, by treating the filtered liquid with a solution of nitrate 
silver or of chloride of mercury; but as both these reagents 
Produce precipitates with various kinds of organic matter, which 
Plesent in the original mixture might distill over, it is always 
cst, when examining a suspected mixture, to convert the phos- 
loUs acid into phosphoric acid before testing. For this pur- 
l°s<b the distillate is treated with a few drops of nitric acid, 
°Ocentrated to a small volume, filtered if necessary, and then 
xainined by molybdate of ammonia or any of the other tests 
ned out hereafter for the detection of phosphoric acid. 202 
PHOSPHORUS. 
When in the examination of a suspected mixture, a lumin- 
osity has been observed during the distillation, and globules of 
phosphorus have collected in the receiver, it is wholly unneces- 
sary to examine the condensed liquid. On the other hand, if 
no luminosity or globules of phosphorus have been obtained, 
great care should be exercised in regard to any deductions from 
the detection of a mere trace of phosphoric acid in the distil- 
late, since it may have been carried over mechanically from the 
mixture submitted to distillation. It may be remarked, that it 
is only when the original mixture contains unoxidised phos- 
phorus that a luminosity and globules of phosphorus will be 
obtained, as neither phosphorous acid nor phosphoric acid, yield 
either of those results ; nor will either of these oxides appear 
in the distillate, even when present in the original mixture in 
large quantity, unless they be carried over mechanically with 
the vapor of water. 
Delicacy of this Method.—Mitscherlich distilled five ounces 
of a mixture . containing the fortieth part of a grain of pure 
phosphorus—that is, one part of phosphorus in little less than 
one hundred thousand parts of the mixture—and the luminosity 
continued until three ounces of liquid distilled over, which 
required about half an hour. In another experiment, he dis- 
tilled five ounces of a mixture containing one-third of a grain 
of phosphorus, and obtained such a number of globules of phos- 
phorus in the distillate, that one-tenth part of them would have 
sufficed to establish their true nature. 
In one of our own experiments, the fiftieth part of a grain 
of phosphorus was distilled with two thousand fluid-grains of 
water, acidulated with sulphuric acid. As soon as the mixture 
was brought to the boiling temperature, a phosphorescent light 
some inches in length appeared in the tube, within the con- 
denser, and continued without intermission for thirty-four min- 
utes, at which time the distillation was stopped, and eighteen 
hundred and twenty grains of fluid had distilled over. The 
distillate had a strong alliaceous odor, but it contained no 
globules of phosphorus; it however readily furnished evidence 
of the presence of oxides of phosphorus. The amount of 
phosphorus that passed through the tube per second, in this HYDROGEN TEST. 
203 
experiment, must have been something less than the 100,000 th 
part of a grain ; yet this gave a luminosity many times greater 
than would have sufficed to recognise its presence with absolute 
certainty. 
Interferences.—It has already been remarked that the pres- 
ence of certain vapors may entirely prevent the luminosity of 
phosphorus. Thus if the mixture subjected to distillation con- 
tained alcohol, ether, or oil of turpentine, no luminosity would 
he observed as long as these distilled over. Alcohol and ether, 
being very volatile, would soon be separated, and the light 
Ayould then appear; but this would not be the case in regard to 
the presence of oil of turpentine : this liquid, however, is not 
at all likely to be present in a medico-legal examination for 
phosphorus. M. Lipowitz has shown that the phosphorescence 
is also interfered with by the presence of ammonia; but this 
substance would be neutralised by the sulphuric acid added. 
According to Dr. F. Hoffman, who has made a series of over 
°Ue hundred and fifty experiments after Mitscherlich’s method, 
the reaction is not interfered with by the presence of either 
tartar emetic, magnesia, oxide of iron, musk, castor, opium, 
albumen, any of the metallic salts, volatile organic acids, nor 
. I fi’ee acids; but it is interfered with or entirely prevented by 
lQdine, calomel and corrosive sublimate in large quantity, and 
Metallic sulphurets in the presence of free sulphuric acid, and 
Particularly oil of wormseed. (London Chern, News, Jan., 1861, 
P- 50.) Jim same" observer remarks, that numerous experi- 
ments, by distilling the brain of various animals, blood, albu- 
Uien, casein, fibrin, legumen, and other proteine compounds, 
dilute sulphuric acid, failed to yield the least phosphor- 
escence. 
2. Hydrogen Method. 
This method, first devised by E. Dusart and since improved 
T 1 resenius, is based upon the property possessed by free 
1 °sphorus, and the lower oxides of phosphorus, of forming 
mth nascent hydrogen phosphurettcd hydrogen, which burns 
mth a greenish flame. The color of the flame is not dimin- 
led in intensity by conducting the mixed gases over hydrate 204 
PHOSPHORUS. 
of potash or caustic lime: these latter substances would retain 
any sulphuretted hydrogen present, which burns with a blue 
flame and thus interferes with the phosphorus reaction. 
An ordinary gas-evolution flask is charged with pure diluted 
sulphuric acid and zinc, and the evolved hydrogen, after being 
conducted over pumice-stone moistened with a saturated solution 
of caustic potash, ignited as it escapes from a drawn-out tube 
provided with a platinum burner. If the gas burns with a 
colorless flame, the phosphorus mixture is introduced, by means 
of a funnel-tube, into the flask, when the evolved gas will burn 
with a characteristic green color, which disappears if the tube 
becomes heated. For this reason the end of the tube should be 
surrounded with moistened cotton. If a piece of cold porcelain 
be depressed in the flame, the latter burns with an emerald-green 
color at the points of contact, until the porcelain becomes heated. 
On following this method, E. Dusart obtained from about 
the sixth of a grain of the paste of matches, a flame that not 
only burned for an hour and a half with a visible green tint, 
but also produced on porcelain spots of a yellowish-red color, 
which resembled finely reduced phosphorus. (Jour, de China. 
Med., 1868, p. 663.) The evolved gas has a peculiar odor, and 
is luminous in the dark. The peculiar odor of hydrogen when 
obtained from iron and dilute acids, according to Dusart is due 
to the presence of phosphuretted hydrogen. 
The phosphide of silver yields by this method the same 
results as free phosphorus. The silver compound may be ob- 
tained by gently heating the phosphorus mixture, acidulated 
with sulphuric acid, for some hours in a flask through which n 
slow stream of carbonic acid gas is being passed, and collecting 
the evolved vapor in a solution of nitrate of silver. In this 
operation, the vaporised phosphorus passes through the atmos- 
phere of carbonic acid without undergoing any change ; but on 
coming in contact with the silver solution, it gives rise to solid 
phosphide of silver and free phosphoric acid. The jfliosiflnde 
of silver is collected and washed on a filter, which has pre- 
viously been washed in diluted nitric acid and water; it is then 
suspended in a little water and introduced into the hydrogen 
apparatus. The presence of phosphoric acid in the filtrate, LIPOWITZ’S TEST. 
205 
separated from the silver compound, may be determined in the 
manner heretofore indicated. 
Fresenius states that he obtained by this process the clearest 
evidence of the presence of phosphorus in a large quantity of 
putrid blood mixed with the composition scraped from the tip 
°1 a common lucifer-match; and this even in the presence of 
substances which prevent the luminosity of the phosphorus in 
experiments by Mitscherlich’s method. 
3. Lipoioits’s Method. 
This method is based upon the property possessed by sulphur 
mhen heated with free phosphorus, of combining with it, even 
mhen present in very complex mixtures and in a highly com- 
minuted state, and producing a compound in which the presence 
°f the poison is readily determined. The phosphorus mixture, 
slightly acidulated with sulphuric acid, is gently boiled for about 
lialf an hour in a retort with a few small pieces of sulphur, the 
distillate being collected in an ordinary receiver. 
The fragments of sulphur are then separated from the cooled 
mixture, and washed with water. They will now emit the pecu- 
Hur odor of phosphorus, and be luminous in the dark. When 
gmitly heated with strong nitric acid, they yield a solution con- 
taining phosphoric acid, together with more or less sulphuric 
acud. The presence of phosphoric acid in this mixture may be 
shown by evaporating the liquid to a small volume, diluting 
Mlth a little water, filtering, neutralising the filtrate with am- 
monia, and applying the magnesia test, hereafter described. 
dhe liquid that distills over into the receiver will usually 
Contain one or more of the oxides of phosphorus, and have 
till 11* x A. / 
alliaceous odor. When however only a minute quantity of 
t °sphorus is present in the original mixture, the whole of it 
11 be retained by the sulphur. 
% this method, Lipowitz states that he detected phosphorus 
complex organic mixtures containing only the 140,000 th part 
fheir weight of the poison. 
P Since in medico-legal investigations for phosphorus, it often 
ccoines necessary to recover the poison, in part at least, as 206 
PHOSPHORIC ACID. 
phosphoric acid, before describing the methods of separating the 
former from organic mixtures, the general nature and chemical 
properties of the latter will he considered. 
Phosphoric Acid. 
General Chemical Nature.—Phosphoric acid is a com- 
pound of one chemical equivalent of phosphorus with five 
equivalents of oxygen (P05); it is the highest oxide of phos- 
phorus known. In its anhydrous state, it forms a snow-white 
amorphous mass, which has a strong affinity for water, and 
rapidly deliquesces when exposed to the air, forming a hydrate. 
Hydrated phosphoric acid is usually prepared by boiling phos- 
phorus with diluted nitric acid, and evaporating the solution 
until on cooling, it solidifies to a hard transparent mass; in 
this state, the acid is commonly known as glacial phosphoric 
acid, and contains these equivalents of water (8 HO; P05). 
Phosphoric acid, at least in its common form, is capable 
of uniting with three equivalents of a metallic base, for each 
equivalent of the acid; it is therefore tribasic. The salts of 
this acid, except those of the alkalies, are insoluble in water; 
but they are freely soluble in the presence of a free acid, even 
in most instances of acetic acid. 
Special Chemical Properties.—ln the following investiga- 
tions of the reactions of reagents with solutions of phosphoric 
acid, the latter was employed in the form of common phosphate 
of soda. The fractions indicate the amount of anhydrous phos- 
phoric acid in solution in one grain of water; the results, 
unless otherwise stated, refer to the behavior of one grain of 
the solution. 
1, Nitrate of Silver. 
This reagent fails to produce a precipitate in solutions of 
free phosphoric acid; but in neutral solutions of the alkali*l6 
phosphates, it occasions a light-yellow precipitate of tribasic 
phosphate of silver (BAgO; P05). The precipitate is readily 
soluble in ammonia, and also in nitric, acetic, and free phos- 
phoric acids; hydrochloric acid changes it to white chloride of MAGNESIAN TEST. 
207 
silver. From dilute solutions, the formation of the precipitate 
18 much facilitated by the aid of a gentle heat. 
1* nhr grain of phosphoric acid, in one grain of water, yields 
a copious, yellow deposit, which remains amorphous. 
TToTo grain, yields a very good precipitate. 
T Tcr;Wo grain: a very satisfactory deposit, of a very pale- 
yellow color. The precipitate from ten grains of the 
solution, has a very satisfactory yellow color, 
Torlnro grain: after a very little time, a quite distinct cloudi- 
ness appears. Ten grains of the solution, yield a very 
satisfactory turbidity, but the yellow color is not apparent. 
Nitrate of silver also throws down from neutral solutions of 
Hi’senious acid a yellow precipitate, which, however, usually 
becomes crystalline. The arsenical precipitate, like that from 
phosphoric acid, is readily soluble in ammonia, and in free 
acids; but when dried, and heated in a reduction-tube, it yields 
f sublimate of octahedral crystals, of arsenious acid, in which 
dis readily distinguished from the phosphorus compound. The 
Reagent produces yellowish-white precipitates in solutions of 
yidides and of bromides; but these precipitates are insoluble 
111 dilute nitric acid, and only sparingly soluble in ammonia. 
2. Sulphate of Magnesia. 
This reagent throws down from strong solutions of the alka- 
lle phosphates, but not of free phosphoric acid, a white amor- 
-1 mus precipitate of phosphate of magnesia. The quantity of 
e precipitate is much increased by boiling the mixture. One 
Slaui of a 100 th solution of phosphoric acid, in the form of an 
vahne phosphate, yields a very good precipitate, without the 
aPplication of heat. Ten grains of the same solution, yield 
n boiling the mixture, a very copious deposit. Ten grains 
a I?000th solution remain clear on the addition of the re- 
built, but when the mixture is boiled, it yields a quite good 
°cculent precipitate. 
N mixture of sulphate of magnesia, chloride of ammonium, 
. free ammonia, produces in solutions of free phosphoric 
and of alkaline phosphates, a white crystalline precipitate 208 
PHOSPHORIC ACID. 
of ammonio-phosphate of magnesia (2MgO; NH40, P05, 12 Ag)- 
This reaction is much more delicate and characteristic than 
that produced by sulphate of magnesia alone. The formation 
of the precipitate from very dilute solutions, is much facilitated 
by stirring the mixture with a glass rod. The precipitate is 
readily soluble in free acids, but insoluble in ammonia, even 
more so than in pure water. 
1. j-g-o grain of phosphoric acid, when treated with the above 
mixture, yields a very copious, gelatinous precipitate, which 
in a little time becomes crystalline. 
2. iTohro grain: a copious precipitate, which immediately begins 
to crystallise, and soon becomes entirely converted into 
feathery and stellate crystals, Plate IV, tig. 3. 
3. 37(fo“(j grain: an immediate crystalline precipitate, which soon 
becomes rather abundant. 
4. i 0,0 o o grain, yields an immediate cloudiness, and in a little 
time a crystalline deposit. 
5. T3Tsiro grain: in a very little time the mixture becomes tur- 
bid, and crystals can be seen by the microscope ,• after a 
few minutes, there is a quite satisfactory crystalline deposit. 
6. ;vtr,wo grain: after a few minutes crystals appear to the mi- 
croscope, and after some minutes they are quite obvious to 
the naked eye. 
7. ywoToito grain: after about fifteen minutes, crystals are per- 
ceptible to the naked eye. 
This reagent mixture also produces a similar crystalline 
precipitate in solutions of arsenic acid. When, however, the 
arsenical precipitate is dissolved in just sufficient acetic acid; 
and the solution treated with nitrate of silver, it yields a reddish- 
brown deposit; whereas, the phosphoric precipitate, when treated 
in the same manner, yields a white deposit. The same reddish- 
brown precipitate is produced by nitrate of silver from normal 
solutions of arsenic acid. 
8. Molybdate of Ammonia. 
To apply this test, molybdate of ammonia is mixed with 
sufficient hydrochloric or nitric acid to redissolve any precipitate MOLYBDIC ACID TEST. 
209 
that first forms; or according to Sonnenschein, who first pointed 
old the test, one part of molybdic acid is dissolved in eight 
parts of ammonia solution and twenty parts of nitric acid. A 
small quantity of this mixture is then placed in a test-tube, and 
a few drops of the phosphoric acid solution added, when, if the 
reagent is greatly in excess, the mixture will acquire a yellow 
c°lor and yield a yellow pulverulent precipitate of phospho- 
of ammonia. From very dilute solutions of the acid, 
the precipitate is slow to appear; the reaction is greatly pro- 
moted by a gentle heat. The precipitate consists of molybdic 
acid, ammonia, water, and phosphoric acid. According to M. 
(Chem. Gaz., 1856, p. 427), it contains 3T42 per 
Cent. of the latter, its formula being 60 Mo03; 2 (3NH4O; P05); 
ioHO. 
In the presence of excess of the reagent, phospho-molybdate 
°f ammonia is insoluble in nitric, hydrochloric, and most other 
acids, even on boiling; but it is readily soluble in excess of free 
phosphoric acid and of alkaline phosphates, the caustic alkalies 
and their cai’bonates, and in the alkaline tartrates. (Chem. 
(ia5S vol. x, 1852, pp. 216, 390.) 
In examining the limit of the reaction of this test, a very 
strong solution of molybdate of ammonia was prepared by dis- 
solving the salt in large excess of hydrochloric acid ; one fluid- 
of the phosphoric acid solution was then added to about 
Srains of the test-fluid, placed in a small test-tube. 
Ton grain of phosphoric acid produces an immediate yellow 
solution, and a bright-yellow precipitate, which in a little 
time becomes quite copious. The precipitate is much 
0 mcreased in quantity by warming the mixture. 
i.'o'oo grain: the mixture immediately assumes a yellow 
c°lor, and in a little time yields a copious yellow de- 
posit. If the precipitate be dissolved in the mixture by 
excess of ammonia, and then a mixture of sulphate of 
ftmgnesia and chloride of ammonium added, it yields an 
immediate crystalline precipitate of ammonio-phosphate 
°f magnesia, not to be distinguished from that thrown 
down from a pure solution of phosphoric acid of the same 
strength. 210 
PHOSPHORUS. 
3. I o.'o o'o grain: the mixture immediately assumes a yellow tint, 
which increases in intensity, and in a little time a yellow 
precipitate separates. Upon gently heating the mixture, 
it yields a good, yellow deposit. 
4. s-ounro grain: after a little time the mixture acquires a yellow 
tint; by heat, the yellow color becomes very distinct, and 
yellow flakes separate. These gather upon the surface of 
the fluid and form an adherent, yellow pellicle. 
5. rooVoo grain: after several minutes, no perceptible change. 
But if the mixture be heated, it assumes a distinctly yel- 
low color, and after a time small yellow flakes appear upon 
the surface of the liquid. 
This reagent also produces a yellow coloration and precipi- 
tate in solutions of arsenic acid, but only, however, as first 
pointed out by Sonnenschein, when the mixture is heated to 
about the boiling temperature. The absence of this acid may 
be shown by nitrate of silver, in the manner already indicated. 
So also, on the application of heat, the reagent imparts a yellow 
color to solutions of silicic acid; but this substance yields no 
precipitate, nor does it even yield a yellow coloration unless the 
mixture be heated. 
Other Reactions.—Phosphoric acid is also precipitated, at 
least from neutral solutions, by acetate of lead, soluble salts of 
baryta, strontia, lime, and of several other metals. The lead 
precipitate is almost wholly insoluble in acetic acid, but most 
of the other precipitates are readily soluble in this acid. These 
reactions, however, are common to solutions of several other 
acids, and in most instances are much inferior in delicacy to 
the tests already mentioned. 
Separation of Phosphorus from Organic Mixtures. 
The odor emitted by phosphorus is so peculiar that it 
often serve to detect the poison with considerable certainty? 
even when present in very complex mixtures. It must be 
remembered, however, that the presence of other odors ®a) 
entirely conceal that of this substance, especially if it is present SEPARATION FROM ORGANIC MIXTURES. 
211 
only in minute quantity. We have even found tins to be the 
case when comparatively large quantities of the poison were 
purposely added to animal mixtures which were undergoing de- 
composition. According to Dr. F. Hoffman (Chem. News., iii, 
coffee, mustard, smoked meat, highly seasoned food and 
beverages, and medicines containing odorous gum-resins, vola- 
tile oils, musk, castor, camphor, and chlorine, have the property 
°f concealing the odor of the poison, at least if present only in 
uflnute quantity. 
Organic mixtures containing free phosphorus, when exposed 
to the air, usually evolve vapors which are luminous in the dark, 
specially if the mixture be gently heated, and stirred. If on 
thus examining the mixture, any' solid particles of the poison 
are found, they may be washed in water, then in alcohol, and 
preserved for future examination if necessary. If the mixture 
Under examination is ammoniacal from putrefaction, before being 
examined in regard to its luminosity, it should be acidulated 
Uoth sulphuric acid. Should these means fail to prove the 
Presence of the poison, the suspected mixture is examined by 
°Ue or other of the following methods. 
Mitscherlich’s Method.—A comparatively large portion of the 
uuxture, acidulated with sulphuric acid, may be examined after 
hds method. As this is the most satisfactory process yet pro- 
posed for the detection of free phosphorus, it should never be 
Quitted, unless the poison has already been discovered in its 
state. If during the distillation, the contents of the flask 
ecome thick, they should be diluted with water, and the 
luocess continued as long as any luminosity appears in the 
condensing-tube. If the distillate thus obtained, contains any 
°oules of phosphorus, they are carefully separated from the 
then washed, dried between folds of bibulous paper, and 
eighed. The liquid may then, after the addition of a few 
°PS of nitric acid, be concentrated to a small volume, and a 
Poition of it examined by molybdate of ammonia, for phos- 
ai \IIC another portion may be neutralised with ammonia, 
? treated with a mixture of sulphate of magnesia and 
_^.^11ue of ammonium, which will precipitate any phosphoric 
u present, as ammonio-phosphate of magnesia. 212 
PHOSPHORUS. 
When this method yields a distinct luminosity or furnishes 
globules of phosphorus, it is certain that the poison was present 
in its free state. Should, however, the phosphorus have already 
undergone oxidation, this method will yield no evidence of its 
presence. Under these circumstances, the remaining contents 
of the flask are examined for oxides of phosphorus, in the 
manner described hereafter. It must also be borne in mind, 
that the luminosity may be entirely prevented by the presence 
of certain volatile substances. These substances, however, 
would not prevent any free phosphorus present from passing 
over into the receiver, and there appearing at least in the form 
of an oxide. That the luminosity of phosphorus is not readily 
interfered with by the ordinary products of decomposition, is 
shown by the following experiment. 
The putrid mass resulting from exposing a human stomach 
with its contents, free from phosphorus, to the action of the air 
for six weeks, was made into a thin paste by the addition of 
water. Twenty-five hundred fluid-grains of this highly offensive 
mixture, acidulated with sulphuric acid, were then distilled with 
about the thirtieth part of a grain of phosphorus, added in a 
finely divided state. Nearly as soon as the mixture reached 
the boiling temperature, a very distinct phosphorescence ap- 
peared within the condenser, and continued without interruption 
for twenty-six minutes, when the contents of the flask having 
become very thick and black, the distillation was discontinued. 
The distillate thus obtained measured nearly eighteen hundred 
fluid-grains, had a milky appearance, and very offensive odor, 
but no odor or globules of phosphorus were detected. When, 
however, this liquid was treated with a few drops of nitric 
acid, and evaporated to a small volume, then neutralised with 
ammonia and treated with a mixture of sulphate of magnesia 
and chloride of ammonium, it gave a fine crystalline precipitate, 
which when further examined was found to represent very 
nearly the fiftieth part of a grain of phosphorus. 
Method of Lipoivitz.—lf in the application of this method, 
the suspected mixture, after the addition of the fragments of 
sulphur, be boiled in a retort with a long neck, or the latter 
be connected with the receiver by means of a glass tube, and SEPARATION FROM ORGANIC MIXTURES. 
213 
the operation performed in the dark, the vapors as they pass 
through the tube, if they contain phosphorus, will be phosphor- 
escent, even, as we have in several instances found, when only 
a very small quantity of the poison is present. In this manner, 
this process may, as it were, be combined with that of Mit- 
sclierlich. Yet, as the poison would thus be divided, part of 
d remaining in the retort with the sulphur and part passing 
over into the receiver, this method is only advisable in the 
nbsence of facilities for the application of Mitscherlich’s 
method, in which the whole of the poison may be collected in 
the distillate. 
Hydrogen Method.—A portion of the suspected mixture, 
diluted with water if necessary, may be mixed in a test-tube 
0r small flask, with a few fragments of zinc and a quantity 
°f pure sulphuric acid equal in volume to about one-eighth of 
the fluid present. Any phosphorus present will now be evolved 
as phosphuretted hydrogen, which is luminous in the dark, and 
ymlds a black precipitate with a solution of nitrate of silver. 
The evolved gas may be ignited and the flame examined in 
the manner already described {ante, p. 203). 
Recovery as an Oxide of Phosphorus.—lf the phosphorus has 
undergone oxidation, the method of Mitscherlich, as already 
stated, will fail to reveal its presence. But, if the poison has 
°uly passed to the state of phosphorous acid, it may still be 
detected by the hydrogen method, just mentioned. Should it, 
°wever, have passed to the state of phosphoric acid, then this 
Method will also fail. 
Under these circumstances, the mixture, after the addition 
°f Water, and filtration if necessary, is treated with a few drops 
°f nitric acid and concentrated to a small volume. It is then 
leated with slight excess of pure carbonate of soda, evaporated 
dryness, and the residue slowly heated to fusion, by which 
e organic matter will be destroyed, while any phosphoric acid 
Plesent will remain as tribasic phosphate of soda. The residue 
ls then dissolved in a small quantity of water, and the solution 
Gambled by the usual tests for phosphoric acid. If, however, 
y a. minute quantity of phosphoric acid be thus detected, 
ls m. itself will be no evidence that the phosphorus originally 214 
PHOSPHORUS. 
existed in its unoxidised state, since that acid in minute quantity 
is normally present in most organic mixtures. 
Failure to detect the poison.—ln fatal poisoning by phos- 
phorus, as by most other substances, the whole of it may be 
eliminated from the body previous to death, even when death 
takes place with the usual rapidity. Then, again, as this 
substance readily undergoes oxidation, it may thus, at least as 
free phosphorus, speedily disappear from the dead body. In 
Dr, Lewinsky’s case, already cited, in which death occurred on 
the sixth day, a chemical examination of the stomach and its 
contents, by Dr. Schauenstein, failed to yield any indication of 
the presence of phosphorus. So also, in a case reported by 
Dr. Nitsche, in which a soldier purposely swallowed the ends 
of six ordinary packets of phosphorus-matches and died on the 
fourth day, a chemical examination of the stomach and a por- 
tion of the intestines, with their contents, two days after death, 
revealed no evidence of the presence of the poison. (Amer. 
Jour. Med. Sci., Jan., 1858, p. 288.) Early in the history of 
this case, a large quantity of the phosphorus mixture was 
expelled from the stomach by vomiting. 
Cases are reported, however, in which this poison was de- 
tected after comparatively long periods. Thus, in a case quoted 
by Wharton and Stille, it was detected in the contents of the 
intestines on the tenth day after it had been taken; and in 
another, cited by Dr, Taylor, it was found in its free state, in 
the stomach of a body that had been buried fourteen days, and 
which was in an advanced state of decomposition. And in a 
case reported by Dr. Ludwig, in which a child, three years and 
a half old, was poisoned by phosphorus-paste, about one grain 
of phosphorus in substance, was obtained from the contents of 
the stomach and intestines, although the body had been buried 
three weeks. (Jour, de Chim. Med., 1863, p. 584.) This is the 
longest period we find recorded after which the poison has yet 
been detected. 
Quantitative Analysis.—Any phosphorus found in its solid 
state, or obtained by Mitscherlich’s method, may, of course, be 
weighed as such. When, however, the phosphorus has been QUANTITATIVE ANALYSIS. 
215 
converted into phosphoric acid, it may he determined as pyro- 
phosphate of magnesia (2MgO; P05). For this purpose, the 
solution is treated with slight excess of a clear mixture of 
sulphate of magnesia, chloride of ammonium, and ammonia, and 
allowed to stand for several hours, in order that the precipitate 
may completely separate. The precipitate is then collected upon 
a filter, washed with water containing a little ammonia, dried, 
lgnited, and after cooling, weighed. Every one hundred parts 
the ignited residue, if pure, correspond to sixty-four parts 
°f anhydrous phosphoric acid or twenty-eight parts of free 
phosphorus. 216 
ANTIMONY. 
CHAPTER IT. 
ANTIMONY. 
History.—Antimony is a bluish-white, hard, brittle metal, 
having a density of about 6-7 : its symbol is Sb, and its com- 
bining equivalent, according to Schneider, 120-3. When heated 
to near redness, it takes fire and burns with the evolution of 
dense white fumes of teroxide of antimony. The metal is un- 
acted upon by cold sulphuric acid, but the hot acid converts it 
into an oxide with the evolution of sulphurous acid gas. Hot 
concentrated nitric acid oxidises it chiefly into antimonic acid; 
hydrochloric acid, even at the boiling temperature, has little 
action upon it, but it is readily soluble in nitro-muriatic acid. 
When taken in its pure state into the system, antimony 
seems to be inert. But several of its preparations are more or 
less poisonous. The only one of these, however, likely to be- 
come the subject of a medico-legal investigation, is tartar emetic. 
Tartar Emetic. 
Composition.—This substance, known also as tartarised anti- 
mony or tartrate of antimony and potash, is a combination of 
potash, teroxide of antimony, and tartaric acid, with two equiv- 
alents of water of crystallisation: KO, Sb03, C 8H4O,0, 2 A<l- 
- of antimony, in its free state, is a white crystallisable 
substance, which is insoluble in water, and only sparingly sol- 
uble in nitric acid, but readily soluble in hydrochloric and tar- 
taric acids, and in the caustic alkalies. The poisonous effects of 
tartar emetic are entirely due to the presence of this s.ubstance. 
Symptoms.—As a summary of the symptoms usually pro- 
duced by tartar emetic, when swallowed in large quantity, may 
be mentioned the following: nausea, violent and continuous PHYSIOLOGICAL EFFECTS. 
217 
vomiting, burning pain in the stomach and bowels, profuse 
purging, great thirst, violent cramps, small and feeble pulse, 
coldness of the extremities, great prostration, and in some in- 
stances convulsions and delirium. The matters discharged from 
tie bowels are usually very fluid, and frequently contain bile. 
The urine is generally increased in quantity, and its passage 
sometimes attended with pain. It is a remarkable fact that in 
several of the reported instances of poisoning by this substance, 
there was neither vomiting nor purging; in these, however, the 
other symptoms were present in an aggravated form. 
A man of strong constitution, aged fifty years, for the pur- 
pose of self-destruction, swallowed about thirty-seven grains of 
tartar emetic. Violent vomiting, excessive purging, and con- 
vulsions soon ensued. On the morning of the third day, he 
complained of violent pain in the epigastrium, which was much 
; spoke with difficulty, and appeared as if intoxicated; 
ilo pulse was imperceptible. During the day the bowels be- 
came tympanitic and more painful, and delirium supervened. 
uo next morning all the symptoms were aggravated, and in 
ile evening the delirium became furious ; convulsions then set 
and death occurred during the night, nearly four days after 
lc poison had been taken. (Orfihds Toxicologic, 1852, vol. i, 
P- 623.) 
The following most remarkable case of recovery is reported 
T T)r. J. X. Gileaves (Western Jour, of Med. and Surg., Jan., 
p. 23). A young man of strong constitution swallowed 
üblespoonful of tartar emetic (about an ounce). In an hour 
° half afterwards, although he drank freely of warm water 
repeatedly tickled his fauces with his finger, no vomiting 
°ccurred. During the first three hours he vomited only 
0r three times, and the matter ejected was chiefly the warm 
er taken to induce vomiting. Two hours after taking the 
olb there was violent involuntary purging, and he became 
aft G*ess’ sPeechless, and was apparently dying. Three hours 
er the occurrence, when the case was first seen by Dr. 
°aves, the breathing was slow and difficult, the face pale, 
ColfillreS s^run^en7 eJes tixed, pupils dilated, and the surface 
5 there was no pulse, and the patient was apparently 218 
ANTIMONY. 
unconscious. In seven hours, the purging ceased, consciousness 
returned, and there was great thirst, and a sense of burning 
pain in the throat, oesophagus, stomach and bowels. Great irri- 
tability of the stomach ensued, and the matters vomited were 
tinged with blood. On the evening of the following day, the 
patient was again pulseless and speechless; and the abdomen 
was tympanitic and painful to the touch. The vomiting con- 
tinued, but the purging was arrested. On the third day, there 
was occasional vomiting, and the throat was sore and covered 
with pustules 5 there was also painful micturition, the urine 
being copious and highly colored. On the fourth day, the 
whole body was covered with genuine tartar emetic pustules. 
After a few days these began to heal, and in about two week8 
the patient was perfectly well. 
Period when Fatal.—A child, recovering from measles, died 
in an hour from the depressing effects of three-quarters of a 
grain of tartar emetic, prescribed as a medicine. In a case 
reported by Dr. C. Ellis, an unknown quantity of the poison 
proved fatal to a young lady, aged twenty-one years, in seven 
hours. The symptoms were violent vomiting and purging, ac- 
companied with a sense of burning in the mouth, dryness of the 
throat, and great thirst. Death took place apparently from ex- 
haustion, without convulsions or any cerebral symptoms. (Bos- 
ton Med. and Surg. Jour., Dec., 1856, p. 400.) In a case 
reported by Dr. Pollock, in which sixty grains of tartar emetic 
had been taken, death occurred in ten hours (London Med. Gaz., 
May, 1850, p. 801). In this instance, the patient, a robust, 
healthy man, aged about thirty years, was very soon seized 
with violent vomiting and retching. In two hours after the 
poison had been taken, there was still violent retching, at short 
intervals, and the man complained of heat and constriction 111 
the throat, and pain in the epigastrium; the respiration was fre' 
quent; the skin covered with perspiration; the pulse rapid and 
small. In a few hours afterwards, the vomiting ceased, and the 
patient became insensible; the respiration slow and labored, hut 
not stertorous; pulse very rapid and almost imperceptible; and 
the power of swallowing had ceased. Death took place tran- 
quilly, and without convulsions. FATAL QUANTITY. 
219 
The cases now cited are among the most rapidly fatal yet 
Reported. Instances are recorded in which death did not occur 
lllltd after the lapse of several days; and Dr. Deutsch relates 
a case, in which a woman, who took by mistake a scruple of 
tartar emetic, was brought exceedingly low by its violent action, 
and died in the course of a year in consequence of its irritant 
effects upon the intestinal canal. (Wharton and Stille Med. 
Jur-, p. 553.) 
Fatal Quantity.—Several instances are on record in which 
ei7 small doses of tartar emetic produced most violent symp- 
toms. Thus in an instance related by Dr. A. Stille (Mat. Med., 
lb a dose of not more than half a grain produced violent 
Vomiting and purging, and a state closely resembling the col- 
apse of cholera. The patient was an insane female, whose 
general health, however, was perfect. Of thirty-seven cases of 
acute poisoning by tartar emetic collected by Dr. Taylor, six- 
tcen proved fatal. Of the fatal cases, the smallest dose was in 
child, three-quarters of a grain, and in an adult, two grains; 
t m this case, there were circumstances which favored the 
al operation of the poison. (On Poisons, p. 543.) In a case 
jolated by Dr. C. A. Lee, a child a few weeks old, who swal- 
Ved about fifteen grains of the salt, in solution, was seized 
A'itli violent vomiting and purging, attended with convulsions, 
lch soon proved fatal. (New York Med. and Phys. Jour., 
;h?- Xxx> p. 302.) Two cases have already been cited in which 
lrty-seven grains and sixty grains respectively, proved fatal 
0 Wealthy adults. 
The following remarkable case of recovery is related by 
l* McCreery: A physician swallowed half an ounce of tartar 
lc? put up by mistake for Rochelle salt. In about thirty- 
-6 or forty minutes after taking the poison, he experienced 
P e nausea, which in about five minutes more was succeeded 
tau^°m^ing. Copious draughts of green tea and large doses of 
exVm Were then administered; and these were followed by the 
y Jition of albumen and an infusion of flaxseed. But the 
nfiy • which was very distressing, continued with little inter- 
ydtlj1011 or several hours. There was also very severe purging, 
most violent cramps of the legs, and slighter ones of the 220 
ANTIMONY. 
wrists. The first evacuation from the bowels was purely serous; 
those which followed were of a bilious character, but very loose: 
there were no cramps of the stomach. These symptoms gradu- 
ally subsided, and after several days the patient was quite well* 
(Amer. Jour. Med. Sci., Jan., 1853, p. 131.) It is well known 
that in certain inflammatory diseases, tartar emetic may be ad- 
ministered in very large doses without producing any of ds 
ordinary effects. 
Treatment.—lf there is not already free vomiting, it should 
be promoted by the administration of large draughts of warm 
water; or the stomach may be emptied by means of the 
stomach-pump. As a chemical antidote, various vegetable 
astringents, such as a strong infusion of Peruvian bark, green 
tea, nut-galls, or of oak-bark, have been highly recommended; 
and instances are reported in which their exhibition was appar- 
ently attended with very great advantage. It has, however, 
been denied that these substances serve to neutralise the poison- 
After the poison has been expelled from the stomach, opium 
may be administered to check the excessive vomiting. For 
this purpose, a strong decoction of coffee has also been highly 
recommended. 
Post-mortem Appearances.—ln the case cited from Orfila? 
which proved fatal in about four days, the mucous membrane 
of the stomach, except near the gullet, where it was healthy? 
was red, tumefied, and covered with a viscid coating, which 
was easily separated; the duodenum was in a similar condition? 
but the other intestines were healthy. The intestines were 
entirely empty. The brain was congested and softened. The 
organs of the chest were healthy. 
In the case related by Dr. Lee, in which fifteen grains 
of the poison had been taken, the mucous membrane of the 
stomach was red and softened, and on holding it up to the light? 
it appeared of a bright crimson color. The stomach contained 
a small quantity of slimy mucus, and, like the mucous mem' 
brane, was softened. The texture of the cardiac orifice seemed 
more changed than that of the pyloric. The duodenum was 0 
a deep brown color, almost livid, and contained the same kind 0 
substance as found in the stomach. The inflammation extende CHEMICAL PROPERTIES. 
221 
n° further than the colon. The vessels of the scalp, as well as 
those of the brain, and the right side of the heart, were dis- 
tended with blood. The ventricles of the brain were half filled 
noth fluid, and there was effusion between the pia-mater and 
arachnoid membranes. 
In Dr. Ellis’ case, thirty-nine hours after death, the body 
ivas quite rigid, and there was considerable bluish discoloration 
about the back of the neck and the hands. The stomach con- 
fined a quantity of gruel-like, acid liquid, in which a consider- 
able quantity of antimony was found. No well-marked morbid 
aPpearances were detected in any of the abdominal organs. 
The brain was not examined. 
Chemical Properties. 
General Chemical Nature.—Tartar emetic, as found in 
shops, is usually in the form of a white amorphous powder, 
n its pure state it crystallises in large, transparent, odorless 
Cfhedrons, having a rhombic base. The crystals are slightly 
efflorescent at ordinary temperatures, and when heated to 212°, 
econie anhydrous, 
j When heated in a reduction-tube, by the flame of a spirit- 
tartar emetic readily blackens, from the decomposition of 
e organic acid, and is soon reduced to a mixture of charcoal 
fly, I ' 
a Metallic antimony. It undergoes a similar change when 
eated upon platinum-foil, quickly destroying the platinum in 
with the heated mass. Heated on charcoal before the 
°*-pipe flame, the charred mass burns with the production 
a widely diffused incrustation, the thicker portions of which 
aVe a whitish color, while the thinner ones have a bluish 
Ppoarance; at the same time, it yields globules of metallic 
which boil and are slowly dissipated by the continued 
<* °f the heat. If the globules are allowed to cool, they 
be found exceedingly brittle, 
q According to R. Brandes, tartarised antimony is soluble in 
,^rn welve to fourteen parts of water at the ordinary temper- 
a e’ an(i in less than three parts of boiling water. From 
AVarni saturated solution, the salt separates on cooling, in 222 
ANTIMONY. 
beautiful bold crystals, Plate IV, fig. 4. The same crystals 
separate when one grain of a I,oooth or stronger solution of 
the salt is allowed to evaporate spontaneously to dryness; frolll 
more dilute solutions, the residue is usually destitute of any 
well-defined crystals. Aqueous solutions of tartar emetic are 
colorless, have a nauseous, metallic taste, and a feeble acid 
reaction, even when the liquid contains only the I,oooth pal 
of its weight of the salt. These solutions after a time undergo 
decomposition, the organic acid giving rise to a filamentous 
growth: we have found this formation make its appearance, 
after several days, in solutions containing even less than the 
50,000 th part of their weight of the antimony compound. 
It is insoluble in alcohol. If this liquid be added to an 
aqueous solution of tartar emetic containing even something 
less than the 100 th part of its weight of the salt, the latter i® 
precipitated in the form of plumose crystals; sometimes, how- 
ever, the precipitate also contains octahedral crystals. 
Special Chemical Properties.—When tartar emetic in ks 
solid state is moistened with a solution of sulphuret of amnio- 
nium or of sulphuretted hydrogen, it immediately acquires an 
orange-red color, due to the production of a sulphuret of anti- 
mony. This reaction is peculiar to antimony, and will manifest 
itself with the least visible quantity of the salt. Even the 
residue left on evaporating one grain of liquid containing only 
the 10,000 th part of a grain of the pure salt, will yield a very 
satisfactory coloration. 
In the following investigations in regard to the special reac- 
tions of reagents with solutions of tartar emetic, pure aqueous 
solutions of the salt were employed. The fractions 
indicate the amount of teroxide of antimony (Sbo3) present 111 
one grain of the solution. The amount of tartar emetic repc6' 
sented in these cases, may be readily obtained by multiply 
the fractions by 2‘35. 
1. Sulphuretted Hydrogen. 
From somewhat strong normal solutions of tartar emetic? 
this reagent throws down a deep orange-red precipitate 0 SULPHURETTED HYDROGEN TEST. 
223 
tersulphuret of antimony (SbS3); in more dilute solutions, it 
produces an orange-red turbidity, but no precipitate, at least 
f°r several hours. The formation of the precipitate from dilute 
s°lutions is much facilitated by heat. From solutions acidulated 
AVlth hydrochloric acid, however, even when very dilute, the 
1 ©agent produces an immediate precipitate. 
The precipitate is insoluble in diluted hydrochloric acid; 
the hot concentrated acid readily decomposes it with the 
formation of terchloride of antimony and the evolution of sul- 
phuretted hydrogen gas. Fuming nitric acid converts it into 
f Ayhite insoluble compound of antimony. It is readily soluble 
111 the fixed caustic alkalies, but insoluble in ammonia: at least 
o find that when one part of the moist precipitate is frequently 
for some days with 10,000 parts of ammonia solution, 
does not entirely disappear; and that one part with even 
parts of ammonia requires some hours for solution. 
ben dried and fused with nitrate of soda, it gives rise to 
aiitimoniate and sulphate of soda. 
In the following examination in regard to the limit of this 
*est, five grains of the antimony solution, placed in a small 
t©st-tube, were acidulated with hydrochloric acid, and then 
with the reagent. 
100 th solution of teroxide of antimony {=yo grain Sb03), 
yields a very copious, light orange-red precipitate. Solu- 
tions of tartar emetic as strong as this require about half 
their volume of hydrochloric acid to redissolve the precip- 
itate first produced by the acid. When tartaric acid is 
employed as the acidifying agent, the precipitate produced 
by the sulphur reagent has a much deeper red color than 
s) when produced in the presence of hydrochloric acid. 
I?000th solution: an immediate precipitate, which very soon 
becomes quite abundant. A normal solution of tartarised 
antimony of this strength, yields with the reagent a deep 
©range solution, but no precipitate, even after standing 
o twenty-four hours. 
jOOOth solution: an immediate turbidity, and after a little 
time a good deposit. If the mixture be warmed, the pre- 
cipitate separates almost immediately. When the solution 224 
ANTIMONY. 
is acidulated with tartaric acid, the precipitate requires 
several hours for its separation. 
4. 25,000 th solution: in a very little time the mixture acquires 
an orange tint; and after several hours there is a satisfac- 
Tory deposit. 
5. 50,000 th solution: in a little time the liquid assumes a yellow 
tint, then a reddish hue, and after several hours yields a 
quite perceptible orange-yellow deposit. 
6. 100,000 th solution: after some minutes the liquid acquires a 
faint yellow tint, but undergoes no further change for at 
least several hours. 
The reaction of this reagent, as already intimated, is quite 
characteristic of antimony. If the precipitate be dissolved m 
hot hydrochloric acid, and the solution after cooling treated 
with several times its volume of water, it yields a white pre- 
cipitate, consisting of teroxide and terchloride of antimony? 
which after a time becomes crystalline, and is readily soluble 
in tartaric acid. 
Sulphuret of Ammonium, also, throws down from compara- 
tively strong normal solutions of tartar emetic a precipitate ol 
tersulphuret of antimony, which is soluble in excess of the 
reagent. In live grains of a I,oooth solution of teroxide of 
antimony, the reagent produces a good, yelknv-orange deposit* 
In more dilute solutions, it fails to produce a precipitate, but 
communicates to the liquid an orange or yellowish-red color* 
In the presence of a free acid, however, it precipitates even 
highly dilute solutions of the salt. 
2. Acetate of Lead. 
This reagent produces in normal solutions of tartar emetic 
a white amorphous precipitate of tartrate of antimony and lend 
(PbO, Sb03, C 8H40,()), which is readily soluble in acetic and 
tartaric acids, and decomposed by nitric acid with the produc- 
tion of a white llocculent deposit. 
1. j-qh grain of teroxide of antimony, as tartar emetic, in one 
grain of water, yields a very copious precipitate. 
2. TTchro grain: a very good llocculent precipitate. ZINC AND COPPER TESTS. 
225 
Tovliir o grain, yields a very satisfactory deposit. 
2T.V00 grain: after a little time, the mixture becomes quite 
Acetate of lead also produces white precipitates in solutions 
°f various other substances. But the antimony deposit differs 
from, all these in that when washed and moistened with sul- 
pWet of ammonium, it immediately assumes an orange-red 
c°lor; after a little time however this color changes to a dark 
brown or nearly black hue. 
turbid. 
3. Metallic Zinc. 
When a drop of a solution of tartar emetic is placed on a 
of platinum-foil and acidulated with a small drop of 
hydrochloric acid, the addition of a fragment of zinc causes 
the separation of metallic antimony, which adheres to the plati- 
-1111111 covered by the liquid, forming a black or brownish stain 
(hh'esenius). The deposit is readily soluble in warm nitric acid, 
aiid when washed and dried, easily dissipated by heat. 
T<nr grain of teroxide of antimony, in solution in one grain 
of water, when treated in the above manner, yields a very 
0 copious, deep black deposit. 
TToTo grain: a very good deposit. 
' * sToiro grain: after a very little time, there is a very satisfac- 
tory dark-brown stain. 
ryoTo grain: after a few minutes, a very distinct brownish 
stain makes its appearance. 
The antimonial nature of these deposits may be shown, 
y moistening the washed stain with nitric acid, and evapo- 
atmg to dryness at a gentle heat, when the residue, on being 
eked with sulphuret of ammonium, will assume an orange- 
re<i color. 
4. Metallic Copper. 
chi a solution of tartar emetic is acidulated with hydro- 
?llc acid, and boiled with a slip of bright copper-foil, the 
0£ lnony compound undergoes decomposition with the deposition 
Metallic antimony upon the copper, in the form of a violet or 
15 226 
ANTIMONY. 
grey coating, the color depending upon the thickness of the de- 
posit. It is obvious that the thickness of the deposit produced 
by a given quantity of the metal, will depend on the size of 
the copper-foil employed in the experiment. 
When one grain of the tartar emetic solution, placed in a 
thin watch-glass, is acidulated and heated with a very minute 
portion of the foil, it yields as follows : 
1. yo"o grain of teroxide of antimony: the copper immediately 
assumes a violet color, and soon receives a thick, dark- 
grey coating. 
2. i~.(fo'o grain, yields much the same results as 1. 
3. rovVoU grain: in a little time, the copper presents a beautiful 
violet color. 
4. 5-orlnro grain? yields a very distinct reaction. 
5. riToVoi) grain: when the liquid is evaporated to near dry- 
ness, the copper acquires a perceptible violet tarnish. 
The production of a metallic deposit upon copper under the 
above conditions, is common to antimony, arsenic, mercury, and 
some few other metals. The violet color of the antimony de- 
posit is rather peculiar; but the deposit from this metal does 
not always present this color, and, moreover, very thin deposits 
of arsenic may present a similar hue. When the coated copper 
is washed, dried, and heated in a narrow reduction-tube, the 
antimony deposit, if present in comparatively large quantity? 
yields a white amorphous sublimate. Arsenic under similar 
circumstances yields a sublimate of octahedral crystals; and 
that from mercury appears in the form of minute metallic glob- 
ules. The other metals referred to, fail to yield a sublimate 
when thus treated. 
The true nature of the antimony deposit may be shown? 
as first advised by Mr. Watson, by boiling the coated copp61’ 
in a dilute solution of caustic potash, the coated metal being 
occasionally withdrawn from the liquid and exposed to the 
air, to favor the oxidation of the antimony, when after a 
time the deposit will be entirely dissolved, as antimoniate oi 
potash. On now removing the copper-foil, and acidulating the 
liquid with hydrochloric acid, concentrating to a small volume? 
and then treating it with sulphuretted hydrogen, pentasulphuret HYDROGEN TEST. 
227 
of antimony, of an orange-red color, will be precipitated. This 
method will serve to identify even very small deposits of the 
metal. 
5. Antimonuretted Hydrogen. 
When a solution of tartar emetic, or of any of the soluble 
salts of antimony, is mixed with zinc and sulphuric acid, in the 
proportion to evolve hydrogen, the salt is decomposed and the 
antimony evolved as antimonuretted hydrogen gas (SbH3). This 
decomposition may be effected in the apparatus of Marsh, first 
devised for the detection of arsenic, Fig. 3. 
Apparatus for the detection of Antimony. 
Pure zinc, and sulphuric acid, previously diluted with about 
our volumes of water, are placed in the flask A, which is fur- 
with a drying-tube c, and a reduction-tube d, the latter 
°f which is of hard glass and made to terminate in a drawn-out 
P°mt. The drying-tube should be loosely filled with cotton 228 
ANTIMONY. 
containing fragments of chloride of calcium. When only a 
minute quantity of antimony solution is to be examined, the 
glass flask may be replaced by a test-tube. After the appa- 
ratus has become completely tilled with hydrogen, a small quan- 
tity of the’ antimony solution is introduced into the flask, by 
means of the funnel-tube «, when in a few moments the evolved 
gas will contain antimonuretted hydrogen, the presence of which 
may be shown by three different methods. 
1. If the gas as it escapes from the end of the reduction- 
tube be ignited, it burns with a bluish flame, and, unless the 
amount of antimony present is very minute, evolves white fumes 
of teroxide of antimony. If these fumes be received upon a 
cold surface, as a piece of porcelain, they yield a white amor- 
phous deposit, which immediately acquires an orange-red color 
when moistened with sulphuret of ammonium. If a piece of 
cold porcelain, held in a horizontal position, be brought in 
contact with the flame, the antimony will condense in the form 
of a black, nearly circular spot or stain, which is usually sur- 
rounded by a greyish ring; as soon as a spot has thus formed, 
the flame should be received upon a fresh portion of the por- 
celain. 
If the experiment be performed in a small apparatus, fifty 
grains of a fluid mixture containing the 10,000 th part of its 
weight of teroxide of antimony (= grain Sb03), will yield 
quite a number of spots of the metal. 
Antimony and arsenic are the only metals that under the 
above conditions will yield metallic spots upon a cold surface. 
The spots from these two metals usually differ somewhat in 
regard to their physical appearance, those from antimony being 
usually dull, whereas those from arsenic have generally a bright 
metallic luster. They differ greatly, however, in regard to some 
of their other properties. Thus, the antimony stains are slowly 
and with difficulty dissipated by the flame of a spirit-lamp? 
whilst those from arsenic are readily volatilised. Again, the 
antimony spots readily dissolve in yellow sulphuret of ammo- 
nium, and the solution, even from very small stains, when gently 
evaporated to dryness, leaves a red or orange-red residue of 
sulphuret of antimony, which is soluble in strong hydrochloric HYDROGEN TEST. 
229 
acid, but insoluble in ammonia; whereas, the arsenic stains dis- 
solve but slowly in yellow sulphuret of ammonium, and the 
solution leaves upon evaporation a yellow residue of sulphuret 
of arsenic, which is insoluble in hydrochloric acid, but readily 
soluble in ammonia. Moreover, the antimony stains are insol- 
able or dissolve with great difficulty in a solution of hypochlorite 
of lime or of soda, whilst the arsenic spots readily disappear 
when touched with a solution of this kind. 
2. When a portion of the reduction-tube is heated to red- 
aess, the antimonuretted hydrogen passing through the tube is 
decomposed with separation of metallic antimony, which, when 
only 
in small quantity, is deposited within the tube wholly on 
the inner side of the part to which the flame is directly ap- 
plied, but when in larger quantity, on both sides of the flame. 
Arsenic under like circumstances yields a somewhat similar 
deposit; but in this case, the whole of the metal is deposited 
ln the tube on the outer side of the part to which the flame is 
aPplied. 
A much smaller quantity of antimony will in this manner fur- 
lllsh a deposit than will produce spots from the ignited jet upon 
porcelain. Fifty grains of a mixture containing the 500,000 th 
part of its weight of teroxide of antimony totWo grain Sb03), 
When treated in a small apparatus, will yield a very distinct 
brownish stain; and a similar quantity of a 50,000 th solution 
Will yield a very good brownish-black deposit, within the heated 
tube. Deposits of the metal produced by this method, exhibit 
the same chemical reactions as those produced on porcelain by 
the ignited gas. 
3. If the antimonuretted hydrogen be conducted into a solu- 
tion of nitrate of silver, the whole of the antimony is precipi- 
tated as antimonide of silver (Ag, Sb), in the form of a black 
P°wder. The chemical reaction in this case is as follows; 
3+ 3 AgO, N05 = Ag3 Sb +3HO + 3 NOs. When only a mi- 
trace of antimony is present, the whole of the precipitate 
collects in the lower end of the delivery-tube, in the form of a 
black ring. 
bhis reaction is extremely delicate, and the method can be 
aPplied with a much smaller quantity of fluid than either of 230 
ANTIMONY. 
those just mentioned. When the operation is performed in a 
small test-tube and the evolved gas conducted into a few drops 
of the silver-solution, five fluid-grains of a 10,000 th mixture 
of teroxide of antimony will produce a quite large, black de- 
posit, much of Avhich remains in the end of the delivery-tube. 
A similar quantity of a 50,000 th mixture produces after sev- 
eral minutes, a very satisfactory deposit; and a 100,000 th 
mixture will produce in about fifteen minutes, a very distinct 
reaction. 
Solutions of arsenic, sulphurets, and of several other sub- 
stances, will also under similar conditions evolve gaseous com- 
pounds, which produce black precipitates in a solution of nitrate 
of silver. In the action of the arsenic compound, the precipitate 
consists alone of metallic silver, the arsenic being oxidised into 
arsenious acid, which remains in solution. 
The true nature of the antimony precipitate, or antimonide 
of silver, may be shown by collecting the deposit on a filter, 
washing with warm water, and boiling with dilute hydrochloric 
acid, in which the antimony will dissolve, while the silver will 
remain in an insoluble form. If the quantity of precipitate 
present is too minute to be separated from the filter, the portion 
of the latter containing the deposit is boiled in the dilute hydro- 
chloric acid. When the acid mixture has cooled and the deposit 
completely subsided, it is transferred to a filter which has pre- 
viously been moistened with water, and the filtration repeated if 
necessary, until the filtrate is perfectly clear. On now treating 
the solution with sulphuretted hydrogen, tersulphuret of anti- 
mony, of its peculiar color, will be thrown down. 
Professor Hofmann has recommended to boil the washed 
antimonide of silver with a solution of tartaric acid, in which 
the antimony readily dissolves, while the silver remains un- 
changed ; the solution is then filtered and treated with sulphu- 
retted hydrogen. (Quart. Jour. Chem. Soc., April, 1860, p. 79.) 
By either of the methods now considered, an exceedingly minute 
quantity of antimony may be recovered from the silver pre- 
cipitate. 
From what has already been stated, it is obvious that the 
method under consideration will serve to detect antimony in the CHEMICAL PROPERTIES. 
231 
presence of arsenic, and the latter in the presence of the former. 
And this may he effected even when the metals are present in 
very minute and disproportionate quantities. 
Antimonuretted hydrogen is also decomposed by an alcoholic 
solution of potash, with the production of a black precipitate. 
Arsenic under similar conditions fails to produce a precipitate. 
Other Reactions of Tartar Emetic.—Nitric acid produces 
In somewhat strong solutions of tartar emetic, a white amorphous 
precipitate, which according to Geiger, consists of a basic nitrate 
°f antimonic oxide. The precipitate is soluble only in very 
large excess of the acid, but is readily soluble in tartaric acid; 
111 solutions containing free tartaric acid, therefore, the reagent 
fails to produce a precipitate. When the washed precipitate is 
touched with sulphuret of ammonium, it immediately assumes 
ail orange-red color. One grain of a 100 th solution of teroxide 
°f antimony when treated with a drop of the acid, yields a 
hmte copious deposit, which does not disappear on the further 
addition of several drops of the reagent. One grain of a I,oooth 
solution, yields with a small drop of the acid, a very fair pre- 
cipitate. 
Hydrochloric acid occasions in concentrated solutions of the 
salt a white precipitate, which is much more readily soluble in 
excess of the reagent than in the preceding reaction; it is also 
Very readily soluble in tartaric acid. One grain of a 100 th 
solution of teroxide of antimony yields with a drop of the re- 
agent a qUite good precipitate, which disappears when the mix- 
ture is stirred. This acid also produces white precipitates in 
solutions of silver, lead, and of sub-combinations of mercury. 
fAe silver precipitate is readily soluble in ammonia, and that 
from mercury is turned black, whilst the precipitates from lead 
Hrid antimony are unchanged by this reagent. Sulphuret of 
armnonium immediately changes the antimony precipitate to an 
orange-red color, whilst it turns the lead-deposit black. The 
aßtimony precipitate is the only one of these that is soluble in 
tart£iric acid. 
Sulphuric acid throws down from similar solutions, a white 
attiorphous precipitate, which becomes orange-red when touched 232 
ANTIMONY. 
with sulphuret of ammonium. The production of a white pre- 
cipitate by this acid is common to solutions of several other 
metals. 
Ammonia precipitates from solutions of tartar emetic, white 
teroxide of antimony, which is insoluble in excess of the pre- 
cipitant. One grain of a 100 th solution of teroxide of antimony 
yields a very good precipitate; and a similar quantity of a 
I,oooth solution yields a quite fair, granular deposit, especially 
if the mixture be stirred. Carbonate of ammonia fails to pro- 
duce a precipitate, even in concentrated solutions of the anti- 
monial compound. 
Potash and Soda produce in quite concentrated solutions of 
the salt, white amorphous precipitates, which are readily soluble 
in excess of either reagent. The carbonates of these alkalies, 
however, throw’ down white precipitates that are insoluble in 
excess of the precipitant; the limit of these reactions is about 
the same as that of ammonia. 
When a solution of tartar emetic is treated with sufficient 
excess of potash to redissolve the precipitate first, produced, 
and a solution of nitrate of silver then added, it produces a 
brownish-black precipitate, consisting of a mixture of suboxide 
and protoxide of silver, while the antimony remains in solution 
as antimoniate of potash. If the precipitate thus produced be 
treated with ammonia, the protoxide of silver is dissolved, while 
the suboxide remains as a dense black powder. One grain ol 
a 10,000 th solution of teroxide of antimony, Avhen treated after 
this method, will yield a very satisfactory black deposit; and the 
reaction is visible when a similar quantity of even a 25,000 th 
solution of the antimony compound is employed. Nitrate ol 
silver alone, produces in solutions of the antimony salt, a white 
precipitate. 
Corrosive sublimate slowly throws down from solutions of 
the salt, even when quite dilute, a white flocculent precipitate. 
Chromate and bi-chromate of potash impart to very strong solu- 
tions, a greenish color, and throw down a slight, greenish pre- 
cipitate. Ferro- and ferri-cyanide of potassium fail to produce 
a precipitate, even in concentrated solutions of the antimony 
compound. SEPARATION FROM ORGANIC MIXTURES. 
233 
Separation from Organic Mixtures. 
Suspected Solutions.—The same method of analysis is equally 
applicable for the examination of suspected articles of food or 
drink, vomited matters, and the contents of the stomach. The 
mixture, after the addition of water if necessary, is acidulated 
with hydrochloric acid, a little tartaric acid added, and the whole 
exposed to a gentle heat for about fifteen minutes. When the 
mixture has cooled, it is thrown upon a muslin strainer, the 
strained liquid filtered, and the filtrate, after concentration if 
necessary, exposed to a current of sulphuretted hydrogen gas 
as long as a precipitate is produced, and then allowed to stand 
m a moderately warm place for several hours, in order that the 
Precipitate may completely subside. 
If antimony is present in comparatively large quantity, the 
precipitate thus obtained will have a more or less orange-red 
color 5 if, however, the metal is present in only minute quantity, 
°r the deposit contains much organic matter, it will present a 
yellow or brownish appearance. The precipitate is now col- 
lected upon a filter, washed with water containing a little hydro- 
chloric acid, then boiled with strong hydrochloric acid, when 
aily tersulphuret of antimony will be decomposed and the metal 
dissolved as terchloride. After solution has taken place, the heat 
should be continued until the odor of the sulphuretted hydrogen, 
evolved by the decomposition, has entirely disappeared. 
A small portion of the clear liquid may now be examined 
hy the zinc and copper tests in the manner already described, 
except that it is not necessary to add hydrochloric acid since 
this is already present. Another portion of the liquid may be 
located with large excess of water, when the antimony, unless 
Present in only very minute quantity, will be precipitated as 
vhite oxychloride, the true nature of which is fully established 
Jy its assuming an orange-red color when moistened with sul- 
phuret of ammonium, as well as by its ready solubility in tar- 1 
aric acid. Should these tests yield positive reactions and it be 
esired to further pursue the investigation, the whole of the 
actiinony may be precipitated in the form of oxychloride, by 234 
ANTIMONY. 
treating the hydrochloric acid solution with water, and the pre- 
cipitate collected, washed, and then agitated for some time with 
a very dilute solution of carbonate of soda. In this operation, 
the oxychloride of antimony will be entirely converted into ter- 
oxide of the metal, the chlorine being taken up as chloride of 
sodium: care should be taken to employ only a very dilute solu- 
tion of the soda-salt, since otherwise more or less of the anti- 
mony compound might be dissolved. The precipitate is now 
collected, washed, and digested at a moderate heat with a little 
water containing an appropriate quantity of tartrate of potash, 
or cream of tartar, when it will be dissolved as tartar emetic, 
the presence of which may be determined by the usual tests. 
Should the precipitate produced from the original solution 
by sulphuretted hydrogen have a dark color, it should not be 
concluded, from this fact alone, that the metal is entirely ab- 
sent ; since it might be present even in very notable quantity, 
and the peculiar color of its sulphuret entirely masked by the 
presence of organic matter. 
Under these circumstances, the washed precipitate, placed 
in a thin porcelain dish, may be treated with a few drops of 
concentrated nitric acid, and the mixture cautiously evaporated 
to dryness, the operation being repeated if necessary until the 
organic matter is well carbonised. Any antimony present will 
now exist as an oxide of the metal. The residue is then moist- 
ened with a few drops of a strong solution of potash, the liquid 
expelled by a moderate heat, and the dry residue very gradu- 
ally heated to fusion. The cooled mass is stirred with a little 
water, the mixture acidulated with tartaric acid, then boiled 
for some minutes, and the solution filtered. The whole of the 
antimony will now be present in the filtrate, which, if the oper- 
ations have been conducted with care, will be perfectly colorless. 
A portion or the whole of the solution, may now be treated with 
a few drops of hydrochloric acid and exposed to a current of 
sulphuretted hydrogen, when any sulphuret of antimony thrown 
down will exhibit its characteristic color. 
By this method the sulphuret of antimony produced from 
the 100 th of a grain of the teroxide of the metal, may be 
recovered from a very complex organic mixture without any SEPARATION FROM ORGANIC MIXTURES. 
235 
apparent loss. Should the final solution obtained by the above 
method be highly colored, then instead of treating it with sid- 
phuretted hydrogen, it may be mixed with zinc and diluted 
sulphuric acid in the apparatus of Marsh, and the evolved gas 
conducted into a solution of nitrate of silver, as long as a black 
precipitate is produced. Any antimonide of silver thus obtained, 
is collected on a small filter, and well washed ; the point of the 
filter is then pierced and the precipitate washed, by means of a 
jet of water from a wash-bottle, into a small dish, then boiled 
with a little tartaric acid, the solution filtered, and, after con- 
centration if necessary, examined in the usual manner. The 
sulphuret representing the 100 th of a grain of teroxide of anti- 
mony, may be carried through both these processes, and still 
yield perfectly satisfactory results. 
Should it be desired in case the investigation for antimony 
should fail, to provide for the detection of other poisonous 
metals whose sulphurets are also precipitated from acidified 
solutions by sulphuretted hydrogen, such as arsenic, mercury, 
lead, and copper, the following method may be pursued. The 
hher containing the washed and still moist precipitate is spread 
°ut in a dish, the deposit well stirred with a solution of yellow 
Sulphuret of ammonium, and the solution filtered. As the sul- 
phurets of antimony and arsenic are readily soluble in sulphuret 
ammonium, these metals if present would be in the filtrate, 
"rhile the sulphurets of mercury, lead, and copper, being insol- 
able in this menstruum, would remain on the filter, which should 
therefore be reserved for future examination if necessary. The 
amrnoniacal filtrate is now evaporated to dryness, and the resi- 
due treated with nitric acid and potash in the manner already 
described. Any arsenic present would now exist as arsenate of 
P°tash, and the solution when treated with sulphuretted hydro- 
gen yield a yellow precipitate of pentasulphuret of arsenic. If 
this metal was not present, and the mixture contained anti- 
m°ny, the results already described would of course be ob- 
tained. Should these two metals occur in the same solution, 
ey may be separated by treating the mixture with zinc and 
acid and receiving the evolved gas in a solution of 
titrate of silver, in the manner heretofore pointed out. 236 
ANTIMONY. 
From the Tissues.—The investigations of Orfila, and others, 
have shown that antimony, when taken into the stomach, is 
rapidly absorbed by the blood and deposited in the tissues ; and 
that the absorbed poison may be entirely eliminated from the 
living body within a very few days, the elimination taking place 
chiefly through the urine. Of the different tissues of the body, 
the liver and kidneys usually contain the largest proportion of 
the absorbed poison. 
About one-third of the liver, cut into very small pieces and 
placed in a porcelain dish, may be made into a thin paste with 
water containing about one-fifth of its volume of pure hydro- 
chloric acid. The mixture is then exposed to a moderate heat, 
with frequent stirring and the occasional addition of small quan- 
tities of powdered chlorate of potash, until the organic solids 
have become entirely disintegrated. The cooled mixture is 
transferred to a muslin strainer, and the organic matter left 
upon the cloth well washed with water, the washings being col- 
lected with the first-strained liquid; the solution is then filtered, 
the filtrate concentrated, allowed to cool, and if necessary again 
filtered. The solution is now exposed for several hours to a 
slow stream of sulphuretted hydrogen gas, after which it lS 
allowed to repose for about twenty-four hours, in order that the 
precipitate may fully subside. Any precipitate thus obtained 
is collected, charred by nitric acid, fused with potash, and the 
residue examined in the manner described above. 
For the recovery of absorbed antimony, Orfila recommended 
to decompose the organic matter by nitric and sulphuric acids* 
The tissue, cut into small pieces, is boiled with nitric acid, the 
homogeneous mixture evaporated to dryness, and the residue 
well charred with concentrated sulphuric acid. The dry car- 
bonaceous mass is then boiled with hydrochloric acid containing' 
a few drops of nitric acid, when any antimony present will be 
dissolved as chloride. The solution thus obtained is introduced 
into the apparatus of Marsh, and the evolved gas examined b1 
the usual manner. 
Absorbed antimony may also be recovered by boiling tb6 
finely divided tissue with pure hydrochloric acid diluted with 
about six volumes of water, and introducing into the boiling QUANTITATIVE ANALYSIS. 
237 
fixture separate slips of bright copper-foil as long- as they con- 
tinue to receive a metallic coating. Only a small slip of the 
copper should at first be employed. Should this after several 
minutes fail to receive a deposit, it is removed from the mix- 
ture and the boiling continued until the organic tissue is entirely 
broken up. The cooled mixture is then strained, and the 
strained liquid again boiled with a fresh slip of copper, the 
boiling being continued if necessary until the liquid is evap- 
orated to near dryness. It may be remarked that this method 
Would not apply to organic mixtures which had been prepared 
by means of chlorate of potash, since the products of this salt 
'Would prevent the deposition of the antimony. 
Quantitative Analysis.—The solution, acidulated with hy- 
drochloric acid, is treated with sulphuretted hydrogen gas as 
bmg as a precipitate is produced, and the mixture gently 
Warmed until the supernatant liquid has become perfectly clear. 
The precipitate is then collected on a filter of known weight, 
Washed, thoroughly dried on a water-bath, and weighed. Every 
°lle hundred parts by weight of tersulphuret of antimony thus 
obtained, correspond to 85-74 of the teroxide, or 202-85 parts 
°f pure crystallised tartar emetic. 238 
ARSENIC. 
CHAPTER Y 
ARSENIC. 
I. Metallic Arsenic. 
History and Chemical Nature.—By the term arsenic, the 
chemist understands a certain simple or elementary form of 
matter, having metallic properties; this term, however, is pop' 
ularly applied to an oxide of the metal—arsenious acid. The 
symbol for arsenic is As; and its combining equivalent 75. 
According to Walchner, minute quantities of this metal are 
present in all chalybeate waters and the deposits formed from 
them, and in a great variety of ferruginous clays, marls, and 
slates. (Grmelin’s Hand-Book, vol. iv, p. 250.) The statement 
formerly made by Orfila that arsenic occurred as a normal con- 
stituent in the bones and muscles of animals, was afterwards 
retracted as incorrect. 
In its pure state, arsenic has a steel-grey color, a bright 
metallic luster, and a density of about 5-8; it has a crystalline 
structure, and is readily reduced to powder, being very brittle- 
It remains unchanged in dry air; but in the presence of moist- 
ure, it slowly absorbs oxygen and assumes a dull dark-gi’Y 
appearance. When heated, it volatilises, without fusing, into a 
colorless vapor, which on coming in contact with the air emit8 
a garlic-like odor; if strongly heated in the open air, it takes 
fire and burns with a bluish flame and the evolution of dense 
white fumes of arsenious acid. It is generally stated that 
arsensic volatilises at a temperature of about 400° F.; 
according to the observations of Dr. J. K. Mitchell it requiroB 
for this purpose a dull red heat. Hot sulphuric and nitric acid8 
oxidise and dissolve the metal, the former as arsenious and the 
latter as arsenic acid. Hydrochloric acid has no action np°n 
it; but free chlorine converts it into chloride of arsenic. CHEMICAL PROPERTIES. 
239 
Physiological Effects.—Metallic arsenic, when taken into the 
system, is capable of acting as a powerful poison; but, perhaps, 
°nly in so far as the metal becomes oxidised and converted into 
arsenious acid. From the experiments of Bayen and Deyeux, 
and others, it would appear that the metal in its uncombined 
state was inert. The substance sold in the shops under the 
name of fly-powder, consists essentially of a mixture of metallic 
arsenic and arsenious acid, the latter usually being present, it 
18 said, in the proportion of about five per cent. Numerous 
instances of poisoning by this substance have occurred, chiefly, 
however, as the result of accident. In a recent case of crim- 
inal poisoning by fly-powder, in which we were consulted, death 
took place in thirty-six hours; and although there had been 
almost incessant vomiting for over thirty hours, a quantity of 
arsenic equivalent to forty-two grains of arsenious acid remained 
m the stomach at the time of death. The symptoms and morbid 
changes produced by this substance are much the same as those 
occasioned by arsenious acid. 
Special Chemical Properties.—There is little difficulty in 
recognising metallic arsenic. When volatilised in a narrow 
reduction-tube, it condenses in the cooler portion of the tube, 
forming a very characteristic sublimate. This sublimate usually 
consists of two well-defined but conjoined parts, the lower of 
which has a steel-like appearance, and when viewed on the 
xoside presents a crystalline structure, 
resembling somewhat that of fractured 
lr°ft| the upper part of the deposit, 
>vhen viewed exteriorly, is destitute 
°f luster, and of a dark color, which 
gradually fades into a light-grey mar- 
£>l]b in which crystals of arsenious 
acid are sometimes found. When the 
Climate is quite thin, it presents a brown appearance. On 
le application of heat, the sublimate is readily chased up and 
°Wn the tube, and sooner or later becomes converted into 
"Ifite, octahedral crystals of arsenious acid; this conversion is 
hastened if the closed end of the tube has been separated, 
uese reactions are peculiar to arsenic. 
Tubes for Sublimation of Arsenic. 240 
ARSENIC. 
If metallic arsenic be dissolved, by tbe aid of heat, m 
strong nitric acid, and the solution evaporated to dryness, d 
leaves a white residue of arsenic acid, which when moistened 
with a strong solution of nitrate of silver, assumes a brick- 
red color. A portion of the arsenic acid obtained by this 
method, may be dissolved in water and submitted to the liquid 
tests for .this acid, mentioned hereafter; or, the solution may 
be saturated with sulphurous acid gas, the excess of the gas 
expelled by heat, and the solution then examined for arse- 
nious acid. 
Compounds of Arsenic.—Arsenic forms with oxygen, two well- 
defined oxides, ilamely, arsenious acid (Aso3) and arsenic acid 
(Asos). A lower, or suboxide, has also been described, but its 
existence is doubtful. Arsenic unites with sulphur in several 
proportions; the most important of these compounds are: bisul- 
phuret of arsenic, or Realgar (AsS2), which has a ruby-red 
color; tersulphuret of arsenic, or Orpiment (AsS3), having a 
bright-yellow color; and pentasulphuret of arsenic (AsS5), the 
color of which closely resembles that of orpiment. With hydro- 
gen, the metal forms arsenuretted hydrogen (AsH3), which is a 
colorless, highly poisonous, gaseous compound. Arsenic also 
enters into various other combinations. 
All the soluble compounds of this metal, and such insoluble 
combinations as undergo decomposition when taken into the 
system, are poisonous. As a general rule, their activity in 
this respect is in proportion to their solubility. Some of the 
insoluble compounds as usually met with, not unfrequently con- 
tain arsenious acid. This is the only compound of the metal 
that will be considered in detail; in its consideration, however, 
the chemical properties of several of the other compounds wdl 
be very fully described. 
11. Arsenious Acid 
Arsenious acid, commonly called white arsenic, and also 
known as rats-bane, is a compound of one chemical equivalent 
of arsenic with three equivalents of oxygen; its combining 
equivalent is 99. It is readily obtained by volatilising metalhc PHYSIOLOGICAL EFFECTS. 
241 
arsenic in a free supply of air. For commercial purposes, it 
is usually prepared by roasting some one of the ores of the 
metal in a reverberatory furnace communicating with large 
chambers, in which the acid condenses. 
This substance is found in the shops under two different 
forms; either as a white or dull white, opake powder, or in the 
form of large, hard masses. If recently prepared, these masses 
are colorless, and transparent; but on exposure to the air, they 
become opake, and of a white or yellowish-white color. This 
change, from the transparent to the opake state, has been 
ascribed to the absorption of moisture. Arsenious acid seems 
to be nearly or entirely destitute of taste. At least, it has 
frequently been swallowed in large quantity without any marked 
taste being perceived; in other instances, however, its taste 
fas been variously described as sweetish, rough, hot, acrid, or 
metallic. 
Symptoms.—These are subject to great variation. Sooner 
°r later after a large dose of the poison has been swallowed, 
there is usually a sense of heat and constriction in the throat, 
With thirst, nausea, and burning pain in the stomach. The 
Pain becomes excruciating, and is attended with violent vomit- 
and retching; the matters vomited present various appear- 
ances, being sometimes streaked with blood, and at others of 
a bilious character; the pain in the stomach is increased by 
pressure. As the case progresses, the pain extends throughout 
le abdomen, and there is generally severe purging, and tenes- 
mus; the matters passed from the bowels not unfrequently con- 
fain blood. The thirst usually becomes very intense; in some 
there is great difficulty of swallowing. The features 
'le collapsed and expressive of great anxiety; the pulse is 
Tuck, small, and irregular; the eyes red; the tongue dry, and 
lri'ed; the skin cold and clammy, but sometimes hot; the 
espiration difficult; and sometimes there are violent cramps 
the legs and arms. The urine is frequently diminished in 
Tmntity, and, its passage attended with great pain. Stupor, 
j miuin, paralysis, and convulsions have also been observed, 
j many instances, death takes place calmly, and the intel- 
ectual faculties remain clear to the last. 242 
ARSENIC. 
Such are the symptoms usually observed in poisoning by 
arsenic; but cases are reported in which the abdominal pain? 
thirst, vomiting, and purging were either very slight or entirely 
absent. In these instances, the symptoms are usually not very 
unlike those commonly observed in poisoning by a narcotic. 
There is generally great prostration of strength, and faintness, 
or even actual syncope; often convulsions, and sometimes delir- 
ium or insensibility. It was formerly believed that well-marked 
gastric symptoms were absent only when a very large dose of 
the poison had been taken; but this is by no means always 
the case. 
In a case of arsenical poisoning mentioned by Dr. Christi- 
son, an individual expired in five hours without at any time 
having vomited, although emetics were administered. The fol- 
lowing case of this kind is reported by Mr. Fox. (London 
Lancet, Nov. 4, 1848.) A stout, healthy young man, took a 
teaspoonful of arsenious acid, mistaking it for flour. No marked 
symptom of the action of the poison appeared for nearly six 
hours afterwards, when purging suddenly supervened, and he 
vomited two or three times. He then became drowsy; coun- 
tenance sunken and livid; pulse rapid, and extremely feeble; 
surface of the body cold, and watery stools of a greenish hue 
passed involuntarily. He answered questions rationally, and 
neither complained of pain, tenderness of the abdomen, tenes- 
mus, nor any of the usual irritative symptoms of arsenical 
poisoning. Soon afterwards he complained of dimness of sight? 
laid down on the bed, and in a few minutes expired. 
In most cases of acute poisoning by this substance, the 
symptoms steadily run their course; yet sometimes there is a 
remission or even an entire intermission of the more prominent 
symptoms. This remission may extend through a period of 
several hours, and the symptoms then return with increased 
violence. The remission has even been repeated several times 
in the same case. 
Considerable variety has also been observed in regard to 
the time within which the symptoms first manifest themselves- 
In most instances, however, they appear in from half an honi 
to an hour after the poison has been taken. In a case cited EFFECTS OF EXTERNAL APPLICATION. 
243 
by Dr. Beck, a woman, who had swallowed a quantity of the 
poison mixed with wine and an egg, experienced extreme dis- 
tress immediately after taking the mixture. (Med. Jur., ii, p. 
595.) In another instance, quoted by the same writer, twelve 
persons in one family, were seized with symptoms immediately 
after eating some soup containing the poison. Dr. Christison 
quotes a case in which the symptoms appeared in eight inm- 
ates; and two others in which violent symptoms were present 
m ten minutes after the poison had been taken. 
On the other hand, instances are related in which the 
symptoms were delayed much beyond the usual period. A 
case of this kind, in which they did not appear for nearly six 
hours, has already been cited. In a case related by Dr. Ryan, 
where half an ounce of arsenic was taken in porter, the first 
symptom, which was vomiting, did not occur until nine hours 
afterwards. (Wharton and StilD, Med. Jur., p. 513.) A case 
18 also quoted by Dr. Taylor, from Belloc, in which ten hours 
elapsed before any symptoms appeared. (On Poisons, p. 359.) 
And Dr. Wood mentions an instance (U. S. Dispensatory, 
1865, p. 26), related by Dr. E. Hartshorne, in which at least 
a drachm of arsenious acid had been swallowed, and where the 
symptoms of poisoning were delayed for sixteen hours. This 
seems to be the most protracted case, in this respect, vet 
recorded. 
The external application of arsenic to abraded surfaces has 
n°t been followed by fatal results. In a case 
reported by Dr. McCready, a wash composed of a mixture of 
arsenious acid and gin, applied to the head of a child two 
years old, affected with porrigo favosa, caused death in about 
hours. The most prominent symptoms were swelling 
°l* the face, purging and tenesmus, with paralysis of the lower 
extremities. No local inflammation was produced. Two other 
ebildren who were similarly treated, suffered with redness and 
of the face; but they speedily recovered. (Am. Jour. 
. 6(b Sci., July, 1851, p. 259.) Dr. Christison cites an instance 
111 Ayhich the stearine of a candle containing arsenic, applied to 
a blistered surface, produced local pain, nausea, pain in the 
sf°mach, great thirst, redness of the tongue, spasms of the 244 
ARSENIC. 
muscles of the lower extremities, weakness and irregularity of 
the pulse, followed by death within twenty-four hours after the 
application had been made. 
Arsenic has also proved fatal when applied to the mucous 
membrane of the vagina, and of the rectum, and when inhaled 
in the form of vapor. In a case reported by Dr. Mangor, a 
man poisoned three wives in succession by introducing arsenic 
into the vagina. In at least two of these instances, the poison 
produced its usual symptoms and death in twenty-four hours. 
Within the last several years, numerous instances of chronic 
poisoning by this substance have occurred from persons occu- 
pying rooms hung with paper stained with Scheele’s green, or 
arsenite of copper. In these cases the results are due to por- 
tions of the coloring matter becoming detached and inhaled. 
Period when Fatal.—ln fatal poisoning by this substance, 
death usually occurs in from twelve to thirty-six hours, after 
the poison has been taken. Numerous instances, however, are 
related in which death took place within a very few hours j 
while on the other hand, life has not unfrequently been pro- 
longed for several days. The shortest period within which the 
poison has yet destroyed life, seems to be two hours ; and at 
least three instances of this kind are on record. In a case 
related by Dr. Dymock, death occurred in two hours and a 
half ; and Pyl relates another, which proved fatal in three hours. 
(Christison on Poisons, p. 240.) Ninety grains of the poison 
caused the death of a girl, aged fourteen years, in five hours* 
Several instances are reported in which the patients recovered 
from the primary action of the poison, and died from its second- 
ary effects very long periods afterwards, even in one instance; 
related to Wepfer, after the lapse of three years. 
Fatal Quantity.—According to the observations of Prof* 
LacheSse, of Angiers, a dose of from one to two grains of arse- 
nious acid may prove fatal to a healthy adult; a dose of from 
a quarter to half a grain may induce symptoms of poisoning ? 
and one-eighth of a grain may prove injurious. (Beck’s Med* 
Jur., vol. ii, p. 544.) In a case quoted by Dr. Taylor, two 
grains of the poison, in the form of Fowler’s solution, taken 111 
divided doses during a period of five days, destroyed the life ANTIDOTES. 
245 
a woman. The same writer cites another instance, reported by 
Dr. Letheby, in which two grains and a half killed a robust, 
healthy girl, aged nineteen, in thirty-six hours. (On Poisons, 
p. 877.) In a case mentioned by Dr. Christison, four grains 
and a half caused the death of a child, four years old, in six 
hours. 
On the other hand, recovery has not unfrequently taken 
place after very large quantities of the poison had been swal- 
lowed. In a case recorded by Dr. Pereira, a man swallowed 
half an ounce of powdered arsenic immediately after taking 
bis dinner, and the only effect produced was violent vomiting. 
(Mat. Med., i, p. 682.) So also, Dr. A. Stille (Mat. Med., ii, 
"07) quotes the case of a woman who swallowed about a dessert- 
spoonful of the poison immediately after a hearty meal, and 
although vomiting did not occur, nor were any remedies admin- 
istered for an hour and a half, yet within five days complete 
recovery had taken place. 
The following remarkable case is reported by Dr. W. C. 
Jackson. (Am. Jour. Med. Sci., July, 1858, p. 77.) A young 
man, aged twenty-eight years, took on an empty stomach not 
Dss than two ounces of the poison. Nearly two hours after- 
wards there was slight vomiting, with some traces of the 
arsenic; but the greater part of the poison was retained in 
fbe body for six hours. Great irritability of the stomach then 
aasued, with a burning sensation in this organ and in the throat. 
Jbis condition continued for about six hours, after which the 
patient rapidly recovered. 
Treatment.—This consists in the first place in the speedy 
administration of an emetic j or the stomach may be emptied 
means of the stomach-pump. As an emetic, sulphate of 
mnc or of copper may be employed; if neither of these is at 
band, powdered mustard or a mixture of salt and water should 
e administered, or vomiting may be induced by tickling the 
tbroat with a feather. The vomiting should be assisted by the 
bee exhibition of demulcent drinks. For this purpose, a mix- 
bire of milk and white of egg has been highly recommended. 
tbe poison has passed into the bowels, a dose of castor oil 
may be highly useful. 246 
ARSENIC. 
Of the various chemical antidotes that have been proposed 
for arsenious acid, the hydrated sesquioxide of iron (Fe2o3, 3 HO), 
is much the most important. Drs. Bunsen and Berthold, m 
1834, were the first to assert the antidotal properties of this 
substance. When it is added to a solution of arsenious acid, 
the latter is rendered wholly, or very nearly so, insoluble in 
water. In support of this statement, we may adduce the fol- 
lowing experiments. 1. One grain of arsenious acid, in solu- 
tion, was agitated for a very little time with five grains of the 
iron preparation suspended in half an ounce of water, and the 
mixture quickly filtered. The filtrate was then examined and 
found to contain less than the 100 th part of a grain of the 
poison. 2. When ten parts of the iron preparation were em- 
ployed, and the filtrate concentrated to one hundred fluid-grains, 
then acidulated with hydrochloric acid, and saturated with sul- 
phuretted hydrogen gas, it failed to yield any distinct evidence 
of the presence of the poison, even after standing at a moderate 
temperature for several hours. These experiments do not, of 
course, prove that the compound thus produced is insoluble in 
the acid secretions of the stomach ; yet, the excess of the iron 
preparation administered, might neutralise any free acid present. 
The antidotal action of this substance seems to be due to 
the sesquioxide of iron giving up a portion of its oxygen to the 
arsenious acid, whereby the latter is converted into arsenic 
acid, while the former is reduced to the protoxide of iron 
(2 Fe2 03 +AsO3 = 4 FeO + As05). The arsenic acid thus pro- 
duced, by uniting with a portion of the protoxide of iron, forms 
an arsenate of iron, which, being insoluble, is inert. Theoret- 
ically, therefore, one part of arsenious acid requires 2T5 parts 
of the pure hydrated sesquioxide to render it inert. The anti- 
dote should however be given in its moist state, and be admin- 
istered in large excess. It is usually stated that about twelve 
parts of the moist compound are required for one part of arse- 
nious acid. 
Hydrated sesquioxide of iron may be readily prepared by 
precipitating the muriated tincture of the shops by an excess 
of ammonia, collecting the precipitate on a muslin strainer, and 
washing it with water until it no longer emits the odor <4 ANTIDOTES. 
247 
ammonia. A tablespoonful or more of the moist magma, mixed 
with a little water, may be given as a dose. It should always 
be freshly prepared. 
In this connection, we may very briefly refer to some ex- 
periments, kindly undertaken by Dr. Win. Watt, with this 
antidote upon poisoned dogs (For details, see Ohio Med. and 
Surg. Jour., March, 1861). The action of the poison alone was 
hrst determined upon five dogs of average size. To three of 
these, six grains of arsenious acid, in solution, were given to 
each, and proved fatal in one hour and a half, five hours, and 
§ix hours respectively. To the other two, three grains each 
ivere administered, and caused death in six and might hours 
respectively. A solution of the' poison was then administered 
to twelve other dogs, and the dose followed—in some instances 
immediately, in others in ten minutes, and in others still not 
Until symptoms of poisoning had manifested themselves—by a 
single dose of about two tablespoonfuls of the antidote, prepared 
m the manner just described. After vomiting, in some instances 
only once, but in others several times, all these animals recov- 
ered, at most within several hours and without in any instance 
suffering severe symptoms. Two of these dogs received three 
grains • two, four grains; one, five grains; three, six grains; 
two, seven grains ; and two, eight grains each of the poison. 
another experiment, six grains of the poison, in solution, 
ivere mixed with about fifteen parts by weight of the antidote, 
and the mixture, after standing twenty minutes, given to a 
(I°g; no appreciable effect whatever was observed, although 
*be animal was closely watched for many hours. This experi- 
ment, therefore, indicates that the arsenate of iron is not readily 
by the juices of the stomach. 
Numerous instances are reported in which there seems to be 
a° doubt that this antidote was the means of saving life in the 
. Ulnan subject. Mr. Robson relates an instance of this kind, 
111 Avbich more than a drachm and a half of the poison had been 
fallowed, and the antidote was not administered until two 
Urs after the poison had been taken. In this case, about an 
ollr after the ingestion of the poison, the stomach-pump was 
llSed, but unsuccessfully, on account of the instrument becoming 248 
ARSENIC. 
choked with the remains of food. (U. S. Dispensatory, 1860, 
p. 29.) It need hardly be remarked that the antidote can have 
no effect upon any of the poison that has already entered the 
circulation. 
Post-mortem Appearances.—Great variety has also been 
observed in regard to these, even in cases in which the symp- 
toms during life were very similar. The lining membrane of 
the throat and oesophagus has in some few instances been found 
highly inflamed. The mucous membrane of the stomach is gen- 
erally more or less reddened and inflamed; sometimes it has a 
deep crimson color, at others it is of a deep brownish-red, and 
it has presented a dark appearance, due to the effusion of 
altered blood. This membrane is sometimes much softened, 
and easily separated; and in some instances patches of it are 
entirely destroyed. In other instances, however, it is much 
thickened, and corrugated. The inflammation rarely extends 
to the peritoneal covering of the stomach. When the poison 
has been taken in the solid state, small particles of it are fre- 
quently found adhering to the mucous membrane and cov- 
ered with coagulated mucus. Ulceration of the stomach has 
been of rare occurrence, except in protracted cases; how- 
ever, Dr. Taylor observed it in a case that proved fatal m 
ten hours. 
In protracted cases, the intestines, particularly the duode- 
num and rectum, not unfrequently present signs of inflammatory 
action similar to those found in the stomach. The lungs are 
sometimes congested and inflamed; congestion of the brain has 
also been observed. The blood throughout the body is usually 
liquid, and of a dark color. Not a few instances of poisoning 
by this substance are recorded in which after death no well- 
marked morbid appearances were discovered in any part of the 
body. This result has even been observed in cases in which 
there were violent symptoms, and life was prolonged for many 
hours. 
Antiseptic Properties of Arsenic.—The preservative power 
of arsenic when brought in direct contact with animal textures 
is well known; and the poison seems to exert a similar action 
when carried by means of the circulation to the different tissues PRESERVATIVE EFFECTS. 
249 
°f the body. The bodies therefore of those who have died from 
the effects of this poison are not unfrequently found in a good 
state of preservation, even long periods after death. 
We have elsewhere reported a case, described by Dr. 
Douglas Day, in which this preservative action of the poison 
Was well marked in a body that had been buried seventeen 
months. At this time, the body was destitute of odor, and 
the flesh of the extremities had given place to a dark unctuous 
matter. The abdominal walls were in a surprising state of 
preservation and of the color of old parchment; the integu- 
ments upon incision were firm, and the muscles of a pink hue, 
hut very attenuated. The omentum was large and in place, 
aml covered with saponaceous matter. The stomach and intes- 
tines were pale, comparatively dry, and appeared as though the 
convolutions had been pressed together; they were firm and 
flowed free manipulation, and exhaled a peculiar but not offen- 
ce odor. The liver, spleen, and pancreas appeared remark - 
ably recent, and the posterior walls of the abdomen, the mesen- 
tccy and kidneys, were well preserved. The bladder also was 
m a good state of preservation. A very notable quantity of 
arsenic was detected in each of several, of the abdominal organs: 
other parts were submitted to chemical examination. (Ohio 
and Surg. Jour., Nov,, 1863.) 
Dr. Christison quotes a case in which the body after being 
mterred seven years, was found entire. The head, trunk, and 
limbs retained their situation; but the organs of the chest and 
aMomen were converted into a brown soft mass, in which a 
chemical analysis revealed the presence of a considerable quan- 
tity 0f 
arsenic. 
Although the bodies of those who died from the effects of 
fliis poison have thus been found in an unusual state of pres- 
ervation, yet this is by no means always the case, even when 
iim poison remains in the body at the time of death. In fact, 
some cases of arsenical poisoning, the process of putrefac- 
li°n seemed to advance with increased activity. At the same 
it must be borne in mind that the body is sometimes 
preserved in cases in which death resulted from 
01 dinary disease or mechanical injury. 250 
ARSENIC. 
Chemical Properties. 
General Chemical Nature.—lt has already been stated 
that arsenious acid, in its amorphous state, occurs under two 
varieties, known as the transparent and the opake. The spe- 
cific gravity of the transparent variety seems to be some little 
greater than that of the opake, the density of the former, 
according to most observers, being about 3*75, and that of the 
latter about 3'65. These varieties also differ in regard to their 
solubility in water. Arsenious acid volatilises at a temperature 
of about 380° P., into a colorless, odorless vapor, and recon- 
denses on cold surfaces, principally in the form of regular octa- 
hedral crystals. (For an ‘excellent paper on the crystalline 
forms of arsenious acid, by Dr. Guy, see Quart. Jour. Micro. 
Science, July, 1861.) 
Arsenious acid has only feebly acid properties ; nevertheless 
it readily unites with basic oxides forming salts, denominated 
arsenites. These salts are readily decomposed by most other 
acids. The arsenites of the alkalies are freely soluble in water; 
but all other arsenites are either only sparingly soluble or insol- 
uble in this menstruum. The latter salts are readily decom- 
posed and dissolved by nitric and hydrochloric acids. Upon 
the application of heat, most of the arsenites undergo decom- 
position. In this operation, the fixed alkaline arsenites retain 
the greater portion of the arsenic, in the form of an arsenate. 
When ignited with a reducing agent, all arsenites are decom- 
posed with the evolution of metallic arsenic, in the form of 
vapor. 
Solubility. 1. In Water.—The degree of solubility of arse- 
nious acid in water sometimes becomes a matter of considerable 
importance in medico-legal investigations. The results of ob- 
servers in regard to this point have been extremely discordant- 
The exact quantity of the poison that will be taken up and 
retained in solution by a given quantity of water, will depend 
upon a variety of circumstances, among the principal of which 
are the following: 1. The physical state of the acid; 2. The 
relative proportions of the acid and water present; 3. Tune SOLUBILITY IN WATER. 
251 
they have been in contact; 4. The temperature of the mixture; 
If the mixture has been boiled, the length of time the boil- 
lng was continued; and 6. The time that has elapsed since the 
mixture was heated. Among numerous experiments that might 
5e cited showing the influence of these various conditions, the 
following may be mentioned. 
a. One part (50 grains) of finely powdered opake arsenious 
a°id was boiled with ten parts (500 grains) of distilled water 
one hour, the vaporised fluid being condensed and returned 
1° the flask as rapidly as formed, and thus the volume of the 
fluid kept constantly the same. The solution was then filtered 
as rapidly as possible, and a given portion of the filtrate evap- 
orated to dryness on a water-bath. The residue thus obtained 
mdicated that one part of the acid had dissolved in 18T0 parts 
°f water. 
k. A similar experiment with the transparent variety of the 
acid, taken from the same mass as employed in experiment a, 
Save a residue indicating that one part of the acid dissolved in 
parts of water.- According to Bussy, the transparent 
Variety is more soluble than the opake; Guibourt, however, 
states that the reverse is the fact. 
c. A similar experiment with the freshly sublimed crystallised 
acid, indicated that one part of the acid had dissolved in ITSO 
parts of water. 
d. On repeating the last experiment and concentrating the 
filtered solution to about half its volume, a white scum appeared 
apon the surface of the liquid. The clear liquid was then 
Aooanted and a given portion evaporated to dryness, when it 
found that one part of the acid had been held in solution 
y 6*72 parts of water. 
e- After boiling one part of the crystallised acid, from the 
staple used in experiment c, for one hour with ten parts of 
Pure water, without loss of liquid by evaporation, the mixture 
Was allowed to stand twenty-four hours. The solution then 
c°utained one part of the acid in 58*68 parts of water. 
f- One part of the opake acid, from the sample used in 
experinient a, was boiled for one hour with forty parts of water, 
Without loss of liquid by evaporation, and the solution quickly 252 
ARSENIC. 
filtered. The filtrate contained one part of the acid in 43’7 
parts of the menstruum. It will he observed that in this ex- 
periment the conditions were the same as in experiment 
except in the relative proportion of acid and water present. 
Even when one part of the acid is boiled for an hour with one 
hundred parts of water, a portion of the poison will still remain 
undissolved. 
g. One part of the opake acid was treated with twenty parts 
of boiling water and the mixture frequently agitated for twenty- 
four hours. The solution then contained one part of the acid 
in 196 parts of water. 
h. On treating the transparent variety of the acid in the 
same manner as in the last experiment, the solution contained 
one part pf the poison in 93 parts of the menstruum. On 
comparing the experiments g and h with those of a and h, it 
will be observed that under one set of conditions the transparent 
acid dissolved more freely than the opake variety, whilst under 
another the reverse was the case. 
i. One part of the crystallised acid was frequently agitated 
during nine days, at the ordinary temperature, with twenty 
parts of pure water. The resulting solution contained one part 
of the acid in 108 parts of water. 
j. An experiment similar to the last and conducted at the 
same time, with one part of the acid and Jive hundred parts of 
water, yielded a solution which contained one part of acid n1 
810 parts of the menstruum. 
The experiments now cited serve to explain, at least in a 
measure, the discrepant statements of observers in regard to 
the solubility of this substance. Furthermore, it is obvious that 
unless something is known in regard to the conditions under 
which the acid and liquid have been brought in contact, it will 
be impossible to state even approximately how much of the 
poison may have been dissolved, even by pure water. In gen' 
eral terms, if the mixture contained one part of the acid to ten 
or twelve parts of water and has been boiled and concentrated; 
the liquid may hold in solution even as much as one-seventh ol 
its weight of the poison; whilst on the other hand, if there was 
very large excess of water and the mixture was not heated, the SOLUBILITY IN ALCOHOL AND CHLOROFORM. 
253 
liquid may not take up more than the I,oooth part of its weight 
°f the acid. 
Ganelin placed pulverised, opake arsenious acid in various 
proportions of water in closed bottles, and set them aside in a 
cool place for eighteen years, with the following results. One 
Part of the acid in 1,000 parts of water: perfect solution. One 
part of the acid in 100 parts of water: the solution contained 
oae part of acid in 102 parts of water. One part of acid in 
35 parts of water: the solution contained one part of the acid 
lri 54 parts of water. (Hand-book of Chemistry, vol. iv, p. 
According to most observers, the solubility of the poison 
18 more or less diminished by the presence of most kinds of 
organic matter. 
2. In Alcohol.—One part of the crystallised acid, in the state 
°f powder, was frequently agitated for two days with twenty 
parts of alcohol of specific gravity (PBO2 (= 97*5 per cent.). 
The solution thus obtained contained one part of acid in 2,000 
parts of the menstruum. In a similar experiment with the 
aiost common kind of whishj, one part of the acid dissolved in 
380 parts of the liquid. 
3. In Chloroform.—On frequently agitating powdered arse- 
nous acid for two days with twenty parts by weight of pure 
chloroform, two hundred grains of the filtered liquid contained 
less than the I,oooth part of a grain of the acid. 
This experiment would, therefore, indicate that the acid required 
lll°re than 200,000 times its weight of chloroform for solution. 
Absolute ether, under the conditions lust mentioned, failed to 
A* 7 J 7 
absolve a trace of the poison. 
Arsenious acid is readily soluble in solutions of the fixed 
caustic alkalies, but it is much less soluble in ammonia. It is 
also soluble in hydrochloric acid, and in certain of the vege- 
table acids; sulphuric acid dissolves it only in minute quantity, 
nitric acid oxidises and dissolves it to arsenic acid. 
Of Solid Arsenious Acid. 
T If a small quantity of solid arsenious acid be thrown on 
a piece of ignited charcoal or heated on a charcoal support in 254 
ARSENIC. 
the reducing blow-pipe flame, it is dissipated in the form ol 
white fumes and emits a garlic-like odor. In this operation? 
the arsenious acid first gives up its oxygen to the carbon form- 
ing carbonic acid gas ; the metallic arsenic thus set free is then 
reoxidised by the air into arsenious acid, which is evolved and 
gives rise to white fumes. The alliaceous odor emitted is due 
to the reoxidation of the metal, and is only evolved Avhen the 
metal itself is being oxidised. It was formerly supposed that 
this odor was peculiar to arsenic, but it is now known that 
there are several other substances which possess a similar 
odor. 
2. When heated in a reduction-tube, arsenious acid volatil- 
ises without fusing and recondenses in the cooler portion of the 
tube, in the form of minute, octahedral crystals. Under the 
microscope, this sublimate is quite peculiar, and the crystals 
present the appearances illustrated in Plate IV, fig. 5. When 
only a very minute quantity of the poison is thus sublimed, the 
crystals are exceedingly small, but still perfectly characteristic. 
Under an amplification of one hundred diameters, the angular 
nature of a crystal that does not exceed the B,oooth part of an 
inch in diameter may be readily recognised; and with a power 
of two hundred and fifty, crystals measuring only the 15,000 th 
part of an inch in size, may be satisfactorily determined. 
sufficient sublimate be obtained, the portion of the tube contain- 
ing it may be boiled in a small quantity of pure water, and the 
solution thus obtained, after concentration if necessary, exam- 
ined by the liquid tests mentioned hereafter. 
In applying this test to only a minute quantity of the poison, 
the bore of the reduction-tube should not exceed the 16th part 
of an inch in diameter. Or, after placing the arsenious acid n1 
a tube of this kind having thin walls, the tube may be carefull} 
heated at a little distance above the point occupied by the 
poison, in a small blow-pipe flame, and drawn out into a cap!!' 
lary neck; the poison is then sublimed into the contracted p°r' 
tion of the tube. By this method the least visible quantity 
the poison will yield a very satisfactory sublimate ; at the same 
time, this method permits the application of the higher powers 
of the microscope, for the examination of the sublimate. REDUCTION-TE ST. 
255 
Professor Guy recommends (Cliem. News, vol. i, p. 200) to 
heat the arsenious acid in a perfectly dry tube of small diam- 
eter and about three-quarters of an inch in length and having 
hs mouth covered with a warm slide or disc of glass. The 
crystals are deposited partly on the sides of the tube, but chiefly 
011 the glass cover. This method offers the advantage of having 
fhe deposit upon a flat surface for examination by the micro- 
scope ; in point of delicacy, however, it is very far inferior to 
the preceding method. 
In applying this sublimation-test to a suspected substance, 
A must be borne in mind that there are other white powders, 
besides arsenious acid, as salts of ammonia, oxalic acid, and 
corrosive sublimate, which when heated in a reduction-tube may 
yield a crystalline sublimate. But most, if not all, of these fal- 
lacious substances melt before volatilising, and none of them 
condense in the form of octahedral crystals. 
3. Reduction-test.—lf a small quantity of arsenious acid be 
placed in the closed end of a narrow reduction-tube, or in the 
end of a tube drawn out in the form shown in Fig. 5, and a 
''-vedge of recently ignited charcoal, h, 
placed in the tube a little distance 
above the arsenical fragment or powder, 
011 heating the charcoal to redness by 
flame of a spirit-lamp and then 
slowly erecting the outer end of the 
tube so that the flame may still heat the charcoal and at the 
time volatilise the arsenious acid, the latter will be deox- 
idised in its passage over the ignited charcoal and yield , a sub- 
limate, c, of metallic arsenic. This reduction may also be 
effected by mixing the arsenious acid with a perfectly dry 
fixture of powdered charcoal and carbonate of soda, and heat- 
-IXIS the whole in a plain or bulbed reduction-tube. 
The sublimate thus obtained usually consists of two well- 
defined parts, the lower of which has a bright mirror appear- 
ailCe resembling polished steel; while the upper has a darker 
c‘°lor, is destitute of luster, and is gradually lost in a light-grey 
Tim inner surface of the sublimate, especially of the 
"er ring, presents a bright crystalline appearance. Sometimes 
Tube for the reduction of Arseni- 
ous Acid by Charcoal. One-third 
natural size. 256 
ARSENIC. 
the upper portion of the sublimate, when very thin, has a 
brownish color. So also, sometimes its upper margin contains 
crystals of arsenious acid. 
If the closed end of the tube be removed and the sublimate 
then heated, it is readily volatilised and oxidised into arsenious 
acid, which condenses in octahedral crystals. The metallic 
sublimate is soluble in a solution of hypochlorite of soda or of 
lime. This confirmatory test may be applied by removing the 
lower end of the tube, and then immersing the latter in a small 
quantity of the soda solution; or, a few drops of the solution 
may be drawn into the tube, after the removal of its closed 
end, by suction with the mouth. The upper portion of the 
sublimate readily disappears when moistened with this liquid, 
but the lower part requires some little time for solution; some- 
times the deposit becomes detached and drops out of the tube, 
in the form of a metallic ring. The arsenical nature of the 
sublimate may also be shown by dissolving it in a few drops 
of warm nitric acid, evaporating the solution to dryness by a 
moderate heat, and touching the residue with a drop or two of 
a strong solution of nitrate of silver, when it will assume a 
brick-red color, due to the formation of arsenate of silver. 
One of the best methods yet proposed for the reduction of 
solid arsenious acid, and which is equally applicable for arse- 
nites and the sulphurets of arsenic, is by means of a pW' 
fedly dry mixture of about equal parts of carbonate of soda 
and cyanide of potassium. A small 
portion of the arsenical compound 
introduced into the bulb of a tube of 
the form shown in Fig. G, A, or of 
the form B as first proposed by Ber- 
zelius, and covered with several times 
its volume of the above mixture. 
gentle heat is then applied, first to 
the neck of the tube and afterwards 
to the bulb; if in this operation, any 
moisture condenses within the tube, d 
should be carefully removed. On now strongly heating the nur- 
ture, the compound under examination will be reduced and yield 
Tubes for the reduction of Arsenious 
Acid. FALLACIES OF REDUCTION-TEST. 
257 
a metallic sublimate, at about the point h. This reaction is ex- 
tremely delicate, especially when performed in a Berzelius-tube. 
When only a very minute quantity of the arsenical com- 
pound is to be reduced, it may be placed in the closed end of 
mi ordinary reduction-tube, covered by the reducing mixture, 
aml the tube then heated at a little distance above the mixture, 
111 a blow-pipe flame, and drawn out into a contracted neck, as 
represented in Fig. 6, C. After the neck of the tube has 
cooled, the arsenical mixture is heated in the manner above 
described. A mixture containing only the I,oooth part of a 
grain of arsenious acid when treated after this method, in a 
lube having its neck contracted to about the 20th of an inch 
111 diameter, will yield a very satisfactory metallic sublimate, 
which upon resublimation further up the neck of the tube will 
furnish several hundred crystals of arsenious acid, many of 
them measuring the I,oooth of an inch in diameter. 
As a reducing agent for arsenious acid, arsenites, and the 
srdphurets of arsenic, as well as for other metallic compounds, 
E. Davy, of Dublin, has recently recommended the ferro- 
cyanide of potassium, or yellow Prussiate of potash, previously 
dried at a temperature of 212°. (Chemical News, vol. iii, p. 
-<SB.) This salt has an advantage over the cyanide of potas- 
Slmn, in that it does not readily absorb moisture from the 
utmosphere. The arsenical compound is mixed with about six 
°r eight times its volume of the dried salt, and the mixture 
fused in one or other of the reduction-tubes already described. 
Tl • */ 
J-ue mixture blackens before fusing. In point of delicacy, the 
faction of this reducing agent is quite equal to that of the 
Cyanide of potassium. 
Fallacies.—When, by either of the above methods of re due- 
*lolb a metallic sublimate having the physical and chemical 
Properties described, is obtained, there is no doubt whatever 
°f the presence of arsenic. Compounds of mercury, cadmium, 
Curium, and selenium may under similar circumstances yield 
Sublimates. These however may be readily distinguished from 
e arsenical sublimate, even by the naked eye; under, the 
they would be found to consist of globules or drops. 
°reover, neither of these sublimates when revolatilised. will, 258 
ARSENIC. 
like arsenic, furnish octahedral crystals ; nor are they soluble 
in a solution of hypochlorite of soda. Neither will they, when 
dissolved in hot nitric acid and the solution evaporated to dry- 
ness, leave a residue which assumes a brick-red color when 
moistened with a solution of nitrate of silver. 
It has also been stated, that a crust of charcoal or the 
employment of a reduction-tube containing lead, might lead to 
error; but it is difficult to conceive how either of these results 
could be mistaken for an arsenical sublimate by any one at all 
conversant with the physical appearances of the latter. Anti- 
mony, which as we shall see hereafter is a source of fallacy 
to some of the tests for arsenic, fails to yield a sublimate when 
it or any of its compounds is exposed to the action of either ot 
the above reducing agents, in the manner described. 
Of Solutions of Arsenious Acid. 
Pure aqueous solutions of arsenious acid have only a feeble 
acid reaction. This reaction is common to both varieties of the 
acid, and is still manifest in a solution containing only the 
I,oooth part of its weight of the poison. On allowing a drop 
of a solution of this kind to evaporate spontaneously to dryness, 
for convenience on a glass-slide, the acid will be left chiefly 111 
the form of white, octahedral crystals, which are readily dissi- 
pated by heat. The residue thus obtained from the 100 th purl 
of a grain of the acid, will usually contain many crystals that 
measure the I,oooth of an inch in diameter. Equally sat- 
isfactory results may be obtained from the I,oooth part of a 
grain of the poison, but the crystals are usually quite small- 
From the 10,000 th part of a grain of the acid, the crystals are 
very minute, but under the higher powers of the microscope 
their true nature may be very satisfactorily determined. The 
production of these octahedral crystals, completely vaporisable 
by heat, is peculiar to arsenious acid. The dry residue thus 
obtained may, of course, be examined by any of the tests 
already mentioned for the poison in its solid state. 
In the following investigations in regard td the behavior ot 
solutions of arsenious acid, solutions of the pure crystallised AMMONIO-NITRATE OF SILVER TEST. 
259 
acid were employed. The fractions indicate the amount ot 
anhydrous acid present in one grain of the solution. The 
results, unless otherwise stated, refer to the reactions of one 
grain of the solution. 
1. Ammonio-Nitrate of Silver. 
This reagent is prepared by cautiously adding a dilute solu- 
tion of ammonia to a solution of nitrate of silver, until the 
merest trace of the precipitate first produced remains undis- 
solved. It is important that the proper quantity of ammonia 
be added: since if there is deficiency, the reagent will also 
produce yellow precipitates with solutions of the alkaline phos- 
phates and silicates; whilst, on the other hand, if there is 
excess, it occasions no precipitate or only a partial one, with 
arsenious acid. The reagent should always be freshly prepared. 
Nitrate of silver alone produces at most only a slight turbidity 
rn solutions of free arsenious acid; but with neutral arsenites, 
d behaves in the same manner as the ammonio-nitrate with the 
free acid. This test was first proposed, in 1789, by Mr. Hume, 
°f London. 
Ammonio-nitrate of silver throws down from aqueous solu- 
tions of arsenious acid a bright yellow precipitate of tribasic 
ursenite of silver (3 AgO ; As03), which is readily soluble, to a 
colorless solution, in ammonia and in nitric and acetic acids. 
-The precipitate is sparingly soluble in nitrate of ammonia, 
sut insoluble in the fixed caustic alkalies. Hydrochloric acid 
decomposes it with the formation of white insoluble chloride of 
silver. 
N Tow grain of arsenious acid, in one grain of water, yields 
with the reagent a copious, bright yellow, amorphous pre- 
cipitate, which after a little time becomes converted into 
yellowish-brown crystals, of the forms illustrated in Plate 
IY, fig. 6. The crystals closely adhere to the glass upon 
which they have formed, and are insoluble in large excess 
of ammonia and of acetic acid. 
'' IToWo grain, yields a rather copious precipitate, which partly 
becomes crystalline. 260 
ARSENIC. 
3. 3700-0 grain: a quite good deposit, which remains amorphous. 
4. ToToiTo grain: an immediate, yellowish turbidity, and in a 
5. grain: after a little time, the mixture becomes very 
little time, small, yellow flakes. 
distinctly turbid, and when viewed over a white surface, 
as white paper, presents a slight yellow tint. Ten grains 
of the solution yield an immediate yellowish turbidity, and 
after a little time small flakes having a decided yellow 
color. When examined in large quantity, solutions even 
much more dilute than this, will yield very distinct re- 
actions. 
If the arsenite of silver thrown down by this reagent be 
decomposed by slight excess of hydrochloric acid and the chlo- 
ride of silver separated by a Alter, the clear acid filtrate will 
yield with sulphuretted hydrogen gas, a bright yellow precipi- 
tate of tersnlphuret of arsenic, having the properties to be 
pointed out hereafter. When the arsenite of silver is washed, 
thoroughly dried, and heated in a reduction-tube, it undergoes 
decomposition with the production of a sublimate of octahedral 
crystals of arsenious acid ; when heated in a similar manner 
with a reducing agent, such as ferrocyanide of potassium, it 
yields a sublimate of metallic arsenic. By either of these 
methods, the arsenical nature of very minute quantities of .the 
silver-precipitate may be fully established. 
Fallacies.—Ammonio-nitrate of silver also produces in solu- 
tions of free phosphoric acid a yellow, amorphous precipitate, 
which is readily soluble in nitric acid and in ammonia*, this 
precipitate always remains amorphous. So, also, the reagent 
produces a somewhat similar precipitate in solutions of free 
vanadic acid; but these solutions, unlike those of arsenious 
acid, have a yellow color. Both free phosphoric and vanadic 
acids, especially the latter, are extremely rare, and therefore 
not likely to be met with in medico-legal investigations. The 
properly prepared reagent fails to produce a precipitate in solu- 
tions of the salts of either of these acids. Again, solutions of 
the alkaline iodides and bromides yield with the reagent yellow- 
ish precipitates; but these precipitates are insoluble in dilute 
nitric acid, and only slightly soluble in caustic ammonia. AMMONIO-SULPHATE OF COPPER TEST. 
261 
It need hardly he remarked that neither of the above pre- 
cipitates, when dried and heated either alone or with a reducing 
agent, in a reduction-tube, will yield an octahedral or metallic 
sublimate. Neither of the above acids is a source of fallacy to 
any of the other tests for arsenic. 
Should arsenious acid and a chloride, as common salt, occur 
in the same solution, the latter compound will yield with the 
silver reagent a white precipitate of chloride of silver, which 
will obscure the arsenical reaction. From a mixture of this 
kind, the chlorine may be removed by treating the solution, 
after the addition of a drop of nitric acid, with slight excess of 
pure nitrate of silver, and filtering. On now exactly neutral- 
ising the filtrate Avith ammonia, the yellow arsenite of silver 
will separate. 
Since ammonio-nitrate of silver is decomposed with the 
production of a precipitate, even in the absence of arsenious 
acid, by most organic solutions, the test is not applicable to 
mixtures of jliis kind. 
2. Ammonio-Sulphate of Copper. 
This reagent is prepared by cautiously adding ammonia to 
a someAAdiat dilute solution of sulphate of copper, until the pre- 
cipitate first produced is very nearly all redissolved; the clear 
liquid is then decanted. The- reagent produces in solutions of 
arsenious acid a green, amorphous precipitate of arsenite of cop- 
per, also known as Scheele’s green. The precipitate is nearly 
insoluble even in large excess of the precipitant, but readily 
soluble in ammonia and in free acids. From very dilute solu- 
tions of the poison, the precipitate does not appear of its char- 
acteristic color, until the mixture has stood for some time. The 
same precipitate is thrown down from solutions of neutral arsen- 
ics, by sulphate of copper alone. 
k Tour grain of arsenious acid, in one grain of Avater, yields 
washed acquires a bright green color, 
k T:«fot grain: a rather copious, green deposit, 
k 37(1 0~0 grain: a good, bluish-green precipitate, which after a 
a very copious, yellowish-green precipitate, which when 262 
ARSENIC. 
little time assumes a distinct green color, the blue tint 
disappearing. The true color of these precipitates is best 
seen when examined over a white surface. 
4- ToTFcTo grain: an immediate, bluish, flocculent precipitate, 
which after a little time acquires a light green color. The 
precipitate from ten grains of the solution soon acquires a 
Ten grains of a 25,000 th solution of the acid, yield an im- 
mediate, blue precipitate, which in a little time acquires a light 
green hue. 
fine green color. 
Fallacies.—There is no other metallic substance, besides 
arsenic, known, that yields with this reagent a similar precipi- 
tate. But various organic substances yield with the reagent a 
precipitate, having in some instances a color somewhat Resem- 
bling that of the arsenite of silver. So far, therefore, as the 
mere production of a greenish precipitate is concerned, no reli- 
ance whatever could be placed in the test when applied to 
organic solutions. , 
The arsenical nature of the arsenite of copper may be shown, 
by heating the dried precipitate, either alone or with a reducing 
agent, in a reduction-tube, when it will yield a sublimate of 
octahedral crystals of arsenious acid or of metallic arsenic, as 
the case may be. When dissolved in hydrochloric acid and 
boiled with a slip of bright copper-foil, arsenite of copper is 
decomposed with the deposition of metallic arsenic upon the 
copper-foil: the true nature of this deposit may be shown in 
the manner to be described hereafter, under the consideration 
of Reinsch’s test. If the hydrochloric acid solution of the 
arsenite be treated with sulphuretted hydrogen gas, it will yield 
a brown or dark brown precipitate, consisting of a mixture of 
the sulphurets of arsenic and copper. If this precipitate be 
collected on a filter, washed, and then digested with ammonia? 
the latter will dissolve the sulphuret of arsenic, while the sul- 
phured of copper will remain undissolved. On now filtering the 
arnmoniacal solution and carefully neutralising it with hydro- 
chloric acid, the sulphuret of arsenic will separate in the form 
of a bright yellow precipitate. SULPHURETTED HYDROGEN TEST. 
263 
3. Sulphuretted Hydrogen. 
Sulphuretted hydrogen gas, or Hydrosulphuric acid, throws 
down from solutions of arsenious acid, previously acidulated 
With hydrochloric acid, a bright yellow, amorphous precipitate 
°f tersulphuret of arsenic, or Orpiment, the reaction being: 
As03 +3HS= B HO + AsS3. For the application of this test, 
a small quantity of sulphuret of iron may be introduced into an 
ordinary gas-evolution flask and covered with pure water; the 
rooutli of the flask is then closed by a cork having two per- 
forations, one of which carries a funnel-tube, and the other, an 
exit-tube bent twice at right angles. Sufficient sulphuric acid 
18 then added to the contents of the flask, by 
aieans of the funnel-tube, to cause the evolu- 
tion of a moderate stream of sulphuretted hy- 
drogen ; this is conducted into the acidulated 
arsenical solution, contained in a test-tube or 
any convenient vessel. When the quantity of 
ttiaterial to be examined is very small, the ap- 
paratus illustrated in Fig. 7, may be em- 
ployed. From very dilute solutions of the 
poison, the precipitate does not separate, until 
the excess of the reagent added is expelled by 
a gentle heat or by exposure to the air. In all cases, a gentle 
heat hastens the complete separation of the precipitate. 
The tersulphuret of arsenic is insoluble in cold hydrochloric 
acid, and only very slightly soluble in the boiling concentrated 
acid; hot nitric acid decomposes and dissolves it to arsenic acid. 
is readily soluble, to a colorless solution, in the caustic alka- 
hes, and in the alkaline sulphurets and carbonates. 
When ten grains of a pure aqueous solution of arsenious 
at‘id are placed in a small test-tube, acidulated with two drops 
°f hydrochloric acid, and treated with a slow stream of the 
Washed sulphuretted gas, the following results are obtained. 
A 100 th solution, or yg- grain of arsenious acid, in ten grains 
Apparatus for detecting 
Arsenic by Sulphuret- 
ted Hydrogen. 
of water, yields a very copious, bright yellow precipitate, 
which remains amorphous. 264 
ARSENIC. 
2. l7oooth solution: an immediate precipitate, which very soon 
becomes quite copious. 
3., 10,000 th solution: an immediate, yellow turbidity; if the 
mixture, after being saturated with the gas, be allowed to 
stand at the ordinary temperature for several minutes, 
quite good, yellow flakes appear, and these after a time 
fall to a very good deposit. If the mixture be heated, 
the precipitate separates almost immediately. 
4. 25,000 th solution : very soon, a yellow turbidity; after stand- 
ing about ten minutes, yellow flakes are just perceptible; 
and after a few hours, there is a quite satisfactory deposit. 
If after the introduction of the gas, the mixture be heated, 
the deposit appears within a very few minutes. 
5. 50,000 th solution: after a little time, a perceptible yellowish 
turbidity; in about an hour, distinct flakes appear sus- 
pended in the liquid, but their color is not satisfactory; 
after a few hours, they assume a distinct yellow hue, bid 
still remain suspended in the fluid, from which, however, 
they almost immediately separate on the application ot 
heat. 
6. 100,000 th solution: after a few minutes, the mixture pre- 
sents a perceptible cloudiness; after several minutes, a 
distinct turbidity and a just perceptible yellow tint; after 
a few hours, distinct flakes appear, but their true color is 
not apparent; after thirty-six hours, there is a quite-dis- 
tinct yellow deposit. One hundred grains of the solution 
yield in a little time, a very perceptible yellowish turbid- 
ity; after a few hours, a decided yellow deposit; in twenty - 
four hours, the deposit is about the same as that from ten 
grains of a 10,000 th solution which has stood the same 
length of time. 
When normal solutions of the acid are treated with the 
reagent, they also yield tersulphuret of arsenic; but under 
these conditions, the arsenical sulphuret, except when from con- 
centrated solutions, entirely remains in solution, imparting a 
yellow color to the liquid. Ten grains of a 100 th solution of 
this kind, yield after a little time,' a quite good yellow precipi- 
tate; but the same quantity of a I,oooth solution yields only an 265 
SULPHURETTED HYDROGEN TEST. 
intensely yellow liquid; a 257OOOth solution yields a quite dis- 
tinct yellow coloration; and a 50,000 th solution, after a little 
time, acquires a perceptible yellow tint. Alkaline solutions of 
the acid, even when highly concentrated, altogether fail to yield 
a precipitate, when treated with the reagent. 
The limit of the visible reaction of this test, when applied 
to acidulated solutions of the poison, has been variously stated 
by different observers. Thus, Lassaigne placed it, for solutions 
acidulated with hydrochloric acid, at one part of arsenious acid 
in 80,000 parts of liquid; Reinsch, at one part in 90,000; 
fb’andes, one part in 100,000; Devergie, one in 500,000; and 
Horsley, at one part in 1,120,000 parts of fluid. Dr. Taylor 
states, that the 400 th part of a grain of the poison in half an 
ounce of water, produced a scarcely perceptible yellow tint. In 
this case, the acid was present in something less than 100,000 
parts of liquid. 
As neither of these observers, except Dr. Taylor, states 
file quantity of solution operated upon, these discrepancies are 
easily reconciled. The effect of quantity is well illustrated 
under experiment G, in which ten grains and one hundred 
grains respectively of the same solution were employed. Here 
d will be observed that although the degree of dilution was the 
same, yet the absolute quantity of arsenic in one case was ten 
times greater than in the other, and the results differed corre- 
spondingly. It is obvious that a similar difference would be 
observed between different quantities of any other solution, until 
the degree of dilution equaled the solubility of the tersulphuret 
°f arsenic, when no quantity, however great, would yield a 
precipitate. 
Confirmation of the Precipitate.—The arsenical nature of the 
tersulphuret of arsenic may be established by either of the fol- 
lowing methods : 
1. When the hydrochloric acid mixture containing the pre- 
Update is boiled with a slip of bright copper-foil, the sulphuret 
18 decomposed with the deposition of metallic arsenic upon the 
popper; if the coated copper be then washed, dried, and heated 
ui a reduction-tube, the metallic arsenic is volatilised and yields 
a sublimate of octahedral crystals of arsenious acid. In this 266 
ARSENIC. 
manner, the nature of the precipitate from less than the I,oooth 
part of a grain of the poison maj be fully established. 
2. When tersulplmret of arsenic is dissolved in a few drops 
of hot nitric acid, the solution cautiously evaporated to dryness, 
and the dry residue treated with a few drops of a strong solu- 
tion of nitrate of silver, it assumes a brick-red color, due to the 
formation of arsenate of silver. 
3. When washed, dried, and heated in a reduction-tube, 
tersulphuret of arsenic readily fuses to an orange-colored mass, 
then entirely volatilises, yielding a sublimate, the lower portion 
of which generally has an orange color and consists of • micro- 
scopic globules or drops; the upper part of the sublimate has a 
yellow color and its upper margin contains crystals of arsenious 
acid. Small precipitates of the sulphuret are most readily 
recovered, as recommended by Devergie, by collecting them 
on a small filter, dissolving in ammonia, and evaporating the 
solution at a gentle heat to dryness, in a watch-glass, when the 
sulphuret remains as a yellow residue. 
4. When the dried precipitate is mixed with several times 
its volume of well-dried ferrocyanide of potassium, or of a 
thoroughly dried mixture consisting of one part of cyanide of 
potassium and three parts of carbonate of soda, and heated in 
a reduction-tube, it undergoes decomposition with the produc- 
tion of a sublimate of metallic arsenic. If this operation be 
performed in a reduction-tube having a narrowly contracted 
neck, the precipitate from the I,oooth part of a grain of arse- 
nious acid, will yield very satisfactory results. 
For the reduction of tersulphuret of arsenic by a mixture of 
cyanide of potassium and carbonate of soda, Fresenius recom- 
mends to heat the arsenical mixture in an atmosphere of dry 
carbonic acid gas. For this purpose he employs-the apparatus 
illustrated in Fig. 8, next page. 
The flask A is charged with a mixture of water and lumpß 
of solid marble, and sufficient hydrochloric acid added, through 
the funnel-tube a, to evolve a moderate stream of gas; the car- 
bonic acid thus evolved, is conducted by means of the tube 
1) into strong sulphuric acid contained in the flask B, where if 
is thoroughly dried; the tube c conducts the dried gas into the FALLACIES OF THE SULPHUR TEST. 
267 
reduction-tube C, in which is placed the arsenical mixture d. 
When the apparatus is filled with the gas, the tube C is heated 
m its whole length very gently until the '•contained mixture is 
fluite dry ; when every trace of moisture is expelled, and the 
stream of gas has become so slow that the single bubbles pass 
through the sulphuric acid in B at intervals of about one second, 
the reduction-tube is heated to redness at the point e, by means 
a spirit-lamp ; when e is red-hot, the flame of another lamp 
18 applied to the mixture, proceeding from h to e, until the whole 
the arsenic is expelled. The far greater portion of the vola- 
tilised arsenic recondenses at /, while a small portion escapes 
through 77, imparting to the surrounding air a peculiar garlic- 
hke odor. By slowly advancing the flame of the second lamp 
UP to /, the whole of the condensed arsenic, collects in the nar- 
i’°w neck of the tube. The author of this process states that 
T will yield a perfectly distinct metallic mirror from the 300 th 
Part of a grain of tersulphuret of arsenic. (Qualitative Anal- 
ysis, 1864, p. 142.) 
Fallacies.—The only metal besides arsenic, with which sul- 
phuretted hydrogen produces a bright yellow precipitate, is 
cadmium. But, as the sulphuret of arsenic when precipitated 
from organic solutions may have only a dull yellow color, it is 
Fresenius’ Apparatus for the reduction of Sulphuret of Arsenic. 268 
ARSENIC. 
important to bear in mind that certain other sulphurets, either 
in their pure state or when mixed with organic matter, may 
also present a similar appearance. The only substances that 
under any circumstance could thus be confounded with arsenic, 
are cadmium, selenium, tin, and antimony. The sulphurets of 
these substances possess the following properties : 
1. The sulphuret of cadmium is precipitated by the reagent 
from moderately acid solutions of the salts of the metal, but 
strongly acidulated solutions fail to yield a precipitate. The 
precipitate is readily decomposed and dissolved by hydrochloric 
acid; so, also, unlike sulphuret of arsenic, it is insoluble in the 
alkalies and their sulphurets, and it is, therefore, produced m 
solutions containing a free alkali. When boiled with copper- 
foil in water acidulated with hydrochloric acid, it fails to pro- 
duce a deposit upon the copper. Fused in a reduction-tube 
with a reducing agent, it yields a metallic sublimate, which, 
however, in its physical appearance, is very unlike the arsen- 
ical deposit, and which when resublimed in the open tube failB 
to yield octahedral crystals. 
2. Acidulated solutions of selenious acid, yield with sulphu- 
retted hydrogen a precipitate of bisulphuret of selenium, which 
at first has a yellow color, but soon changes to reddish-yellorr, 
and finally to orange-red. In dilute solutions, the precipitate 
may remain suspended for some time, and jmesent a yellow ap- 
pearance, much like the arsenical compound; but after a time 
it separates of its characteristic color. The same precipitate 
separates from neutral’ and alkaline solutions. The precipitate, 
like the arsenical sulphuret, is insoluble in hydrochloric acid, 
even on the application of heat. Unlike the arsenical com- 
pound, however, it is wholly insoluble in ammonia. It also failB 
to yield a metallic deposit when boiled with diluted hydrochloric 
acid and copper-foil. When fused with a reducing agent in a 
reduction-tube, it yields a sublimate which may resemble some- 
what that produced by arsenic, but the deposit fails to yield 
octahedral crystals upon resublimation. 
3. Per-combinations of tin yield with the reagent from acid- 
ulated solutions, a precipitate of bisulphuret of tin, the color of 
which in the moist state somewhat resembles that of su 
Iphuret REINSCH’S TEST. 
269 
°f arsenic, but when dried, it has a very dull yellow color. 
The same precipitate separates from neutral, but not from alka- 
line solutions. The precipitate is slowly soluble in cold hydro- 
chloric acid, but readily in the hot concentrated acid. It is 
very sparingly soluble in ammonia, but readily soluble in potash. 
When boiled with water containing hydrochloric acid and a slip 
°f copper-foil, it may impart to the latter a slight stain, but 
when the stained metal is heated in a reduction-tube, it fails to 
yield a crystalline sublimate. The precipitate also fails to yield 
a metallic sublimate when heated in a reduction-tube with a 
reducing agent. 
4. The sulphurets of antimony, as thrown down from pure 
acidulated solutions, have an orange-red color; the same pre- 
cipitates are partially deposited in neutral and alkaline solutions 
°f the metal. The precipitates, unlike the sulphuret of arsenic, 
are slowly soluble in cold concentrated hydrochloric acid, and 
nearly wholly insoluble in ammonia; they are readily soluble in 
caustic potash. When boiled with diluted hydrochloric acid 
and copper-foil, they impart to the latter a metallic coating, 
which usually has a violet color; when the coated copper is 
heated in a reduction-tube, it fails to yield octahedral crystals. 
Nor will the precipitates when heated in a reduction-tube with 
a reducing agent, yield a metallic sublimate. 
4. Beinsclis Test. 
When a solution of arsenious acid or of an arsenite is 
strongly acidulated with hydrochloric acid, and the mixture 
hoiled with bright metallic copper, the latter decomposes the 
arsenical compound and receives a coating of metallic arsenic. 
This fact was first observed, in 1843, by Reinsch ; but Dr. 
haylor was the first to apply it as a test in medico-legal inves- 
tigations. The proportion of hydrochloric acid employed, should 
f°rm about one-eighth of the volume of the arsenical solution; 
Without the addition of the acid, the metal is not deposited. 
The copper may be employed either in the form of fine wire 
0r of very thin foil; the latter, however, is preferable. It is 
essential that the copper have a bright surface : this is readily 270 
ARSENIC. 
effected by means of a fine file or of sand-paper. The color of 
the metallic deposit will depend much upon the thickness of the 
latter: when quite thin, it presents a bluish or violet appear- 
ance, but when comparatively thick, it has a steel-like or iron- 
grey color. When the metallic coating is very thick, continued 
boiling causes it to separate from the copper, in the form of 
greyish or black scales. 
This deposit is not, as was formerly supposed, pure metallic 
arsenic, but a combination of this metal and copper. M. Lip* 
pert, from recent researches, maintains that it has a constant 
composition, being a definite alloy, consisting of 82 per cent, of 
arsenic and 68 per cent, of copper, its formula being Cu5As- 
The large proportion of copper contained by the deposit, adds 
very much to the delicacy of the test. This reaction will serve 
to withdraw the whole of the arsenic from solutions of arse- 
nious acid and of arsenites; but when the metal exists in the 
form of arsenic acid, it is deposited only from somewhat strong’ 
solutions. 
The arsenical nature of the deposit may be shown in the 
following manner: the coated copper, after being carefully 
washed with pure water and dried in a water-bath, is heated 
by means of a spirit-lamp in a narrow, perfectly dry and clean 
reduction-tube, when the arsenic volatilises, and becoming oxid- 
ised yields a sublimate of octahedral crystals of arsenious acid- 
This sublimate usually forms within from a quarter to half an 
inch above the point at which the heat is applied. When the 
sublimate is not exceedingly minute, it presents a well-defined 
ring of sparkling crystals to the naked eye. Under the micro- 
scope, these crystals present the appearances illustrated in Plate 
IV, fig. 5. The absolute size of the crystals will depend some- 
what upon the quantity of the metal present, as well as upon 
the diameter of the reduction-tube. The portion of the tube 
containing the sublimate may be separated with a file, boiled m 
a very small quantity of water, and the solution examined by 
the ammonio-nitrate of silver or any of the other tests for arse- 
nious acid. 
When one grain of a pure aqueous solution of arsenious acid 
is acidulated with pure hydrochloric acid, and the mixture REINSCH’S TEST. 
271 
heated in a thin watch-glass with a small fragment of bright 
copper-foil, it yields the following results. 
1- T¥ur grain of arsenious acid, yields a copious, iron-grey de- 
posit, which when heated in a narrow reduction-tube fur- 
nishes a very good sublimate, consisting of innumerable 
octahedral crystals. 
2- yinra grain, yields a good, steel-like deposit, which when 
sublimed in a reduction-tube yields results similar to 1, 
only that the crystals are generally somewhat smaller. 
3* ro,o o u grain: as soon as the mixture is heated to the boiling 
temperature, the copper shows a distinct deposit, which in 
a little time becomes quite satisfactory ; when this is vola- 
tilised in a very narrow reduction-tube, it yields a subli- 
mate visible to the naked eye, and which under the 
microscope is very satisfactory. 
When deposits smaller than the one just mentioned are 
Seated in a reduction-tube of the ordinary form, even of very 
narrow bore, the results are not uniform, due to the fact that 
the sublimate is distributed over a comparatively large space, 
aud part of it seems to entirely escape condensation, at least in 
the lower portion of the tube. With such deposits, however, 
very uniform results may be obtained by the following method. 
A thin, perfectly clean and dry tube, of about y0- inch in diam- 
eter, is drawn out into a capillary neck having an internal bore 
°f about the 40th part of an inch, as illustrated in Fig. 9, A. 
hhe coated copper is then in- 
troduced through the wider 
portion of the tube to the 
point c, and the neck of the 
tube at a little distance above 
the copper moistened with 
Water or wrapped with wet 
c°tton. The wide end of the 
is then cautiously fused shut by a very small blow-pipe 
flume, and the fusion slowly advanced to the point occupied by 
the copper, as shown in B. The capillary end may now be 
fused shut. When wiped and examined by the microscope, the 
arsenical sublimate will be found at about the point m, forming 
Tubes for Sublimation of Arsenic. Natural size. 272 
ARSENIC. 
a very narrow ring of octahedral crystals. As these tubes may 
readily be formed with walls less than the 100 th part of an 
inch in thickness, they permit the application of the higher 
powers of the microscope. They may be reserved for future 
examination; after a time, however, the sublimate deteriorates 
somewhat, and may even, if the deposit is very small, wholly 
disappear. 
4. 2T7V00 grain: when a fragment of copper-foil measuring 
about yo by yo inch is employed, and the mixture kept 
at a boiling heat for some time, with renewal of the evap- 
orated fluid by pure water, the copper acquires a decided 
steel-like coating; when this is sublimed in a tube of the 
form described above, it yields to the naked eye a visible 
mist, which under an amplification of seventy-five diam- 
eters is found to consist of many hundreds of well-defined 
octahedral crystals. In a number of instances, over one 
hundred crystals, varying in size from the 2,000 th to the 
B,oooth of an inch in diameter, were counted in a single 
field of a 2-3ds inch objective, without change of focus; 
most of the crystals measured about the 4,000 th of an 
inch in diameter. 
5. jieWo grain, when treated for some minutes as under 4, im- 
parts to the copper a distinct steel-like tarnish, which 
when volatilised, in the manner described above, yields 
a very satisfactory microscopic sublimate. In many in- 
stances, over fifty crystals, measuring from the 3,000 th to 
the 10,000 th part of an inch in diameter, were counted m 
a single field of the objective. So far as the evidence of 
the presence of octahedral crystals is concerned, this sub- 
limate, under the microscope, is as satisfactory as that 
from the 100 th part of a grain or larger quantity of the 
poison, the only difference being in the size and number 
of the crystals. 
G. riroVoi) grain: the copper receives a very slight tarnish? 
which when volatilised sometimes yields a satisfactory 
crystalline sublimate; but frequently the crystals are so 
minute that their angular nature can not be satisfactorily 
determined. FALLACIES OF REINSCH’S TEST. 
273 
For the examination of these sublimates, a magnifying power 
°f about seventy-five diameters is generally the most useful. 
Under this amplification, the angular nature of a crystal meas- 
uring the 5,000 th of an inch in diameter, is perfectly distinct 
and satisfactory: the weight of such a crystal would not exceed 
the 200,000,000 th part of a grain. Under the same power, a 
Crystal measuring the 10,000 th of an inch, appears only as a 
distinct point; but with a power of one hundred and fifty, its 
angular form may be distinctly recognized: its weight would 
he less than the 1,000,000,000 th of a grain. On account of 
the curvature of the glass tube, crystals but little less in size 
than the last-mentioned, are not easily determined, even with 
the higher powers of the microscope. It is not, of course, 
intended to imply that quantities of the poison in themselves as 
small as those just mentioned could be recovered from a solution 
and reproduced in the crystalline form j but only that these 
crystals may thus be recognised and identified when they form 
separate portions of a sublimate. The least quantity of the 
poison that will furnish these crystals, even with the greatest 
care and under the most favorable circumstances, according to 
the above method, is about the 50,000 th part of a grain. 
Various and very discordant limits have been assigned to 
test, by different observers. However, as these experi- 
mentalists only state the degree of dilution, without mentioning 
cither the quantity of solution examined, the size of the copper 
°r the diameter of the reduction-tube employed, these discrep- 
ancies are readily explained. 
Fallacies.—The production of a sublimate of octahedral crys- 
tals by this test, is perfectly characteristic of arsenic. Various 
°ther metals, however, as antimony, mercury, silver, bismuth, 
platinum, palladium, and gold, are deposited upon copper under 
the same conditions as arsenic. Tin may also impart a slight 
stain to the copper; so, also, organic matter, especially if it 
c°ntain sulphur; and the prolonged action of boiling hydro- 
chloric acid alone may produce a distinct tarnish. The antimo- 
lilal deposit has usually a peculiar violet color, while the deposits 
hom mercury, silver, and bismuth have generally a bright sil- 
Very appearance, and that from gold a yellow hue. Under 
18 274 
ARSENIC. 
certain circumstances, however, most of these deposits may 
closely resemble that from arsenic. The platinum and palladium 
deposits present an appearance very similar to that of the 
arsenical coating. 
Of these various metallic deposits, the only ones which when 
heated in a reduction-tube, will, like arsenic, volatilise and yield 
a sublimate, are mercury and antimony. But, the sublimate 
from mercury consists of opake spherical globules, which when 
viewed under incident light with the microscope, have a bright 
silvery appearance ; and that from antimony, is amorphous or 
at most granular : both these sublimates, unlike that from ar- 
senic, are insoluble in water. Moreover, the antimonial subli- 
mate is only obtained from comparatively thick crusts of the 
metal, and deposits in the reduction-tube much nearer the cop- 
per than that from arsenic; it also requires a higher heat lor 
its formation. In this connection it should be remembered, that 
commercial tartar emetic sometimes contains sufficient arsenic? 
as an impurity, to yield in this manner a very distinct subli- 
mate of octahedral crystals, in advance of the antimonial deposit. 
A deposit of organic matter upon the copper, may also give 
rise to a sublimate, but this is amorphous, and its true nature 
is at once revealed by the microscope. When very complex 
organic mixtures strongly acidulated with hydrochloric acid, are 
boiled for some time in contact with metallic copper, the metal 
may present a very distinct stain, and yield an amorphous sub- 
limate which sometimes contains small acicular crystals, con- 
sisting apparently of a compound of copper. This sublimate 
deposits very near the copper, and is not resublimed upon the 
further application of heat. Finally, if the copper-foil or the 
reduction-tube is not perfectly dry, the moisture may condense 
in the form of a mist-like deposit at about the point at which 
the arsenical sublimate usually forms; but the true nature of 
this deposit also is at once revealed by the microscope. 
From what has now been stated, it is obvious that the pres- 
ence of arsenic is not fully established until the coated copper 
yields a sublimate-'of octahedral crystals. In applying this 
confirmatory reaction, however, it should be borne in mind, that 
when a comparatively large arsenical deposit is heated in a very FALLACIES OF REINSCH’S TEST. 
275 
small reduction-tube, the sublimate may consist alone of gran- 
ules, or a portion of the arsenic may even deposit in its metallic 
state. It rarely happens, however, that at least the upper 
margin of an arsenical sublimate does not contain the charac- 
teristic crystals. Should there be any doubt as to the nature 
°f the sublimate, the lower end of the tube may be removed, 
uud the deposit resublimed, when, if consisting of arsenic, it 
will be converted into the crystalline form. In all cases, the 
Slze of the reduction-tube should be in suitable proportion to 
the quantity of deposit to be examined. 
But even should this test, when applied to a suspected solu- 
tion, yield an arsenical sublimate, it, of course, would not follow 
that the poison was really derived from the suspected liquid, 
unless the analyst was perfectly certain of the purity of the 
hydrochloric acid, and in some instances also of the copper, 
employed. As found in commerce, hydrochloric acid not un- 
frequently contains very notable quantities of arsenic. In all 
eases, a portion of the sample of the acid about to be employed, 
should first be diluted with five or six volumes of water and 
hoiled for about ten minutes with a slip of bright copper ; if 
this fails to yield a deposit, the acid may be considered free 
from arsenic. In regard to the purity of copper, it is now 
known, chiefly through the recent researches of Dr. Taylor, 
frat this metal as usually employed in investigations of this 
kind, nearly always contains traces of arsenic. This impurity, 
however, could only lead to error when the copper is acted 
uP°u and dissolved by the liquid with which it is boiled; any 
ar.senic thus dissolved might then deposit upon a fresh portion 
°f the copper. This objection, therefore, has no practical force, 
eXcept in cases in which a very notable quantity of the copper 
has dissolved, and only a very minute trace of arsenic has been 
detected. When, in the application of the test to a suspected 
s°lution, the copper promptly receives an arsenical deposit, 
which after the addition of successive slips of the metal ceases 
to take place, it is quite certain that the poison is not derived 
from the copper. 
For the detection of traces of arsenic in copper, we have 
found the following method, first advised by F. Field (Chem. 276 
ARSENIC. 
Graz., 1857, p. 313), exceedingly delicate. Ten grains of the 
copper are dissolved in slight excess of pure, hot, nitric acid, 
the solution diluted to about three ounces of fluid, and ammonia 
added until the oxide of copper is precipitated, but not redis- 
solved; the precipitate is then redissolved by the addition of 
about twenty-five grains of oxalate of ammonia, the oxalate of 
copper thus produced precipitated by slight excess of hydro- 
chloric acid, and the mixture allowed to stand some hours. The 
solution is then filtered, the filtrate saturated with sulphurous 
acid gas, concentrated to a small volume, and tested for arsenic, 
either by sulphuretted hydrogen or by a fresh piece of copper. 
For this same purpose, Dr. Odling recommends (Jour. Chem. 
Society, Jnly, 1863, p. 248) to distill a few grains of the cop- 
per, cut into small pieces, with an excess of pure hydrochloric 
acid and perchloride of iron, the distillation being carried to 
dryness: the dry residue may be redistilled with a little fresh 
hydrochloric acid. By this treatment, the copper is quickly 
dissolved, and any arsenic present converted into chloride and 
thus carried over with the distillate. The distillate is tested for 
arsenic in the usual manner. Perchloride of iron, Dr. Odling 
adds, may be purified from arsenic, by evaporating it once or 
twice to dryness with excess of hydrochloric acid. 
Interferences.—Should this test fail to yield a metallic de- 
posit upon the copper, it would not follow, from this fact alone, 
that arsenic was entirely absent, since the deposition of this 
metal may be prevented by the presence of certain other sub- 
stances. Thus in even strong solutions of the poison containing 
only a small quantity of a chlorate, as chlorate of potash, the 
copper remains perfectly bright; but the liquid acquires a bluish 
or greenish-blue color, due to the formation of a soluble salt of 
copper. Should arsenic and a chlorate occur in the same mix- 
ture, the solution is cautiously evaporated to dryness, and the dry 
residue fused in a long, narrow, glass tube, until the evolution 
of oxygen ceases: by this operation, the chlorate will be con- 
verted into a chloride, and the arsenic into arsenic acid. The 
tube is then cut into small pieces and boiled with a small quan- 
tity of pure water, until the saline matter has entirely dissolved, 
and the solution thus obtained, after filtration if necessary, ADVANTAGES OF REINSCH’S TEST. 
277 
saturated with sulphurous acid gas, the excess of which is after- 
wards expelled by a gentle heat. The solution, which now con- 
tains the arsenic as arsenious acid, together with the chloride 
resulting from the decomposition of the chlorate, may be acidu- 
lated with hydrochloric acid and examined in the usual manner. 
So also, the presence of binoxide of manganese, and of other 
substances that decompose hydrochloric acid with the elimina- 
tion of free chlorine, may interfere with the reaction of the test. 
And the same is true of free nitric acid. This acid, however, 
has little action upon the test unless present in quite notable 
Quantity or the solution be concentrated to a small volume, when 
acts upon and.dissolves the copper. In case of the presence 
°f free nitric acid, the solution may be neutralised with caustic 
potash, then acidulated with hydrochloric acid, and tested as 
usual; or, the solution may be cautiously evaporated to dryness, 
the residue dissolved in water, this solution saturated with sul- 
phurous acid gas, then gently heated to expel the excess of gas, 
and examined. 
The alkaline nitrates have little or no effect upon the test 
Until the solution is evaporated to near dryness, when they 
oause the solution of the copper. In a mixture containing the 
of its weight of nitrate of potash and the 500 th part of 
Arsenious acid, the reaction takes place much the same as in a 
pure solution of the poison. 
In conclusion, it may be remarked that this method of 
Aeinsch possesses several advantages which entitle it to more 
Consideration than it has usually received at the hands of chem- 
ists. Thus, it is easily and quickly applied, requiring but little 
aPparatus, and that of the most simple kind ; it usually requires 
purity of only one substance, namely, the hydrochloric acid, 
be known, and this is readily established by means of the 
A'td itself • it requires no dilution of the suspected liquid, but 
°U the contrary permits its concentration to almost any extent 
the test is being applied; it may be applied directly to 
unich more complex organic mixtures than either of the other 
for this poison; and finally, it serves to separate from com- 
-1 mixtures and reproduce in an unequivocal form, a less 
quantity of the poison than any other known test, excepting 278 
ARSENIC. 
perhaps, one of the methods of Marsh’s process, with which, 
however, it is equally delicate. 
5. Marsh’s Test. 
When a mixture of zinc and water is treated with sulphuric 
acid, the zinc is oxidised at the expense of the oxygen of the 
water, while the hydrogen of the latter passes off in its free 
state : Zn +HO + S03 = ZnO, S03 +H. If, however, arsenious 
acid, arsenic acid or any of the soluble compounds of the metal 
be present in such mixture, the zinc is partially oxidised at the 
expense of the oxygen of the arsenical compound, and the whole 
of the arsenic thus eliminated unites with part of the nascent 
hydrogen, forming arsenuretted hydrogen gas (AsH3). The re- 
action in the case of arsenious acid, is as follows: 3HO + Aso3 + 
6Zn + 6 S03 = 6 ZnO, S03 + AsH3; with arsenic acid : BHO + 
As05 +BZn + 8 S03 = 8 ZnO, S03 + AsH3. When the arsenic is 
present as a chloride, it yields hydrochloric acid and the arsen- 
uretted gas. Neither metallic arsenic nor the sulphurets of the 
metal, will yield a trace of the gas. The production of arsen- 
uretted hydrogen, under these conditions, has long been known, 
but Mr. Marsh, of Woolwich, in 183G, was the first to employ 
it as a method for the detection of arsenic. 
Arsenuretted hydrogen is a colorless, extremely poisonous 
gas, having a peculiar alliaceous odor, and specific gravity ot 
2-695 ; it is neutral in its reaction, and but sparingly soluble m 
water. It burns with a bluish flame, giving rise to arsenious 
acid, and is readily decomposed by heat, into free hydrogen and 
metallic arsenic; it is also readily decomposed by solutions of 
the easily reducible metallic oxides. These properties serve, ill 
the manner to be pointed out hereafter, for the detection of very 
minute traces of the gas. 
Various forms of apparatus have been proposed for the pro- 
duction of this gas in its application to the detection of arsenic, 
but the most efficient is that advised by Otto, as illustrated, h1 
principle, by Fig. 10, next page. The gas-flask A, which nia} 
be substituted by a simple wide-mouthed bottle or in delicate 
experiments by a long test-tube, is provided with a closely MARSH’S TEST. 
279 
fitting cork carrying the funnel-tube a, and the exit-tube h; 
tbis tube should be tolerably wide, and have its lower end cut 
obliquely, to facilitate tbe dropping back of any condensed 
liquid into the flask, cis a drying-tube containing fragments 
Apparatus for the Application of Marsh’s Test. 
°b hydrate of potash or of chloride of calcium, kept in their 
place by loose cotton. Unless the experiment is to be con- 
tinued for some time, it is only necessary to loosely fill the 
drying-tube with cotton moistened with concentrated sulphuric 
acid. This tube is connected with the tube 6, by means of a 
perforated cork, and with the reduction-tube d, by a short india- 
llibber tube. The reduction-tube (d) should be of hard glass, 
free from lead, and have an internal diameter of about 8-20ths 
°1 an inch, and walls not less than the 20th of an inch in thick- 
ness; its outer portion should be contracted in two or three 
places, as shown in the figure, and terminate in a turned-up, 
drawn-out point, which is fused in a small flame of a spirit-lamp, 280 
ARSENIC. 
until the opening becomes quite small. By preparing the end 
of the tube in this manner, there is no danger of its fusing 
shut, when the jet of gas is afterwards ignited. In very deli- 
cate experiments, the bore of the contracted portions of the 
tube should not exceed the 20th of an inch in diameter. Sev- 
eral of these tubes should be prepared and at hand. 
About two ounces of pure zinc, either granulated or cut into 
small pieces, are now placed in the flask A, and, the apparatus 
being adjusted, covered with a cooled mixture consisting of one 
measure of pure concentrated sulphuric acid and four measures 
of distilled water, added through the funnel-tube a, which 
should extend to near the bottom of the flask. The zinc will 
now immediately begin to decompose the water with the evolu- 
tion of hydrogen, in the manner before described. Should, 
however, the zinc or the sulphuric acid be contaminated with 
arsenic, as not unfrequently is the case, it will give rise to 
arsenuretted hydrogen. Before, therefore, applying the test to 
a suspected solution, the purity of the materials employed must 
be fully established. For this purpose, after the apparatus has 
become completely filled with hydrogen and while the gas is 
still being evolved, the outer uncontracted portion of the reduc- 
tion-tube is heated to redness, as illustrated in the figure, for 
about fifteen minutes. If this fails to produce a metallic de- 
posit or stain in the contracted part of the tube, in advance of 
the part heated, the material may be considered free from 
arsenic. The purity of the materials having been thus estab- 
lished, it may be necessary to wash and renew the zinc, dry 
the tubes, and add a fresh portion of the diluted acid. 
The apparatus being adjusted and completely filled with 
evolved hydrogen, the jet of gas, as it issues from the drawn- 
out end of the reduction-tube, is ignited, care being taken not 
to apply a light until the whole of the atmospheric air is ex- 
pelled from the apparatus, as otherwise an explosion might 
occur. A small quantity of the arsenical solution is then intro- 
duced into the funnel-tube, and washed into the flask by the 
subsequent addition of a few drops of the diluted sulphuric acid. 
The decomposition of the arsenical compound, with the evolution 
of arsenuretted hydrogen, will commence immediately. The MARSH’S TEST. 
281 
presence of the arsenuretted gas may be established by three 
different methods, namely : a. By the properties of the ignited 
Jet; /?. By decomposing it by heat applied to the reduction-tube; 
and y. By its action upon a solution of nitrate of silver. 
a- The ignited jet.—As soon as the arsenical solution is 
introduced into the flask, the evolution of gas increases; this 
increase is quite perceptible, even when the liquid within the 
flnsk contains only the 1,000,000 th part of its weight of arse- 
nious acid. The flame of the ignited jet will now increase in 
Size, acquire a bluish tint, and, unless only a minute quantity 
°f arsenic is present, evolve white fumes of arsenious acid; so 
also, sometimes, the flame emits a peculiar alliaceous odor. If 
the white fumes thus evolved be received upon a cold surface, 
as an inverted watch-glass, they condense to a white powder, 
ii’hich sometimes contains octahedral crystals. The arsenical 
nature of this powder may be shown by any of the methods 
heretofore pointed out for the recognition of solid arsenious 
acid. This, however, is by no means a delicate method for 
detecting the presence of the arsenuretted gas; and it should 
never be employed to the exclusion of that now to be mentioned. 
If the flame be allowed to strike against a cold body, as a 
piece of white porcelain held in a horizontal position, it yields 
a deposit of metallic arsenic on the cold surface. In experi- 
ments with very dilute solutions, the porcelain should be applied 
after the introduction of the arsenical compound, 
Slace the evolution of the arsenuretted gas begins at once, and 
the whole of the metal may be thus rapidly evolved. As soon 
as a well-marked deposit is obtained on the porcelain, the posi- 
tlon of the latter should be changed, so that the flame may 
strike upon a fresh surface; if it can be done, a number of 
these deposits should be collected upon several different pieces 
°t* the porcelain. 
When the amount of arsenic present is not very minute, 
th® central portion of the deposits thus obtained presents a 
right steel-like appearance; this is surrounded by a darker 
less lustrous portion, the outer margin of which has some- 
bfties a brownish color. The exact appearance of these deposits, 
lQWever, depends much upon the quantity of arsenic present, 282 
ARSENIC. 
the character of the flame, and the position occupied by the 
porcelain: sometimes they consist simply of brownish stains, 
whilst at others, they are in the form of rings. From very 
dilute solutions, they are produced only when the gas burns 
with a small, steady, round flame; when the supply of gas is 
so rapid as to produce a long pointed flame, they are sometimes 
not obtained from even strong solutions of the metal. When 
the gas burns with a conical flame, the porcelain should be 
applied at about the center of its upper third or still nearer 
its point; on the other hand, when the flame is short, full, and 
round, the cold surface should be held very near its base. 
Delicacy of this method.—ln investigating the limit of this 
test, in regard to the production of metallic deposits on cold 
porcelain, a gas-flask of about three fluid ounces capacity was 
employed, except when the entire quantity of fluid did not 
exceed one hundred grain-measures, when the flask was sub- 
stituted by a test-tube, three-fourths of an inch in diameter 
and five inches long. For the examination of very minute 
quantities of arsenious acid, or of any other soluble combina- 
tion of the metal, a test-tube has an advantage over a flask, m 
that the arsenical solution can, by means of the funnel-tube, be 
brought in contact with the zinc and be thus decomposed be- 
fore becoming much diffused through the diluted sulphuric acid. 
1. r-oVo grain of arsenious acid, in solution in ten grains oi 
water, when added to an active apparatus containing some- 
thing less than an ounce of pure zinc and exactly ninety 
grain-measures of diluted sulphuric acid, yields in a feur 
moments, from the ignited jet, metallic deposits, which 
continue to be formed, until about sixty can be obtained, 
after which the evolved gas gives no evidence whatever 
of the presence of the metal. The degree of dilution rll 
this case, providing the poison became equally diffused 
throughout the whole of the liquid in the apparatus, would 
be one part of arsenious acid in 100,000 parts of the 
liquid mixture. 
Of six experiments, in each of which the I,oooth part oi 
a grain of arsenious acid, in solution in ten grains of water, 
was added to an active apparatus containing two hundred cind 283 
MARSH’S TEST. 
ninety grain-measures of diluted sulphuric acid—the poison now 
forming only the 300,000 th part of the liquid mixture—the 
highest number of well-defined deposits obtained was sixty- 
seven, the lowest fifty-two. If, therefore, none of the metallic 
arsenic escaped condensation—which however is not the fact— 
a single deposit could not on an average have represented more 
than the 60,000 th part of a grain of arsenious acid, or only 
about the 80,000 th of a grain of the metal; yet they each, 
Vuth very few exceptions, measured from the 10th to the 14th 
°f an inch in diameter. The size of these deposits, will of 
course depend somewhat upon the size of the flame, which in 
As turn will depend upon the supply of gas and the orifice of 
the tube. 
Experiments made with the same quantity of the poison in 
the presence of five hundred grains of liquid—or under a dilu- 
tion of 500,000 parts of fluid—gave much the same results as 
those just described. 
"■ arroo grain of arsenious acid, in an apparatus containing 
one hundred grains of liquid—or under a dilution of 250,- 
000—furnished as the average of six experiments, twenty- 
nine very satisfactory deposits. 
The same quantity of the poison in five hundred grains of 
lcflud, or under a dilution of 1,250,000, gave, in several experi- 
ments, several distinct stains, but in no instance were the results 
satisfactory. 
’ ’ sTooi grain of arsenious acid, in one hundred grains of fluid, 
or under a dilution of 500,000, usually yields several sat- 
isfactory deposits. But the same quantity of the poison 
m three hundred grains of liquid, failed in several instances 
to yield any satisfactory evidence of its presence. 
The limit of this test, as applied in this manner, has been 
Jmiiously assigned; but with few exceptions, the experimenters 
Ve °nly stated the degree of dilution of the solution, without 
mentioning the quantity employed. Thus it has been stated 
la the method will yield satisfactory deposits when the solu- 
contains only the 2,000,000 th part of its weight of arsenic. 
18 18 true, but it requires about one thousand grains of such 
mention to furnish these results; the absolute quantity of the 284 
ARSENIC. 
poison present would therefore be about the 2,000 th part of a 
grain. These statements have generally led to a misappre- 
hension of the real delicacy of this test; and it has, therefore, 
in this respect been much overestimated. It is a fact, that 
this method of Marsh, when referred to the mixture within the 
apparatus, will indicate the presence of the poison under a 
greater degree of dilution than any other known test; but at 
the same time, it requires a much larger quantity of the solution 
for its application than will serve for either of the other tests. 
From the experiments already cited, it would appear that 
when one hundred grains of liquid are employed—and this is 
about the smallest quantity that will evolve sufficient gas for 
the purpose—the least quantity of arsenious acid that will 
yield satisfactory deposits, is about the 5,000 th part of a grain- 
This, therefore, so far as the production of deposits is con- 
cerned, is about the limit of the test. It has generally been 
conceded that this method would reveal the presence of a 
smaller quantity of arsenic than could be recovered by the 
method of Reinsch; but this is not the fact, since the latter 
process, in the manner already described, will serve to detect 
a much less quantity of the poison than can be made to reveal 
any evidence of its presence by at least this part of the method 
of Marsh. 
Fallacies.—Solutions of antimony, under these same condi- 
tions, undergo decomposition with the production of antimony- 
retted hydrogen gas, which, like arsenuretted hydrogen, burns 
with the evolution of white fumes, and yields metallic deposits 
upon cold surfaces applied to the flame. It, however, unlike 
the arsenuretted gas, is destitute of odor, and burns with a 
greenish flame; moreover, when the white fumes evolved are 
condensed on a cold body, they yield an amorphous deposit? 
which is insoluble in water, and immediately assumes an orange' 
red color when moistened with a solution of sulphuret of aiU' 
monium; whilst that obtained from arsenic, under similar cir- 
cumstances, is soluble in water, and undergoes no immediate 
change when treated with sulphuret of ammonium. 
The metallic deposits produced by antimonuretted hydrog611 
upon a piece of cold porcelain, are usually destitute of lustei? FALLACIES OF MARSH’S TEST. 
285 
ancl have a much darker color than those obtained from arsenic. 
These characters readily serve to distinguish between compara- 
tively thick crusts of these metals; but in very thin deposits, 
they may be entirely lost. The deposits of the two metals, 
however, differ greatly in regard to their chemical properties. 
The arsenical crusts, except when very thin, are only very 
slowly soluble in a drop or two of a yellow solution of sulphuret 
pf ammonium; whilst the antimonial deposits are readily soluble 
111 this reagent. When the ammoniacal solution is evaporated 
to dryness on a water-bath, the arsenic remains as a bright 
yellow deposit of tersulphuret of arsenic, which is readily solu- 
in ammonia, but insoluble in hydrochloric acid; under the 
same conditions, antimony yields an orange-red residue, of ter- 
salphuret of antimony, which is insoluble in ammonia, but 
readily soluble in concentrated hydrochloric acid. This method 
'VIH serve for the discrimination of very minute deposits of the 
oietals. 2. The spots produced by arsenic, are readily soluble 
111 a solution of hypochlorite of soda or of lime; whereas those 
s°m antimony, are insoluble or only dissolve after prolonged 
agestion, in a solution of this kind. 3. The deposits from 
. amtals readily dissolve in a drop of warm nitric acid, and 
yield on the cautious evaporation of the liquid, a white residue, 
aen, however, the arsenical residue is touched with a drop 
a solution of nitrate of silver, it assumes a brick-red color*, 
whilst that from antimony remains unchanged. Various other 
Methods have been proposed for distinguishing between these 
s*ains, but in point of delicacy they are much inferior to those 
a r©ady described. 
besides this fallacy of antimony, it has been objected that 
Same matter, certain combinations of iron, phosphorus, and 
. Tmur, may under the above conditions yield stains somewhat 
Sllailar to those produced by arsenic. But neither of these 
stances will yield a succession of spots; nor will either of 
. 111 yield a single stain having the properties described under 
er of the three methods iust mentioned for the identification 
of ti . J 
. 116 arsenical deposit. In experiments for the purpose with 
ares containing iron, phosphorus, and sulphur, we have 
ed to obtain any stain whatever having the most remote 286 
ARSENIC. 
resemblance to that produced by arsenic; nor, in numerous ap- 
plications of the test to animal and vegetable mixtures, have 
we ever found it yield an organic stain. 
/?. Decomposition of the gas by heat.—As originally pro- 
posed by Marsh, this test consisted simply in obtaining metallic 
deposits from the ignited jet of gas, as now described. Berze- 
lius was, perhaps, the first to resort to the decomposition of the 
arsenuretted gas by heat, as a means of its detection. The 
apparatus being filled with hydrogen and the evolution of gas 
quite moderate, a large flame of a common spirit-lamp, wdiich 
we prefer to an argand-burner, is applied to the reduction-tube, 
at a point about half or three-quarters of an inch on the inside 
of the outer contraction. When the part of the tube to which 
the flame is applied is quite red hot, a very small quantity of 
the arsenical solution is introduced, by means of the funnel-tube, 
into the flask. The arsenuretted hydrogen now evolved, as it 
passes through the red-hot portion of the reduction-tube, will 
be decomposed with the production of a deposit of metallic 
arsenic in the contracted part, in advance of the flame. Aftei’ 
a good deposit has thus formed, the heat of the lamp may be 
so changed that the metal may be deposited in the second con- 
tracted portion of the tube. 
The physical appearance of the deposits thus obtained, de- 
pends somewhat upon the quantity of arsenic present, but they 
usually, especially when obtained from very dilute solutions, 
consist of three conjoined portions, the inner of which is trans- 
parent and of a brown color, while the central part has a brill" 
iant metallic appearance, and this fades into a lighter colored 
or grey portion, which is imperceptibly lost. Very thick de- 
posits may present much the same characters as presented b} 
the sublimed metal, already described. When the quantity °1 
arsenic present is comparatively large and the current of 
rapid, sometimes arsenical stains may be obtained from th® 
ignited jet at the same time that a deposit is being formed 111 
the heated tube.. 
Delicacy of this method.—A much smaller quantity of the 
metal will yield deposits by this process than will serve for 
detection from the ignited arsenuretted gas. This difference MARSH’S TEST. 
287 
due to the fact that by the method under consideration, the 
uietal eliminated from the decomposed gas may be collected at 
about the same point for several minutes or longer if necessary; 
udiereas from the gas when ignited, it can be collected at the 
Sanie place for only a few moments. Another advantage of this 
method over the preceding is, that it may be applied with a less 
Quantity of liquid, since it requires only a feeble current of gas. 
In the following experiments, one hundred grain-measures 
°f liquid, including the arsenical solution,' were present in the 
Apparatus, and the reduction-tube was contracted to a bore of 
about the 20th of an inch in diameter. The arsenious acid, as 
lntroduced in the apparatus, was in solution in ten grains of 
crater. 
27/ou grain of arsenious acid, in one hundred grains of liquid, 
or one part of the acid in the presence of 250,000 parts 
of fluid, yields in a very little time a very fine deposit, 
the inner portion of which has a brown color, while the 
outer part has a bright, metallic luster. 
* 5700-5 grain, under a dilution of 500,000 parts of liquid, 
yields much the same results as 1. 
3 i • 
' i~o7ooij grain, under a dilution of 1,000,000, yields a quite 
good deposit. 
* arWo grain, under a dilution of 2,500,000, yields after some 
minutes, a very satisfactory deposit. 
’ sTToito grain, in the presence of 5,000,000 parts of liquid, 
yields after several minutes, a very distinct stain, the 
outer part of which has a dark, metallic appearance, and 
the inner, a brownish color. 
In regard to the delicacy of this method, it may be remarked, 
ct m the whole range of chemical tests there is perhaps no 
that will indicate the presence of a substance under as 
bleal a degree of dilution. It may be proper to state, that the 
materials employed in the above experiments were subjected to 
, e action of the test for more than half an hour, without yield- 
the slightest trace of a deposit in the reduction-tube, 
d . a^ac^es-—Antimonuretted hydrogen also is decomposed un- 
r the above conditions, with the deposition of metallic anti- 
molkv- Since, however, antimonuretted hydrogen is decomposed 288 
ARSENIC. 
at a lower temperature than the arsenuretted gas, the antimony 
eliminated is always, in part at least and from dilute solutions 
wholly, deposited before reaching the part of the reduction-tube 
to which the, flame is applied; when it yields deposits on both 
sides of the flame, the outer one is quite near the flame. On 
the other hand, arsenic deposits about half or three-quarters of 
an inch in advance, or on the outer side of the flame, and never 
before reaching the part of the tube to which the heat is directly 
applied. This difference in itself is quite sufficient to distin- 
guish between these metals, when only one of them is present. 
Again, the arsenical deposit has usually a bright, metallic luster, 
whilst the antimonial has a dull and darker appearance. Very 
thin deposits of the two metals, however, may present very 
similar appearances. 
In regard to the action of heat and chemical reagents upon 
these metallic deposits, they differ in the following respects ; 
a. If the tube, removed from the apparatus, be heated at ft 
little distance from and on the inner side of the crust, and the 
heat then slowly advanced to it, the arsenical dejmsit readily 
volatilises and recondenses a little further on, in the form of 
brilliant, octahedral crystals of arsenious acid. Under the same 
circumstances, the antimonial deposit requires a much higher 
temperature for its sublimation, and yields a white, amorphous 
deposit, quite near the point to which the heat is applied. This 
method will serve for the identification of very minute crusts of 
the metals. The arsenical sublimate thus obtained, may be 
further identified by its ready solubility in a few drops of hot 
water, and by the resulting solution, when acidulated with 
hydrochloric acid and treated with sulphuretted hydrogen gftV 
yielding a yellow precipitate. These characters, however, only 
reveal themselves in sublimates obtained from comparatively 
thick crusts of the metal. 
h. The deposits of the two metals may also be distinguished 
by either a solution of sulphuret of ammonium, hypochlorite of 
soda, or by dissolving the crust in nitric acid, evaporating the 
solution to dryness, and treating the residue with nitrate of sib 
ver, in the manner already described for the discrimination of 
stains obtained on porcelain from the ignited gas. MARSH’S TEST. 
289 
c* If a slow stream of perfectly dry sulphuretted hydrogen 
£>as he conducted through the tube containing the arsenical 
deposit, and the latter heated by the flame of a spirit-lamp ap- 
plied to the tube, beginning at the outer margin of the deposit, 
in vaporising is converted into tersulphuret of arsenic, which 
condenses at a little distance in advance of the heat to a yel- 
low deposit, the inner margin of which, even after cooling, 
Inas sometimes an orange hue. The metallic deposit from the 
°>oooth part of a grain of arsenious acid, will in this manner 
.Held very distinct results. Under these same conditions, the 
•intiinonial crust also decomposes the sulphuretted gas, with the 
loimation of tersulphuret of antimony, which however condenses 
to a reddish-brown or nearly black deposit. To effect this 
change, requires a stronger heat than for the arsenical crust, 
jU|d the sulphuret formed, deposits much nearer the flame of the 
‘imp. In applying this method, it must be borne in mind that 
sulphuretted hydrogen alone, especially if moist, may be decom- 
posed by the heat with the deposition of globules of sulphur, 
j' hich while warm have a yellow color; but when cold, they 
dye only a very faint yellow tint. The tersulphuret of arsenic 
l* readily distinguished from free sulphur in being soluble in 
aTamonia. When exposed to a slow current of dry hydrochloric 
dcid gas, tersulphuret of antimony readily disappears, whilst the 
solphuret of arsenic is unaffected by this gas. These methods 
distinguishing between these deposits, were first pointed out 
y Tettenkofer, and Fr esenius. 
There is no other metal, besides arsenic and antimony, that 
1 7 by this method of Marsh, yield a deposit in the heated 
. "cHon-tubc. Sulphur may yield a yellowish-white, and sele- 
a reddish-brown stain ; but these stains could not be con- 
fided with the arsenical deposit, 
tub ECOMPOSITION by nitrate of silver.—If the reduction- 
‘Ui *1 1C aPParatus he substituted by a tube bent at a right 
be (hig. 10, e), and the arsenuretted hydrogen conducted into 
s°hition of nitrate of silver, both the gas and the silver-salt 
ci go decomposition, with the production of arsenious acid, 
Vv| !C 1 rcrnains in solution, and the elimination of metallic silver, 
lch falls as a black precipitate. The reaction in this case is 
19 290 
ARSENIC. 
as follows : AsH3 + 6 AgO, N05= 3HO + As03 +6Ag + 6 NOs- 
The resulting solution, therefore, contains arsenious acid and 
free nitric acid, together with any excess of nitrate of silver 
employed. In applying this test, which was first proposed by 
Lassaigne, the current of gas should not be rapid, and only a 
quite dilute solution of the silver-salt should at first be em- 
ployed ; more of the salt may afterwards be added, if required. 
The presence of the arsenious acid thus produced, may be 
shown by either of the following methods : 
1. If the solution be filtered, and the filtrate exactly neu- 
tralised with ammonia, it will yield a yellow precipitate of arsen- 
ite of silver, having the properties already described. Should 
the whole of the nitrate of silver have been decomposed by the 
arsenuretted hydrogen, it will of course be necessary to add a 
little of this salt, after the neutralisation by ammonia, before 
the precipitate will appear. Since in the application of this 
test, the neutralisation of the eliminated nitric acid will giye 
rise to nitrate of ammonia, in which the arsenite of silver ig 
sparingly soluble, the reaction will not be quite as delicate as 
when the test is applied to a pure solution of arsenious acid- 
2. If the excess of nitrate of silver in the filtered solution 
be precipitated by slight excess of hydrochloric acid, the solu- 
tion again filtered, and the filtrate treated with sulphuretted 
hydrogen gas, it yields a bright yellow precipitate of tersul- 
phuret of arsenic. The arsenic from the I,oooth part of a 
grain of arsenious acid, can in this manner be recovered with- 
out any appreciable loss. Instead of treating the solution with 
sulphuretted hydrogen, after the removal of the excess 
nitrate of silver by hydrochloric acid, it may be examined by 
Reinsch’s test. 
3. If, after the removal of the excess of nitrate of silver by 
the cautious addition of hydrochloric acid, the filtrate be cau- 
tiously evaporated to dryness, the arsenic will remain as a whit6 
deposit of arsenic acid, which when moistened with a solution 
of nitrate of silver, assumes a brick-red color. 
Delicacy of this reaction.—ln the following investigations? 
the arsenious acid was dissolved in ten grains of pure watei? 
the solution placed in a small test-tube with a few fragments FALLACIES OF MARSH’S TEST. 
291 
2lnc, and then sufficient sulphuric acid added to evolve a slow 
stream of gas. The gas thus evolved, was conducted into five 
S’lams of a dilute solution of nitrate of silver. 
Tftt grain of arsenious acid, yields a gas that produces a 
copious, black precipitate in the silver-solution, 
rrro-u grain, yields a good precipitate. 
roToTTo grain : a black deposit soon appears in the immersed 
end of the delivery-tube, and in a little time black flakes 
appear on the surface of the silver-solution. 
To o7oiro grain: after some minutes, a distinct deposit forms 
m the lower end of the delivery-tube. 
The delicacy of this reaction, depends partly upon the fact 
lat the arsenuretted hydrogen evolved from one part of arseni- 
-oas acid, eliminates six and a half parts of metallic silver. 
Fallacies.—Nitrate of silver is also decomposed by antimon- 
j hydrogen, with the production of a black precipitate. 
9iis reaction, however, as already pointed out {ante, p. 229), 
e whole of the antimony, even to' the last trace, is thrown 
°Ayn as antimonide of silver. This method will, therefore, 
rVe to separate and detect arsenic in the presence of anti- 
sist ’ eV6n accorcbng 1° Hr. Hofmann, when the mixture con- 
Pa t °ne °b ie f°rmer and one hundred and ninety-nine 
8 of the latter metal, and only a minute quantity of the 
l>ctiire is examined. 
, °? also, will sulphuretted hydrogen and the hyduret of 
0£ Poorus, produce black precipitates, in a solution of nitrate 
a bla^6*"' J! 
is obvious, therefore, that the mere production of 
. acb Precipitate, in the silver solution, is not in itself direct 
evi(lence nf Hr • 
or tlie presence ot arsenic. 
l’°si\ 1611 hydrogen is passed into a solution of cor- 
ed • G Sublil*ate, it produces a yellow or brownish-yellow pre- 
rea which according to H. Rose consists of 3Hg2CI; As—the 
AntC.^0n being, perhaps, AsH3 A6HgCl=3 HCI + 3 Hg2 Clj As. 
a . . °nuretted hydrogen, under like circumstances, produces 
gr 1e’ Aecculent precipitate, which almost immediately turns 
ai'Ben8en len or almost black. The reaction of the 
fro U1 Sas *s extremely delicate. Thus the gas evolved 
le eO,oooth part of a grain of arsenious acid in ten grains 292 
ARSENIC. 
of fluid, will produce a quite distinct yellow deposit in the lower 
end of the delivery-tube. 
Since arsenuretted hydrogen is thus decomposed by salts ot 
silver and of mercury, as well as by free chlorine, nitric acid, 
and certain other substances, if either of these be present m 
the flask in which the gas is being generated, the latter may be 
entirely decomposed before leaving the apparatus. It is, there- 
fore, obvious that if in the examination of a suspected mixture 
by the method of Marsh, it should yield negative results, it 
would not follow, from this fact alone, that arsenic was entirely 
absent, even in a soluble form. 
Quite recently M. Z. Roussin has recommended, for the evo- 
lution of the hydrogen in the application of Marsh’s test, to 
substitute for the zinc, metallic magnesium, which may now be 
obtained in its pure state. If this metal be employed, before 
introducing the arsenical or suspected solution into the appara- 
tus, the evolved gas should be examined by passing it througll 
the red-hot reduction-tube for about ten minutes, for the pur" 
pose of testing its purity. This preliminary examination iS 
necessary, since magnesium is sometimes contaminated with 
silicium, which might give rise to silicuretted hydrogen, with 
the deposition of a dark brown deposit in the heated tube- 
This deposit, however, differs from an arsenical crust in that d 
is unaffected by nitric acid and a solution of a hypochlorite, 1 
being insoluble in these liquids. (London Chem. News, July? 
1866, pp. 27, 42.) 
Bloxam’s Method.—When arsenious acid is present in a 
mixture in which water is being decomposed by a galvanic cur- 
rent instead of by zinc and sulphuric acid, the arsenical com- 
pound is also decomposed by the nascent hydrogen with the 
formation of arsenuretted hydrogen gas. Professor Bloxam has 
recently proposed this reaction as a ready means of detecting 
arsenic, and as free from some of the objections that may h( 
urged against the method of Marsh. 
The form of apparatus he employs, consists of a two-ounm 
narrow-mouthed bottle, the bottom of which has been cut BLOXAM’S METHOD. 
293 
'Bid. replaced by a piece of vegetable parchment tightly stretched 
°Ver it and secured by a thin platinum wire. The bottle is 
furnished with a cork, carrying a funnel-tube, and a small tube 
ent at a right angle and connected with the reduction-tube by 
a Ca°ntchouc connection; through the cork also passes a plati- 
num wire bent into a hook, inside of the bottle, for suspending 
negative plate. The bottle is placed in a glass vessel of 
Sllch size as to leave a small interval between the two, and this 
arrangement placed in a large vessel of cold water; an ounce 
°f diluted sulphuric acid is then introduced into the apparatus, 
as to till the bottle and the outer space to about the same 
, Veb the positive plate being immersed in the acid contained 
111 this outer space. 
Ihe apparatus being thus adjusted, the terminal platinum 
Plates, each measuring about two inches by three-quarters of 
lnch, are connected by means of broad strips of platinum- 
-olb with a Grove’s battery of five cells; the one within the 
°ttle being connected with the zinc, and that in the outer ves- 
sel with the platinum extremity of the battery. ’ When the 
°ttle has become filled with hydrogen, the reduction-tube— 
vvhich may be constricted at several places—is heated to red- 
Bess for about fifteen minutes, to test the purity of the sulphuric 
acid employed. The liquid to be tested is then introduced into 
bottle by means of the funnel-tube, and the gas evolved 
in the same manner as in Marsh’s method. If the 
froths, from the presence of organic matter, a little 
Co_ °1 may be added. The author of this method states that 
-j W the I,oooth part of a grain of arsenious acid can be 
e°ted in an organic mixture, with the greatest ease and 
Certainty. 
When the poison exists in the form of arsenic acid, no ar- 
hydrogen is evolved by this process. When in this 
lnb however, the arsenic may be made to respond to the test 
y ti eating the solution, previous to its introduction into the 
with sulphurous acid gas or a few drops of a solu- 
a bisulphite of soda, and heating on a water-bath, until 
jW Sulphurous odor has disappeared. The introduction of a 
drops of a solution of sulphuretted hydrogen gas into the 294 
ARSENIC. 
apparatus also serves to reduce the arsenic acid, as the arsenic 
combines with the nascent hydrogen in preference to the sul- 
phur ; even when large excess of sulphuretted hydrogen ig 
employed, it does not interfere with the evolution of the arsen- 
uretted gas. But under these circumstances, a deposit of sul- 
phur may form in the reduction-tube outside of the arsenical 
deposit, and the latter may consist partly of tersulphuret of 
arsenic; the sulphuret of arsenic may be distinguished from 
free sulphur by its deep yellow color, and ready solubility in a 
warm solution of carbonate of ammonia, in which the sulphur 
is insoluble. 
The addition of sulphuretted hydrogen to the arsenical solu- 
tion, under the above circumstances, would precipitate as a 
sulphuret any antimony or mercury if present, in which form 
neither of these metals interferes with the detection of arsenic. 
Thus, Professor Bloxam states, the I,oooth part of a.grain of 
arsenious acid, converted into arsenic acid by the action 
hydrochloric acid and chlorate of potash, when mixed with one 
grain of tartar emetic and excess of sulphuretted hydrogen, and 
the mixture introduced into the decomposing cell, furnished m 
the reduction-tube a distinct deposit of arsenic free from anti- 
mony. Similar experiments made with mixtures of arsenious 
acid and corrosive sublimate, furnished equally good results- 
Without the addition of the sulphuretted hydrogen, the anti- 
mony and mercury are deposited upon the negative plate J 
when however a comparatively large quantity of the forniei 
metal was present, it yielded a metallic mirror in the reduction- 
tube. (Quart. Jour. Chem. Society, vol. xiii, pp. 12 and 338, 
et seq.) 
Other Reactions of Arsenious Acid.—Various other tests 
have been proposed for the detection of arsenious acid, but both 
in regard to delicacy of reaction and freedom from fallacy, fhe) 
are much inferior to those already described. Among these 
tests may be mentioned the following. 
1. Lime-water produces in solutions of the poison a whhe 
precipitate of arsenite of lime, which is readily soluble in hydro- 
chloric and most other acids. One grain of a 100 th solution 0 lODINE AND REDUCTION TESTS. 
295 
ai'senious acid, yields a copious, flocculent precipitate, which 
soon becomes granular; a similar quantity of a I,oooth solu- 
tion yields a very good, granular deposit ; and the same quan- 
tlt3r °f a 5,000 th solution, a slight cloudiness. The whole of 
tl 7 7 0 
■le arsenic may be withdrawn from the hydrochloric acid solu- 
tl°n of the arsenite, by Reinsch’s test. The lime reagent also 
produces white precipitates in solutions of several other acids, 
-• lodide of potassium slowly throws down from concentrated 
solutions of arsenious acid a white, granular precipitate, which 
aclheres tenaciously to the sides and bottom of the test-tube in 
'vhich the experiment is performed. The deposit, when treated 
Wlth hydrochloric acid, assumes a bright yellow color. Ten 
b'ains of a 50th solution of the poison fail to yield with the 
Ieagent a precipitate for several minutes; after about an hour, 
a Copious deposit has formed. If after the addition of the re- 
cent, the mixture be treated with large excess of hydrochloric 
It yields an immediate orange-yellow or yellow precipitate, 
Uc‘h is insoluble in hydrochloric acid, but readily soluble in 
xcess of arsenious acid. In this manner, the 100 th part of a 
of the poison in one grain of water, yields a copious, 
laUge-yellow deposit; and the I,oooth of a grain, a quite 
b°°d, yellow precipitate. If the arsenious acid be added to a 
ution of iodide of potassium in large excess of hydrochloric 
aci(i, the same yellow precipitate separates. 
Bichromate of potash produces in quite concentrated solu- 
s of arsenious acid a green precipitate of sesquioxide of 
r°raium. This reaction is common to solutions of tartar 
and of several other substances. 
When a solution of arsenious acid is treated with excess 
caustic potash and a drop of a solution of sulphate of copper, 
fixture on being boiled throws down a red precipitate of 
. Xl(le of copper, due to the reducing action of the arsenious 
, ’ /he latter remaining in solution as arsenic acid. In the 
an 1 10n le su^P^a^e copper, care should be taken to avoid 
itateXCOSS? °^ierwise the mixture will also yield a black precip- 
-1 e Protoxide of copper, which may mask the color of the 
Xlde. Solutions of grape-sugar and of certain other sub- 
lces, have a reducing action similar to that of arsenious acid. 296 
ARSENIC. 
Separation from Organic Mixtures. 
Suspected Solutions. Since arsenious acid, under certain 
conditions, is only sparingly soluble in water, before applying 
any chemical tests to a suspected mixture containing solid or- 
ganic matter, it should be carefully examined for solid particles 
of the poison. If the mixture contain much mechanically sus- 
pended matter, the whole may be placed in a large porcelain 
dish, water added if necessary, and the mass thoroughly mixed ? 
the larger organic masses are then carefully removed, the re- 
maining contents gently rotated in the dish, the supernatant 
liquid decanted, and the residue carefully examined, by means 
of a lens if necessary, for the solid poison. Any white masses 
or particles thus found, are washed in pure water, and allowed 
to dry. A very small portion of the dried mass is then heated 
in a small reduction-tube, and any sublimate obtained examined 
by the microscope. Other portions of the mass may be exam- 
ined by any of the other tests already described for the recog- 
nition of the poison in its solid state. So also, a portion nia} 
be dissolved in water and the solution tested. 
Whether the poison is thus discovered or not, the organic 
solids are returned to the liquid and the whole intimately mixed? 
the liquid then filtered, and the solids on the filter washed with 
distilled water, the washings being added to the first filtrate- 
Should the mixture presented for examination be thick from the 
presence of organic matter, after the addition of water and be- 
fore filtration, it may be acidulated with hydrochloric acid and 
gently boiled for ten or fifteen minutes. The filtrate, obtained 
by either of these methods, is concentrated to a convenient vol- 
ume, measured, and a given portion set aside for a quantitative 
analysis if necessary. Another portion, acidulated with hydro- 
chloric acid, is boiled with a very small slip of bright copper" 
foil, the latter not being added until the liquid has reached the 
boiling temperature. If the copper quickly receive a coating? 
it is removed from the liquid, and fresh slips of the metal added? 
as long as they receive a deposit. Should, however, the coppol 
first added not receive a metallic coating, the boiling should hi SEPARATION FROM ORGANIC MIXTURES. 
297 
continued until the liquid is evaporated to near dryness, before 
is concluded that the poison is entirely absent. Any slips of 
copper that have thus become coated, are washed by the aid of 
a gentle heat, first in pure water, then in water containing a 
trace of ammonia, and again in pure water, then drained, placed 
011 filtering paper and dried in a water-bath. One or more of 
tfie coated slips are then heated in an appropriate reduction- 
fabe, when the deposit, if consisting of arsenic, will yield a 
sabliinate of octahedral crystals of arsenious acid, readily iden- 
tified by means of the microscope. 
If the method now considered should fail to reveal the pres- 
ence of arsenic, there would be little doubt of the entire absence 
°f the poison, unless, possibly, there was also some other sub- 
stance present that interfered with its deposition upon the cop- 
Per : at the same time, if the copper remained bright, it would 
e quite certain that mercury and antimony also were absent. 
Should it be desired to pursue the investigation, another 
portion of the above filtrate may be examined after the method 
0 Marsh. Or, the liquid, acidulated with hydrochloric acid, 
be saturated with sulphuretted hydrogen gas, and allowed 
staud in a moderately warm place until the precipitate has 
c°tnpletely subsided; the precipitate is then collected on a filter, 
hashed, and, if it contains organic matter, purified in the man- 
-1161 fioreafter described. 
Vomited matters.—These are carefully collected, and exam- 
lllOrl -P . . . . 
u tor any solid particles of the poison. The mass is then 
Red with water, strongly acidulated with hydrochloric acid, 
kept at the boiling temperature for about twenty minutes; 
er the mixture has cooled, the liquid is filtered, the filtrate 
oncentrated, and then examined in the manner directed above. 
1 lleed hardly be remarked, that a failure to detect the poison 
de Vom*ted matters, would not in itself be conclusive evi- 
GllCe it had not been taken. 
Contents of the Stomach.—Before proceeding to the prepara- 
°l ffie contents of the stomach, for the application of chem- 
tests, they, as well as the inside of the organ, should be 
Cutely examined for any of the poison in its solid state, in 
banner described above. Any white particles or powder 298 
ARSENIC. 
thus found, are washed, dried, and tested in the usual manner 
for the solid poison. The physical appearance and condition of 
the stomach should also be carefully noted. 
The contents are now placed in a clean porcelain dish, and 
the inside of the stomach scraped and washed, the scrapings 
and washings being added to the contents of the dish; or, the 
tissue itself may be cut into small pieces, and these added to 
the contents. After the addition of water if necessary, the 
mass is intimately mixed with about one-eighth of its volume 
of pure hydrochloric acid, and maintained at near the boiling 
temperature until the organic solids are entirely disintegrated. 
The mixture is then allowed to cool, transferred to a clean 
muslin strainer, and the matters retained by the strainer washed 
with water: the strainer, with its contents, may be reserved for 
future examination, if necessary. The strained liquid thus ob- 
tained, if in large quantity, is concentrated at a moderate heat, 
again allowed to cool, and then filtered. 
A given portion of the filtrate thus obtained, is examined 
by the method of Reinsch, successive slips of the copper being 
added as long as they receive a deposit. Any pieces of the 
metal that have thus become coated, after being thoroughly 
washed and dried, are heated in a suitable reduction-tube, and 
the result examined in the usual manner. 
Another portion or the whole of the remaining filtrate, may 
be exposed for several hours to a slow stream of sulphuretted 
hydrogen gas, then gently warmed, and allowed to stand quietly, 
until the supernatant liquid has become perfectly clear. If e 
poison is present in considerable quantity, the precipitate may 
have a bright yellow color and consist of nearly pure tersid- 
phuret of arsenic ; the color of the latter, however, may be 
much modified by the presence of organic matter, which lS 
always more or less precipitated under these circumstances, 
usually of a yellowish-brown color. 
The precipitate thus produced is collected upon a small filteI’, 
washed, and while still moist, digested with pure aqua ammonia- 
this liquid will readily dissolve any sulphuret of arsenic present, 
whilst the organic matter may remain undissolved. The am®0' 
niacal solution is filtered, and the filtrate carefully evaporate SEPARATION FROM THE TISSUES. 
299 
at a moderate heat to dryness. The true nature of the residue 
thus obtained, if consisting of tersulphufet of arsenic, may be 
established by either of the methods heretofore pointed out, 
Under the special consideration of the sulphuretted hydrogen 
test. Should, however, the residue contain organic, matter and 
°nly 
a minute quantity of the sulphuret, it may require further 
purification before its arsenical nature can be satisfactorily de- 
termined. Under these circumstances, the dried residue is col- 
lected in a thin porcelain dish or crucible, moistened with a 
tew drops of concentrated nitric acid, and treated in the’ man- 
|ler described hereafter, for the purification of the sulphuretted 
jurogen precipitate obtained from the tissues. 
The contents of the intestines may be examined in the same 
Ulanner as the contents of the stomach. Sometimes, the poison 
Ulay be detected in these when there has been a failure to show 
Us presence in the stomach. 
From the Tissues.—Whether the examination of the con- 
teilts of the stomach or of the intestines have revealed the 
Presence of arsenic or not, an examination of the tissues or 
Ucls of the body, for the absorbed poison, should not be omit- 
c ’ Any poison found under these circumstances would be 
at which had entered the circulation and had its share in pro- 
ducing death; whereas, this would not be the case with that 
ud in the contents of the stomach or intestines. Moreover, 
it • ' 
s°uietimes happens that the poison is absent from the ali- 
-4 votary canal, and yet readily detected in some of the tissues. 
tfi S°r^ arsenic is deposited, to a greater or less extent, in all 
siib’ ssues the body, and any of these may be made the 
Jcct of analysis; the greatest relative quantity, however, is 
Ua ly found in the liver. The absolute quantity thus found, 
under the most favorable circumstances, rarely exceeds a 
b'Fain in weight. 
QUg 0r recovery of absorbed arsenic from the tissues, vari- 
uiethods have been proposed. In many instances, this may 
d‘l e^ec*ecl hy simply boiling the finely divided tissue with 
teo- GC hydrochloric acid, until the organic matter is well disin- 
and then employing the method of Reinsch. In this 
rier, We have, in several instances, recovered sufficient of 300 
ARSENIC. 
the poison from the liver to permit its confirmation by all the 
other tests. The more certain method of proceeding, however, 
is to entirely destroy, or at least carbonise, the organic matter, 
before applying any tests. For this purpose, the following 
methods have been advised. 
1. Fresenius and JBaho proposed to destroy the organic mat- 
ter by means of hydrochloric acid and chlorate of potash. The 
solid tissue, as about one-fourth of the liver, is cut into very 
small pieces, the mass placed in a clean porcelain dish, then 
treated with an amount of pure hydrochloric acid somewhat 
exceeding the weight of the dry, solid matter present, and 
sufficient water to form the whole into a thin paste. The dish, 
with its contents, is then heated on a water-bath, and about 
twenty grains of powdered chlorate of potash added to the hot 
liquid, and the addition repeated, with frequent stirring, every 
several minutes, until the mass becomes perfectly homogeneous, 
and of a light yellow color; the whole is then heated until tin1 
odor of chlorine has entirely disappeared; during this process, 
a little water should be occasionally added, to prevent concen- 
tration of the mixture. When the liquid mass has entire!.' 
cooled, it is transferred to a linen strainer, and, after the whole 
of the fluid has passed, the solid residue washed with warm 
water, the washings being collected separately. They are no" 
concentrated on a water-bath to a small volume, allowed to cool, 
and then added to the first-strained fluid, and the mixed liquid* 
filtered through paper. Any arsenic originally present, 
now exist in the filtrate as arsenic acid. 
The filtrate thus obtained, is treated with a solution of bisul- 
phite of soda, or exposed to a slow stream of sulphurous acid 
gas—prepared by boiling slips of copper with concentrated sul- 
phuric acid—until it smells strongly of the gas; it is then 
gently heated, until the sulphurous odor has entirely disap- 
peared. By this treatment, any arsenic acid present will be 
reduced to arsenious acid, in which form the metal is not onl} 
much more rapidly, but also, as we know from direct expel1 
ment, more completely precipitated by sulphuretted hydrogen? 
than when it exists in the form of arsenic acid. The solution? 
supposed to contain arsenious acid, may now be concentrate SEPARATION FROM THE TISSUES. 
301 
°n a water-bath at a temperature not exceeding 160° F., to 
about three times the volume of hydrochloric acid employed in 
hs preparation, then allowed to stand in a cool place for several 
hours, and any deposit that forms, removed by a filter. 
The liquid is next placed in a convenient vessel, and a slow 
of washed sulphuretted hydrogen gas transmitted through 
it for several hours ; it is then gently heated, and allowed to 
*tand in a moderately warm place for from twelve to twenty- 
lour hours. The whole of the arsenic, if present, will thus be 
Precipitated as tersulphuret of the metal, together with more or 
less organic matter. Should the liquid have contained mercury, 
Antimony, copper or lead,, these metals would also be precipi- 
tated, as sulphurets, by the sulphuretted hydrogen. It must be 
h')rne in mind, that liquids prepared as the above, usually yield 
Wlth sulphuretted hydrogen a brownish or yellowish precipitate 
°f organic matter, even in the absence of any metal. The pre- 
Clpitate is now collected upon a small filter, and washed, at first 
nith water containing a little sulphuretted hydrogen, until the 
"ashings no longer contain chlorine. 
Tor the purification of the precipitate thus obtained, different 
aiethods have been proposed. The following method, advised 
7 Professor Otto, has in our hands furnished the most satis- 
factory results. The filter containing the moist precipitate is 
spread out in a porcelain dish, and the precipitate stirred first 
Avith sufficient water to make a thin paste, then with excess of 
PUr° aqua ammonia.. Any sulphuret of arsenic present, together 
more or less of the organic matter, will be readily dissolved 
y the ammoniacal liquid, while the sulphurets of the other poi- 
Son°us metals mentioned above, which might be present, would 
‘‘main unchanged: it is usually stated that a portion of sul- 
| lUret of antimony, if present, might also be dissolved, but we 
<lVe already shown that this compound, at least in its pure 
datej requires about 20,000 times its weight of aqua ammonia 
1 s°lution. The ammoniacal mixture is then transferred to a 
lriall, moistened filter, and the solid residue washed with diluted 
arrunonia, the washings being collected with the first filtrate. 
f filter, with its contents, should be reserved for future ex- 
rilillation, if necessary. 302 
ARSENIC. 
The ammoniacal filtrate, which has usually a dark brown 
color, is now placed in a small porcelain capsule or thin evapo- 
rating dish, and evaporated to dryness on a water-bath; after 
this the residue is treated with a small quantity of concentrated 
nitric acid, and the mixture again evaporated to dryness, this 
operation with nitric acid being repeated, if necessary, until 
the moist residue has a yellow color. The residue is then 
moistened with a few drops of a concentrated solution of caustic 
soda, a small quantity of pure powdered carbonate of soda and 
nitrate of soda added, and the well-mixed mass cautiously evap- 
orated to dryness; the heat is then very gradually increased 
until the mass becomes colorless, when the organic matter will 
be entirely destroyed. In the performance of the operations 
now described, it is of the utmost importance that the nitric 
acid and compounds of soda employed be perfectly free from 
chlorine, since otherwise a portion or the whole of the arsenic 
may be volatilised in the form of chloride. 
Any arsenic present will now exist, in the above incinerated 
residue, as arsenate of soda, mixed with more or less nitrate, 
nitrite, carbonate, and sulphate of soda, the latter salt being 
derived from the oxidation of the sulphur. This mixture, when 
cooled, is dissolved in a small quantity of warm water, and the 
solution, after filtration if necessary, strongly acidulated with 
pure sulphuric acid, then evaporated until dense white fumes of 
sulphuric acid are evolved. By this treatment, the carbonic, 
nitric, and nitrous acids will be entirely expelled, the soda com- 
bined with them uniting with the sulphuric acid to sulphate of 
soda: the solution will, therefore, contain only sulphate of soda, 
and arsenate of soda, if present. Should there be any doubt 
as to the entire expulsion of the nitric and nitrous acids, a little 
more sulphuric acid is added, and the solution again evaporated. 
A portion of the strongly acid liquid thus obtained, ma) 
now be introduced into an active Marsh’s apparatus, and the 
evolved gas examined in the manner already described. Before 
submitting any remaining portion of the suspected liquid to the 
action of any of the other tests, it should be diluted somewhat, 
and the arsenic acid reduced to arsenious acid, by sulphurous 
acid gas, in the manner directed above; the solution may then, SEPARATION FROM THE TISSUES. 
303 
thought best, be again concentrated. A portion of the solu- 
ti°u may now be examined by the method of Reinsch; and 
an°ther portion submitted to the action of sulphuretted hydrogen 
gas. Any sulphuret of arsenic precipitated from a solution of 
Oiis kind, especially if only a small quantity of the metal be 
Present, will usually have a more or less orange hue. The 
a*senical nature of any sulphuret of arsenic thus obtained, may 
confirmed by any of the methods heretofore described, espe- 
Cially by the process of reduction. If the first examination of 
le suspected liquid, by Marsh’s method, indicate the presence 
comparatively large quantity of arsenic, a given portion 
°f the solution should be employed for the application of the 
Sldphuretted hydrogen test, and the quantity of the sulphuret 
tllus obtained estimated in the manner hereafter described. If 
aily of the suspected solution, that has been treated with sul- 
phurous acid gas, still remain, and it be desired to apply the 
. Ver and sulphate of copper tests, a small quantity of the liquid 
CXactly neutralised by caustic soda or carbonate of soda, then 
Vloed into two, about equal parts, to one of which a solution 
nitrate of silver, and to the other a solution of sulphate of 
CoPPer is added, when any arsenic present will yield its appro- 
priate precipitates. Since, under the circumstances just men- 
alp16 arsen*c woubl exist in the neutralised liquid as an 
( ah]ie arsenite, the ammonio-compounds of the silver and 
c°Pper salts should not be employed. 
The method now described for the disintegration of the tis- 
Ues’ and the subsequent purification of the precipitate produced 
sulphuretted hydrogen, is, according to our experience, much 
est yet proposed for the recovery, at least of minute traces, 
arsenic. At the same time, it has the advantage 
eluding mercury, antimony, and certain other poisonous 
feu rom the solution tested for arsenic, and yet provides 
their detection if present in the substance submitted to 
j. In illustration of the delicacy of this process, in 
• . r<a to the purification of the sulphuretted hydrogen pre- 
ate, the following experiment may be cited. A partially 
j mP°sed liver, free from arsenic, was boiled with diluted 
r°chloric acid and chlorate of potash, until the organic 304 
ARSENIC. 
matter was well dissolved, and to one thousand fluid-grairis oi 
the complex mixture thus obtained, the 100 th part of a gram 
of arsenious acid, in solution, was added,—the poison forming 
only the 100,000 th part of the mixture. The mixture was 
then gently heated, allowed to cool, and the strained liquid 
treated with a slow stream of sulphuretted hydrogen for twenty- 
four hours; the precipitate thus obtained which purposely 
contained an excess of organic matter—was then treated as 
described above, when the final solution, after treatment with 
sulphurous acid gas, gave with several reagents, results that 
could scarcely be distinguished from those obtained from an 
equal volume of pure water containing the 100 th of a grain ol 
the poison. 
For the purification of the above sulphuretted hydrogen 
precipitate, Fresenius recommends, to moisten it, together with 
the filter, with fuming nitric acid, evaporate to dryness on a 
water-bath, moisten the residue with warmed concentrated sul- 
phuric acid, then heat it for two or three hours on a water- 
bath, and finally on an oil-bath to a temperature of about 338 
F., until the charred mass becomes friable, and a sample of d 
no longer imparts a color when mixed with water. The mass 
is then warmed with a mixture of eight parts of water and one 
part of hydrochloric acid, the solution filtered, the filtrate pre' 
cipitated by sulphuretted hydrogen, the precipitate collected on 
a small filter, washed, redissolved in ammonia, the ammoniacal 
solution evaporated to dryness, and the residue weighed. 4he 
residue may then be reduced by a mixture of cyanide of potas- 
sium and carbonate of soda, in an atmosphere of carbonic acid 
gas, in the manner already described. 
In this connection it may be remarked, that the soft animal 
tissues may be broken up and dissolved by heating them, aft*3l 
being cut into small pieces, with diluted hydrochloric acid alone? 
without the subsequent addition of chlorate of potash. h>ut 
under these circumstances, they require prolonged heating? and 
the resulting solution when strained, is apt to be viscid and 
have a very dark or nearly black color, both of which are 
objectionable if the liquid is to be subsequently treated with 
sulphuretted hydrogen. A more serious objection, however? SEPARATION FROM THE TISSUES. 
305 
that if arsenic be present in the form of sulphuret, which is not 
infrequently the case when the parts have undergone putrefac- 
tion, the whole of it may escape solution. To a liquid prepared 
lri this manner, the method of Reinsch may, of course, be 
directly applied; whereas, this will not be the case, when the 
solution has been prepared by means of chlorate of potash. 
That the method of Reinsch will serve to recover very 
yoinute quantities of the poison from complex solutions, is well 
illustrated by the following experiment. The I,oooth part of a 
gram of 
arsenious acid, in solution, was added to one hundred 
Ulcl-grains of the complex mixture obtained by boiling a 
stomach with its contents, free from arsenic, with diluted 
yurochloric acid. The mixture was then boiled with a small 
ip of bright copper-foil, when after a little time, the foil 
Received a very good steel-like coating, which when heated 
ln a small contracted reduction-tube, furnished a fine octahedral 
CD stalline sublimate, very similar to that obtained in a like 
gunner, from the 100 th of a grain of the poison in solution 
Xli one hundred grains of pure acidulated water. It will be 
observed that in this case the poison was diffused in 100,000 
os its weight of the organic liquid. 
Danger and Flandin proposed to destroy the organic 
fatter of the tissues by means of concentrated sulphuric acid. 
e organic tissue, cut into small pieces, is treated with about 
its weight of the concentrated acid, and the mixture 
eated in a porcelain dish, until the black pasty mass first pro- 
u°ed, becomes dry and carbonaceous; the cooled mass is then 
.ed with a little concentrated nitric acid, or aqua regia, and 
evaporated to dryness. The mass is now treated with 
lng water, the solution acidulated with nitric acid, then 
Porated to dryness, the residue moistened with nitric acid, 
and fi J 7 
bquid again expelled by a moderate heat, this operation 
be Bltric achl being repeated, if necessary, until the mass 
the°llleS co^ol^ess- The mass is then dissolved in a little water, 
s°bition neutralised with carbonate of soda, evaporated to 
bb® residue again heated with a few drops of con- 
a§ la,led sulphuric acid. Any arsenic present will now exist 
arsenate of soda. The residue is then dissolved in a small 306 
ARSENIC. 
quantity of warm water, and the solution examined by the 
method of Marsh; or, the solution may be saturated with sul- 
phurous acid gas, and, after gently heating the liquid to expel 
the excess of gas, treated with sulphuretted hydrogen. 
The objection to the method of Danger and Flandin, is that 
if a chloride, as chloride of sodium, or common salt, be present, 
the carbonisation with sulphuric acid may give rise to the vola- 
tilisation, in the form of terchloride, of any arsenic present. 
The same objection would hold against the employment of aqua 
regia in the process. To meet these objections, it has been 
proposed to conduct the operations in a retort connected with a 
well-cooled receiver. 
3. Duties and Hirsch, in 1842, advised to treat the finely 
divided tissue, placed in a retort, with about an equal weight 
of pure concentrated hydrochloric acid, A cooled receiver, con- 
taining a little water, is then connected with the retort, and the 
latter heated on a chloride of calcium bath, until the contents 
become of a pasty consistency. This residue is mixed with 
about twice its weight of strong alcohol, the mixture allowed to 
digest some time, the liquid then strained through muslin, and 
the solid matter well washed with fresh alcohol. The mixed 
alcoholic liquids are filtered, and the filtrate distilled in a retort; 
until the alcohol passes otf, after which the residue is mixed with 
the acid contents of the receiver of the first distillation. This 
mixture, after cooling, is treated with sulphuretted hydrogen; 
when any arsenic present will be precipitated as tersulphuret. 
Since arsenious acid, when heated with concentrated hydro- 
chloric acid, is converted into terchloride of arsenic, which is 
volatile, it has recently been proposed to take advantage of this 
fact for the complete separation of the poison from the tissues; 
as well as from organic mixtures generally. The finely divided 
tissue, or the residue obtained by evaporating the suspected 
organic solution to dryness, is thoroughly dried on a water-bath; 
then placed in a retort with about its own weight of concentrated 
hydrochloric acid, and the mixture distilled on a sand-bath, to 
almost dryness, the distillate being collected in a well-coole 
receiver, containing a little water; the residue in the retort uia> 
be redistilled with a fresh portion of the acid. FAILURE TO DETECT. 
307 
The distillate thus obtained, contains the arsenic as terchlo- 
ri(ie, together with a large quantity of free hydrochloric acid, 
and more or less organic matter. A portion of the distillate 
be examined after the method of Reinsch. The remaining 
liquid, diluted if necessary, is examined by the sulphuretted 
hydrogen test, or by the process of Marsh, or both, and the 
lesults confirmed in the ordinary manner. Since the liquid 
contains a large quantity of free hydrochloric acid, this may 
interfere with the detection of minute traces of the poison by 
Ihe method of Marsh. The only metals, besides arsenic, that 
c°uld, under these circumstances, appear in the distillate, are 
antimony, bismuth, and, perhaps, tin. Should the arsenic exist, 
ln the substance subjected to distillation, in the form of sulphu- 
let, it would not appear in the distillate. Under these circum- 
stances, the residue in the retort may be heated with diluted 
ydrochloric acid and the occasional addition of chlorate of 
P°tasli, until the organic matter is destroyed; the resulting 
s°lntion is then treated with sulphurous acid gas, and subse- 
quently with sulphuretted hydrogen, in the manner heretofore 
described. 
The Urine.—No special method of analysis is required for 
e separation of arsenic from the urine. The liquid may be 
Concentrated to a small volume, strongly acidulated with hydro- 
.oric acid, and examined after the method of Reinsch, a 
tfi111U*e raS the copper-foil being at first employed. Or, 
le liquid may be evaporated to dryness on a water-bath, and 
e organic matter of the dry residue, destroyed by means of 
Th" roCal°ric acid and chlorate of potash, in the usual manner. 
8 secretion seems to be the principal channel through which 
is eliminated from the system. In a case related by 
l* he detected a trace of the poison in twenty-six 
Ces of urine, as late as the twenty-first day after it had 
een taken. 
jy adure to detect the Poison.—When arsenic is taken into 
s}'st it is rapidly absorbed and diffused through the 
ni> and after a time entirely eliminated from the living 
roin experiments on inferior animals, Orfila concluded 308 
ARSENIC. 
that if there is no suppression of the natural secretions, the 
poison will, in this manner, be entirely removed from the body 
in about fifteen days; and this view has been sustained by 
observations on the poisoned human subject. Independent of 
the action of absorption, the poison may, of course, be rapidly 
removed from the stomach and intestines, by vomiting and 
purging. Thus, Dr. Taylor relates a case in which no arsenic 
was found in the stomach of an individual who died in eight 
hours after taking nearly two ounces of the poison. (On Poisons, 
p. 411.) So, also, instances are reported in which death took 
place within a few days after the taking of the poison, and none 
of it was found in any part of the body. The liver, as hereto- 
fore stated, seems to be the organ in which the absorbed poison 
is principally deposited. According to the observations of Dr- 
Geoghegan, this organ usually receives its greatest quantity m 
about fifteen hours after the poison has been taken, when d 
may contain as much as two grains. It must be remembered, 
however, that the poison may be absent from the liver, and yet 
be present in some of the other organs of the body. In a case 
related by Professor Casper (Forensic Medicine), in which death 
occurred in twenty-four hours, arsenic, both in its solid state 
and in solution, was readily discovered in the contents of the 
stomach, but neither the blood nor the liver revealed d& 
presence. 
Detection after long periods.—lf arsenic be present in |C 
body at the time of death, the metal being indestructible, if 
may be recovered after very long periods. A case has already 
been mentioned in which we detected the poison, both in ltß 
absorbed state and in the stomach, in a body that had been 
buried seventeen months. And M. Ollivier relates a case in 
which it was detected after the lapse of three years. 111 a 
case quoted by Dr. Beck, the body had been buried for seven 
years. At this time, the body was entire; the head, trunk; 
and shoulders had preserved their form and position, but the 
internal organs of the chest and abdomen were destroyed, arl 
there only remained a mass of soft, brownish matter, which nrns 
deposited along the sides of the spine. A chemical examination 
of this matter, by MM. Ozanam and Idt, readily reveale QUANTITATIVE analysis. 
309 
the presence of arsenic. (Med. Jur., ii, p. 594.) So, also, the 
poison has been recovered after the lapse of eight, ten, and 
twelve years respectively. And Dr. J. W. Webster, of Boston, 
found four grains of arsenic in the body of a woman that had 
been buried in a vault for fourteen years. This seems to be 
the longest period yet recorded after which the poison has been 
discovered in the dead body. 
Since arsenic exists in certain soils, it is sometimes objected, 
""hen the poison is detected in an exhumed body, that it may 
have been derived from the surrounding earth. This objection 
however has no practical force, unless only a very minute quan- 
tity of the poison has been discovered and the parts of the body 
oxamined were commingled with the earth. Under these cir- 
cumstances, a portion of the earth may be separately examined, 
f°y the poison. The quantity of arsenic present in arsenical 
s°ds, according to various observers, never exceeds a mere 
Bane, and, in most instances at least, it can be extracted only 
y the stronger mineral acids. 
Quantitative Analysis.—Arsenic, when in solution in the 
rQI of arsenious acid, is most readily estimated as tersulphuret 
the metal. For this purpose, the solution is acidulated with 
yctrochloric acid, and a slow stream of washed sulphuretted 
yarogen gas passed through it, as long as a precipitate is pro- 
. Ced; the mixture is then gently heated, and allowed to stand 
a moderately warm place, until the precipitate has completely 
mhsided, and the supernatant liquid has become perfectly clear. 
f precipitate is then collected on a small filter of known 
"eight, well washed, at first with water containing a little sul- 
p Ur®tted hydrogen, thoroughly dried on a water-bath at 212° 
•? and weighed*, 
Que hundred parts by weight, of dry tersulphuret of arsenic, 
to 80‘48 parts of pure arsenious acid. A portion 
le dried precipitate, when heated in a reduction-tube, should 
""pletely volatilise, without either charring or leaving any 
Ues otherwise it is not perfectly free from foreign matter. 
16 quantity of arsenious acid present in an organic liquid, 
rilost readily estimated by introducing the solution into an 310 
ARSENIC ACID. 
active Marsh’s apparatus, containing just sufficient sulphuric 
acid to evolve a very sloiv stream of gas, and conducting the 
evolved gas into a properly diluted solution of nitrate of silver. 
The whole of the arsenuretted hydrogen thus evolved, as already 
pointed out, will be reconverted by the silver-salt, into arseni- 
ous acid, which will remain in solution, while metallic silver 
will be thrown down as a black precipitate. When the evolved 
gas has ceased to yield any further precipitate, the silver-solu- 
tion, containing the arsenious acid, is filtered, and the excess 
of the metal precipitated, by the cautious addition of hydro- 
chloric acid, as chloride of silver; this salt is then separated 
by a filter, previously moistened with water, and the filtrate, 
after concentration on a water-bath if necessary, treated with 
sulphuretted hydrogen, in the usual manner. 
If, in the above operation, a comparatively large quantity 
of nitrate of silver has been decomposed by the arsenuretted 
gas, the solution may contain so much free nitric acid as to 
decompose the sulphuretted hydrogen, and thus interfere with 
the results. Under these circumstances, the solution should be 
neutralised by caustic soda, and then acidulated with hydro- 
chloric acid, previously to being treated with sulphuretted hy- 
drogen ; and the precipitate produced by the latter, digested 
with diluted aqua ammonia, the ammoniacal solution filtered, 
the filtrate evaporated to dryness in a watch-glass on a water- 
bath, thoroughly dried, and weighed. 
111. Arsenic Acid. 
General Chemical Nature.—Arsenic acid is a compound 
of one equivalent of metallic arsenic with five equivalents of 
oxygen (Asos). In its pure state, it is a white, odorless, deli- 
quescent solid. When perfectly dry, it is only slowly soluble 
in water; but in its moist state, it is very readily soluble m 
that menstruum. Its aqueous solutions are colorless, and have 
a strongly acid reaction, quickly reddening litmus; this reaction 
is quite distinct in a solution containing only the 10,000 th pal* 
of its weight of the free acid. When an aqueous solution o 
arsenic acid is treated with sulphurous acid gas, the arsenic SPECIAL CHEMICAL PROPERTIES. 
311 
acid is reduced to arsenious acid, and the sulphurous acid ox- 
idised to sulphuric acid : As05 + 2 S02 = As03 + 2 S03. When 
exP°sed to a red heat, arsenic acid fuses, and is slowly dis- 
rated, being resolved into arsenious acid and free oxygen: 
As0s=As5=As03 + 02. 
Arsenic acid, like common phosphoric acid, is tribasic, or 
Capable of uniting with three equivalents of a metallic base; 
and one, or two equivalents of the base, may be replaced by 
Corresponding equivalents of water. The arsenates of the alka- 
les ai'e, for the most part, readily soluble in water; the other 
Metallic arsenates are insoluble in water, but soluble in sul- 
phuric, nitric, and hydrochloric acids. The arsenates of the 
Xed alkalies, containing two, or three equivalents of base for 
Ofich equivalent of acid, withstand a strong red heat without 
composition; but when they contain only one equivalent of 
Se> they are reduced to the bibasic or tribasic form, a portion 
°h the acid being decomposed and evolved in the form of free 
°xygen and arsenious acid. Under the action of heat, arsenic 
acid displaces all volatile acids from their basic combinations. 
£ regard to its physiological effects, arsenic acid appears, 
0111 the observations of several experimentalists, to be even 
1101 c poisonous than arsenious acid. As yet, however, there 
to be no instance of poisoning by it in its free state, in 
le human subject. But several instances of poisoning by the 
**ate of potash and of soda, are reported. The symptoms 
Served in these cases, were much the same as those usually 
lr°duced by arsenious acid. The treatment and post-mortem 
PPearances are also much the same. 
ac'qSPECIAL Chemical Properties.—When a mixture of arsenic 
ch °r an arsena^ej a*id carbonate of soda, is heated on a 
aicoal support, in the inner blow-pipe flame, the arsenical 
of i '°llnd is reduced and evolves the peculiar garlic-like odor 
le Vaporised metal. When arsenic acid or any of its com- 
aui18 Ultimately mixed with a reducing agent, as ferrocy- 
j oof potassium, and the thoroughly dried mixture heated 
sin u re^Uc^i°n“tube, it yields a sublimate of metallic arsenic, 
. ai to that obtained under like circumstances from arse- 
acid. 312 
ARSENIC ACID. 
When a drop of an aqueous solution of free arsenic acid is 
allowed to evaporate spontaneously to dryness, the residue usu- 
ally consists of a gummy mass 5 if, however, the evaporation 
has taken place very slowly, the acid is left chiefly in the form 
of long, slender, crystalline needles. If the residue thus ob- 
tained, be moistened with water and exposed to sulphuretted 
hydrogen gas, it acquires a yellow color, due to the formation 
of sulphuret of arsenic ; when moistened with a yellow solution 
of sulphuret of ammonium, and the mixture cautiously evap- 
orated to dryness, it leaves a pale yellow residue, consisting of 
pentasulphuret of arsenic, mixed with more or less free sulphur. 
Nitrate of silver converts the arsenic acid residue into a red 
brown deposit of tribasic arsenate of silver, which seems to 
have a tendency to crystallise. Under this action of nitrate of 
silver, the I,oooth part of a grain of arsenic acid yields a very 
good red brown deposit; and the 10,000 th of a grain, a quite 
distinct reddish-brown coloration. 
In the following examinations in regard to the behavior of 
solutions of arsenic acid, pure aqueous solutions of the free 
acid were employed. 
1. Sulphuretted Hydrogen. 
Normal solutions of arsenic acid, even when highly concen- 
trated, fail to yield an immediate precipitate, when treated with 
sulphuretted hydrogen gas; but sooner or later, the mixture 
becomes turbid, and after some hours, yields a light yellow pre" 
cipitate, the color of which is much lighter than that of the 
precipitate produced from solutions of arsenious acid. From 
solutions acidulated with hydrochloric acid, the precipitate sepa- 
rates more promptly, but even under these conditions, there is 
no immediate deposit. The precipitate, according to Wacken- 
roder, consists of a mixture of free sulphur and tersulphuret of 
arsenic, the sulphuretted hydrogen first reducing the arsenic 
acid to arsenious acid, and the latter then being decomposed? 
and the metal precipitated as tersulphuret: As05 +SHS = 5 
+S2 + AsS3. The formation of the precipitate is much facili- 
tated by a gentle heat. SULPHURETTED HYDROGEN TEST. 
313 
The precipitate, thus produced, is insoluble in hydrochloric 
a°id, but readily soluble, to a clear and colorless solution, in 
allia ammonia, as well as in the sulphurets and carbonates of 
Tat alkali. It is also soluble in the fixed caustic alkalies, and 
111 their carbonates and sulphurets; the fixed alkalies and their 
carbonates, however, leave a little free sulphur undissolved, 
which imparts to the solution a slight turbidity. If either of 
Tese solvent substances be present in the solution, the reagent 
WIH, of 
course, fail to produce a precipitate. 
In the following experiments, in regard to the limit of this 
ten fluid-grains of the arsenical solution, placed in a small 
test-tube, were acidulated with two drops of concentrated hydro- 
chloric acid, and treated with a slow stream of washed sulphu- 
retted hydrogen gas. 
100 th solution (= -jV grain of arsenic acid), yields no imme- 
diate change, but in about five minutes the solution be- 
comes slightly turbid, and in about five minutes more, a 
strong, yellow turbidity appears; if the mixture be now 
allowed to stand for a few hours, a quite copious, pale 
yellow precipitate separates. 
A similar quantity of a normal solution of the acid, 
when treated with the reagent, becomes turbid in about 
the same time as an acidulated solution, but fails to yield 
a precipitate, even after standing many hours. 
IjOOOth solution, when saturated with the sulphuretted gas, 
undergoes no perceptible change for about half an hour; 
Te liquid then becomes turbid, and after several hours 
p Tts fall a good precipitate. 
10,000 th solution: no perceptible change for some hours; 
after about eighteen hours, a quite perceptible, yellowish 
precipitate has formed. 
J-ne arsenical nature of the precipitate produced by this 
' enb niay be* established by either of the following methods, 
anl 6n 1G Precipilate is boiled with diluted hydrochloric acid 
a slip of bright copper-foil, the latter slowly receives a coat- 
b of metallic arsenic. b. If the precipitate be thoroughly 
v ,ec. and heated in a reduction-tube, it first fuses, then wholly 
a 1 ises, yielding a viscid globular sublimate. The lower 314 
ARSENIC ACID. 
margin of this sublimate, while still warm, has a dark color, 
while the central portion appears red, and the upper margin 
yellow; when cool, the whole of the sublimate assumes a yellow 
color, which in the upper portion of the deposit is quite pale. 
C. When dried and heated in a reduction-tube, with a mix- 
ture of cyanide of potassium and carbonate of soda, or with 
ferrocyanide of potassium, it yields a sublimate of metallic 
arsenic. 
On comparing the above results, obtained from solutions of 
arsenic acid by sulphuretted hydrogen, with those obtained from 
solutions of arsenious acid {ante, p. 263), it is obvious that the 
former acid is much more slowly and less completely precipi- 
tated by the reagent than the latter. When, therefore, the poi- 
son exists in the form of arsenic acid, before applying the 
reagent, it should be reduced to arsenious acid, by saturating 
the solution with sulphurous acid gas, and gently heating the 
liquid, until the odor of the gas has entirely disappeared. 
2. Ammonio-Sulphate of Copper. 
This reagent produces in normal solutions of arsenic acid? 
a greenish-blue, amorphous precipitate of arsenate of coppel 
(2 CuO; HO, AsOs). The same precipitate is produced trom 
solutions of neutral arsenates, by sulphate of copper alone, but 
this reagent fails to produce a precipitate in solutions of the free 
acid. The precipitate is readily soluble in nitric acid, and m 
ammonia, also in excess of free arsenic acid. In its general 
deportment with reagents, it is very similar to the corresponding 
precipitate produced from arsenious acid. 
1. ywo grain of arsenic acid, in one grain of water, yields with 
the reagent a copious, greenish-blue precipitate, which 
after a time assumes a more distinctly green tint. T®ll 
grains of the solution yield a bluish-green precipitate? 
which after a little time acquires a green color. 
2. rnnro grain; a good, bluish precipitate, destitute of a green 
tint. The precipitate from ten grains of the solution has 
a distinct greenish hue, which after a time becomes well 
marked. REINSCH’S TEST. 
315 
This test, like the preceding, is much less satisfactory and 
ehcate, when applied to solutions of arsenic acid than to those 
°1 arsenious acid. 
3. Nitrate of Silver. 
Nitrate of sily er throws down from normal and neutral solu- 
tions of arsenic acid, when not too dilute, a reddish-brown 
Precipitate of tribasic arsenate of silver (3 AgO; AsOa). The 
Piecipitate is readily soluble in nitric acid, but nearly wholly 
lns°luble in acetic acid*, it is also freely soluble in ammonia, 
sparingly soluble in the carbonate and nitrate of ammonia. 
Ton grain of free arsenic acid, in one grain of water, yields 
a quite copious precipitate, which aggregates into little 
2 masses, with a tendency to crystallise. 
g* Tono grain: a copious, reddish-brown precipitate. 
T'oTo'ou grain, yields a dirty-white precipitate, which after a 
tune assumes a reddish-brown tint. Ten grains of the 
solution, yield a dirty reddish-brown precipitate, which 
after a time acquires a clear reddish-brown color, 
rpi 1 
ane production of a reddish-brown precipitate by this re- 
abent, is cpiite peculiar to arsenic acid. 
. N>nwonio-nitrate of silver produces, in solutions of arsenic 
Cl(i? much the same results as the silver-salt alone, as above 
Scribed. 
4. Reinsch's Test. 
. hen a solution of arsenic acid or of an arsenate, is strongly 
mated with hydrochloric acid and boiled with a slip of bright 
metallic arsenic is slowly deposited upon the cop- 
q l’ hnuning an iron-grey or steel-like coating, the appearance 
***** on the thickness of the deposit. Without the addi- 
qq 1 hydrochloric acid, the metallic deposit fails to appear, 
in ft aiSeilmal nature of the deposit, may, of course, be shown 
tio ° sanie manner as heretofore pointed out, in the considera- 
j this test for the detection of arsenious acid. 
10 0 grain of arsenic acid, in one grain of water, when 
amdulated with hydrochloric acid, and heated to about the 
miling temperature with a mere fragment of copper-foil, 316 
ARSENIC ACID. 
yields," after a time, a very good metallic deposit upon the 
copper. 
2. itoVo grain: after a time, a quite good deposit 
3. roTS'oo grain, imparts only a slight tarnish to the copper? 
even after prolonged heating, the evaporated liquid being 
frequently renewed. 
It will be observed, on comparing the above results with 
those obtained from solutions of arsenious acid, that the metal 
is much less completely separated by the test from solutions ot 
arsenic acid than from arsenious acid. 
5. Sulphate of Magnesia and Ammonia. 
This reagent may be prepared by precipitating a solution 
of pure sulphate of magnesia by ammonia, and then adding 
sufficient chloride of ammonium to redissolve the precipitate; 
or, according to Fresenius, by dissolving one part of crystal- 
lised sulphate of magnesia and one part of chloride of ammonium 
in eight parts of water and four parts of solution of ammonia? 
allowing the mixture to stand at rest for some days, and then 
filtering. 
Solutions of free arsenic acid, and of neutral arsenates, yield 
with the reagent a white, crystalline precipitate of ammonio- 
arsenate of magnesia, which contains twelve equivalents ot 
water of crystallisation, the formula being: 2 MgO; 
As05, 12 Aq. The precipitate is readily soluble in nitric, hydro- 
chloric, and acetic acids, also in excess of free arsenic acid? 
7 / £ 
but only very sparingly soluble in ammonia, and in chloride ° 
ammonium. The reagent fails to produce a precipitate in solu- 
tions of arsenious acid. 
1. grain of arsenic acid, in one grain of water, yields a 
copious, white, amorphous precipitate, which immediately 
begins to crystallise, and in a little time becomes con- 
verted into a mass of plumose crystals, Plate Y, fig- 1* 
2. itoVo grain: no direct precipitate, but almost immediately 
crystals begin to separate, and very soon there is a copi°UB 
deposit of crystals, having much the same forms as those 
illustrated under 1. QUANTITATIVE ANALYSIS. 
317 
,C*‘ 570V0 grain: almost immediately, a granular cloudiness ap- 
pears, followed in a little time by crystals; after several 
minutes, there is a quite good, crystalline deposit. 
* T075-0-0 grain: in a very little time, a granular turbidity, and 
after some minutes, a satisfactory precipitate, consisting 
principally of small crystalline plates. 
. The reagent also produces a similar crystalline precipitate 
solutions of phosphoric acid. The true nature of the arsen- 
-1(ml crystals may be readily established by dissolving the pre- 
Clpitate in large excess of hydrochloric acid, and boiling the 
s°lntion with a slip of bright copper-foil, when the latter will 
receive a coating of metallic arsenic. 
. Acetate of lead throws down from solutions of free arsenic 
and of alkaline arsenates, a white, curdy precipitate of 
J’lbasic arsenate of lead (3PbO; As05). One grain of a 100 th 
ltion of the acid yields a quite copious precipitate; the same 
rluantity of a I,oooth solution yields a very good precipitate; 
|^nd a 10,000 th solution becomes quite turbid. It need hardly 
. e remarked that this reagent also produces white precipitates 
111 s°h-Uions of most other acids. 
]\,r nc^er the action of zinc and diluted sulphuric acid,, in a 
Sa s apparatus, arsenic acid undergoes decomposition, with 
e production of arsenuretted hydrogen, much in the same 
aimer as arsenious acid. 
Solutions of arsenic acid, unlike those of arsenious acid, fail 
1 educe bichromate of potash; nor do they give rise to red 
°xide of copper, when boiled with caustic potash and sul- 
Phate of COpper 
Quantitative Analysis.—Arsenic acid, when in solution, 
q^ay Pe estimated in the form of ammonio-arsenate of magnesia. 
0£ ° s°lution is treated with excess of a clear mixture of sulphate 
in 1^la^nes^a? ammonia and chloride of ammonium, pi’epared 
a e manner already described, and then allowed to stand in 
tpC for from twelve to twenty-four hours, in order that 
the prec*Pitate may completely separate. The precipitate is 
11 collected on a filter of known weight, washed with water 318 
ARSENIC ACID. 
containing a little ammonia, dried at 212° as long as it loses m 
weight, and its weight then noted. The dried precipitate, h 
pure, will now consist of 2 MgO; NH4 0, As05, Aq, and contain 
6053 per cent., by weight, of arsenic acid. 
Arsenic acid may also be estimated by first reducing it to 
arsenious acid, by means of sulphurous acid gas, and then pre- 
cipitating the metal as tersulphuret of arsenic, by sulphuretted 
hydrogen. One hundred parts by weight of thoroughly dried 
tersulphuret of arsenic, correspond to 98*5 parts of anhydrous 
arsenic acid. MERCURY. 
319 
CHAPTER YI. 
MERCURY. 
-Properties.—In its uncombined state, at ordinary tempera- 
les> mercury, or quicksilver, as it lias been named, is a liquid 
having a silver-white color, high metallic luster, and a 
11Slty of 13'56 : it is the only metal that is fluid at ordinary 
Glllperatures. At —39° F, it solidifies to a crystalline, ductile 
; and at about 660° it boils, being dissipated in the form 
. a c°lorless, transparent vapor, the specific gravity of which 
Water has no action on the metal in its pure state. 
. ed nitric acid oxidises and dissolves it to nitrate of sub- 
?Xlde of mercury; the hot concentrated acid readily dissolves 
to nitrate of protoxide of mercury, with evolution of fumes 
it illlox^e nitrogen. Hydrochloric acid has no action upon 
llt boiling sulphuric acjd readily converts it into sulphate of 
llQtoxide of the metal, with evolution of sulphurous acid gas. 
la typological Effects.—Many instances are reported in which 
tQrge quantities of mercury, even in some instances amounting 
s°nie pounds, wrere taken into the body without producing 
y deleterious effects. If, however, the metal, after being 
owed, becomes oxidised, as is sometimes the case, it may 
Uce active symptoms. When inhaled in the form of vapor, 
cury may give rise to serious results, as has not unfre- 
A been witnessed in those engaged in mining the metal, 
others exposed to its fumes, 
u Ruinations.—Mercury readily unites with most of the 
inoC °lC^S‘ oxygen it combines in two proportions, form- 
ifie 16 ack, or suboxide of mercury (Hg20), and the protox- 
oxide, or red precipitate (HgO). These oxides readily 
s,fipliur in two corresponding proportions : the subsulphuret 320 
MERCURY. 
(Hg2S) has a black color, so also has the protosulphuret (HgS) I 
by sublimation, the latter compound acquires a beautiful red 
color, under which form it is commonly known as vermilion. 
The subiodide of the metal (Hg2I), has a dingy-green color, 
while the protiodide (Hgl) has a brilliant, scarlet hue. The 
compounds of mercury most frequently employed for medicinal 
purposes, are the two chlorides, known at present as subchlo- 
ride, or calomel (Hg2CI), and protochloride, or corrosive subli- 
mate (HgCl). 
All the compounds of mercury are more or less poisonous; 
but of these, corrosive sublimate is one of the most active, and 
in a medico-legal point of view, much the most important. 
Corrosive Sublimate. 
Composition.—Corrosive sublimate consists of one chemical 
equivalent of mercury combined with one of chlorine, and is? 
therefore, the protochloride of mercury, its formula being HgCl* 
Formerly, this compound was known as bichloride of mercury? 
while calomel was considered the protochloride, whereas oX 
present calomel is regarded as a subchloride of the metal. This 
change, in regard to the names of these compounds, is due to 
the fact that formerly the combining equivalent of mercury WaS 
believed to be 200, while at present 100 is considered its true 
combining number. As met with in the shops, corrosive subli- 
mate is usually either in the form of a white, amorphous pon- 
der, or of semi-transparent crystalline masses; but occasional!)’ 
it is found in the form of well-defined crystals. 
Symptoms.—The effects of corrosive sublimate, when swal 
lowed in poisonous quantity, are a nauseous, metallic taste, wit!1 
a sense of heat and constriction in the mouth and throat; na 
sea, and pain in the stomach, attended with violent vomit111® 
and retching, the matters ejected being sometimes of a bib°uS 
character and containing blood; pain throughout the abdomen 
which generally becomes swollen and tender to the touch ; se 
vere purging, sometimes of bloody matters; great anxiety i 
flushed countenance; impaired or difficult respiration; small? f 
quent, and contracted pulse; cold perspirations; intense thir® ? PHYSIOLOGICAL EFFECTS. 
321 
scantiness or entire suppression of urine; cramps in the ex- 
| stupor, and sometimes death is ushered in with con- 
cisions. 
Such are the symptoms usually produced by large doses 
this poison, but they are subject to considerable variation. 
16 vomiting and purging, as well as the pain in the stomach 
fnd bowels, may cease for a time, and afterwards return with 
violence. Instances are also reported in which purg- 
lrig and pain in the abdomen were even entirely wanting. In 
®°aie instances, on account of the local action of the poison, the 
Ullg membrane of the mouth and the surface of the tongue, 
Present a white appearance. In protracted cases, inflammation 
0 mouth and salivation usually supervene. 
Among the more prominent differences usually observed be- 
CGn the symptoms of corrosive sublimate poisoning and those 
occasioned by arsenious acid, Dr. Christison mentions the fol- 
Wlng : 1. The symptoms of the former generally begin much 
®c°ner, the irritation in the throat often manifesting itself during 
e act of swallowing, and that in the stomach either immedi- 
,or within a few minutes; 2. Its taste is much more une- 
Tmvocal and strong; 3. The sense of acridity along the throat 
111 Hie stomach, is much more severe ; and 4. Blood is more 
e(llmntly discharged by vomiting and purging. 
(jj ?^le Allowing case, related by Devergie and quoted by Dr. 
lllsHson, well illustrates the usual course of acute poisoning 
.HHs substance. A woman swallowed three drachms of cor- 
Ve sublimate, in solution. She was soon afterwards seized 
With . . 7 
P vomiting, purging, and pain in the abdomen. In five 
foe 1S? was c°fo and clammy, the limbs relaxed, the 
• ° Pafo? eyes dull, and the expression that of horror and anx- 
he lips and tongue were white and shriveled, and there 
Vl°font fits of pain and spasm in the throat whenever an 
j 11 fo was made to swallow liquids *, also burning and prick- 
Uiatt^ 16 S'folet; frequent vomiting of mucus and bilious 
the Gr.S? wHh burning pain in the stomach and tenderness of 
Mthepi§astriam on the slightest pressure; and profuse purging, 
bre J:fllesrnus. The pulse was almost imperceptible, and the 
Ung much retarded. In eighteen hours, these symptoms 
21 322 
MERCURY. 
still continued without any material change; but the limbs were 
then insensible. In twenty-three hours, the patient died in a 
fit of fainting, the mind having remained clear up to the time 
of death. 
In a very protracted case, reported by Dr. Yigla, the fol- 
lowing symptoms were observed. A man, aged twenty-seven 
years, swallowed, in a state of solution, about fifty grains of 
corrosive sublimate. At once there occurred a strong metallic 
taste, constriction of the throat, nausea, and vomiting; but no 
severe pain. The vomited matters at first consisted of food, 
then of a serous fluid. An emetic was administered, and after- 
wards milk and white of egg. On the following day, there was 
more intense pain and irritation of the throat, coming on m 
paroxysms ; convulsive cough, expectoration of bloody mucus, 
and much suffering. Enteritis also developed itself, with vio- 
lent colic, tenesmus, and frequent slimy and bloody evacuations. 
On the third day, there was great inflammation of the mucous 
membrane of the throat and mouth, oedema of the palate and 
gullet; pseudo-membranous separation from the inflamed parts, 
and salivation; the intelligence was somewhat restored. lhe 
pulse was eighty-six ; the urine normal. Up to the twelfth da} , 
all inflammatory symptoms gradually subsided; but from that 
time great prostration of the powers of life and mercurial ca- 
chexia were presented. On the fifteenth day, ecchymosis upon 
the skin, irregular action of the heart, hiccough, albuminuria, 
and great irritability of the whole body were present. 
man died on the sixteenth day without any convulsion or strug- 
gle, in a state of extreme exhaustion. (Brit, and For. Med-' 
Chir. Rev., October, 1860, p. 380.) 
In poisoning by frequently repeated small doses of corrosU e 
sublimate, or chronic poisoning, as it is termed, the following 
symptoms are usually observed: a coppery taste in the mouth, 
loss of appetite, offensive breath, tenderness of the gums, pain& 
in the stomach and bowels, nausea, inflammation and ulceration 
of the salivary glands, swelling of the tongue, increased flow 
saliva, hot skin, quick pulse, and great muscular debility- 
is well known that some persons are much more susceptible tha*| 
others to the action of mercurial compounds. In a case ci FATAL PERIOD. 
323 
V -Dr. Christison, two grains of calomel caused ptyalism, ex- 
pensive ulceration of the throat, exfoliation of the lower jaw, 
and death. 
The external application of corrosive sublimate has not un- 
frequently been followed by fatal results. Two children, aged 
*evon and eleven years respectively, had an ointment composed 
°f one part of corrosive sublimate to four parts of tallow rubbed 
°Ver the scalp, for the cure of scaled head. Extreme suffering 
alnaost immediately ensued, and in forty minutes they were 
Completely delirious. There was excessive vomiting, great pain 
!n the bowels, with purging and bloody stools, and in one 
complete suppression of urine : there was no ptyalism. 
eath ensued in one instance on the seventh, and in the other, 
the ninth day. (Wharton and Stilhf, Med. Jur., p. 585.) 
n an instance quoted by Orfila, the application of powdered 
corrosive sublimate to the breast of a woman affected with an 
cerated cancer, caused intense pain in the part, nausea, bloody 
v°miting, convulsions, and death on the following morning. 
Period when Fatal.—The fatal period, in acute poisoning by 
corrosive sublimate, is subject to considerable variation; but on 
a:a average, perhaps, death takes place in about twenty-four 
ours. In 
an instance in which three children were accident- 
-3 poisoned by this substance, dispensed by mistake for calo- 
e j the eldest, aged seven years, took eighteen grains, and 
. c 111 three hours; the youngest, aged about two years, took 
Srains, and died in eleven hours; while the second, aged 
fr Ge Tears, received twelve grains, and apparently recovered 
0111 the immediate effects of the poison, but died with second- 
symptoms on the twenty-third day. (Medico-Chirurgical 
p/ATiew, April, 1885.) In a case recorded by Dr. Taylor (On 
ls°ns, p_ 4g2), a man died from the effects of an unknown 
irio t; ie 
poison, in less than half an hour. This is the 
lapidly fatal case yet reported, 
wl ' T re£> to protracted cases, Dr. Beck cites an instance in 
Avj .C 1 death did not occur until the eighth day; and another in 
life 1 a rnan took about six or eight grains of the poison, and 
p 6oaS Pr°l°nged until the twelfth day. (Med. Jur., vol. ii, 
‘ In a case reported by Dr. Coale, death took place 324 
MERCURY. 
on the eleventh day ; and in another, by Dr. Jackson, on the 
thirteenth day. (Wharton and Stille, Med. Jur., p. 534.) In 
Dr. Yigla’s case, already cited, death was delayed until the 
sixteenth day. 
Fatal Quantity.—That the same effects are not always pro- 
duced by equal quantities of corrosive sublimate, is well illus- 
trated in the cases of the three children just cited, in one of 
whom, six grains of the poison caused death in eleven hours, 
whilst in another, tivelve grains did not prove fatal until the 
twenty-third day. In Dr. Coale’s case, ten grains of the poison, 
dispensed by mistake for calomel, “were mixed and partially 
swallowed, but the great distress it caused produced ejection ol 
much of it from the stomach.” (Amer. Jour. Med. Sci., Jam? 
1851, p. 47.) This case is also remarkable in that during the 
eleven days the man survived after taking the dose, there was 
entire suppression of urine. A case has also just been cited m 
which six or eight grains proved fatal to an adult. 
On the other hand, several instances are reported in which 
persons recovered after having taken from half a drachm to two 
drachms of the poison; and Dr. Beck quotes an instance m 
which recovery took place after six drachms, in solution, had 
been swallowed. The writer just mentioned, also cites a case, 
reported by Dr. Budd, in which a female took an ounce of the 
poison, and after suffering the usual severe symptoms, entirely 
recovered. So, also, Dr. Taylor cites an instance, mentioned 
by Dr. Booth, in which recovery followed after a similar quan- 
tity had been taken. It is but proper to add, that in most, H 
not all, these cases of recovery, there was early vomiting. 
Treatment.—Of the various antidotes that have been p1’0' 
posed, in poisoning by corrosive sublimate, albumen, in the form 
of white of egg, seems to be much the most efficient. Orfik? 
who first suggested this antidote, employed it with completc 
success in experiments on poisoned animals; and it has in se%' 
eral instances been, at least apparently, the means of saviUo 
life in the human subject. It should be given in large quan- 
tity, and its administration speedily followed, if necessary, h}: 
the exhibition of an emetic. According to Dr. Peschier, tho 
white of one egg is required to neutralise four grains of the POST-MORTEM APPEARANCES. 
325 
Prison. Dr. Taddei strongly advised, as an antidote, the nse 
wheat flour, or gluten. This remedy also has been success- 
fn]ly administered to animals, and has been resorted to with 
aPParent success in the human subject. The free exhibition of 
uulk has also been highly recommended. 
Dr. Buckler, of Baltimore, in 1842, proposed the use of a 
fixture of gold-dust and iron-filings, and adduced some experi- 
ments on animals in support of its efficacy ; but these results 
"ere not confirmed by the experiments of Orfila (Toxicologic, 
v°s hp. 687). More recently, Dr. C. Johnston, of Baltimore, 
exhibited this mixture to a gentleman who had swallowed eighty 
Slains of corrosive sublimate, and the patient recovered. (Amer. 
J°ur, Med. Sci., April, 1863, p. 840.) Since, however, in this 
case, previous to the administration of the gold mixture, which 
Was not exhibited until about twenty-five minutes after the poi- 
S°R had been taken, there had been violent and almost inces- 
S<tnt vomiting for about fifteen minutes, and a mixture of white 
egg and milk had been freely given, it is by no means cer- 
that the alleged antidote had any part whatever in the 
lecovery of the patient. 
_ Among the other antidotes that have been advised for this 
poison, may be mentioned the protochloride of tin, iron filings 
oither alone or mixed with zinc, the hydrated sulphurets of iron, 
e carbonates of the alkalies, and raeconic acid and its soluble 
'Ats. Neither of these substances, however, possesses any ad- 
N milage over those mentioned above, and in fact some of them 
*Cem t° be entirely inert; moreover, neither of them is as likely 
0 5c at hand as either white of egg, flour, or milk. 
Post-mortem Appearances.—The lining membrane of the 
Ul°uth, fauces, and oesophagus is frequently more or less inflamed 
ar|d softened; but cases are reported in which these, parts were 
n<a hi a perfectly normal condition. The action of this poi- 
-011 upon the stomach and bowels is generally much greater 
lan that usually caused by arsenic. The coats of the stomach 
aie often more or less corroded and softened; and its internal 
oface has presented a dark, ulcerated appearance. In a case 
' ted by Dr. Christison, in which the patient survived thirty- 
le hours, the coats of the stomach were perforated. The 326 
MERCURY. 
intestines, especially the colon and rectum, often present signs of 
violent inflammatory action. This condition has been observed 
in cases in which the stomach was found but little affected. 
The urinary organs also are often much inflamed, and the blad- 
der greatly contracted and nearly or altogether empty. An 
instance is related in which the bladder was reduced to the size 
of a walnut; and another, that of a child, in which this organ 
was no larger than a marble. 
In the two cases of the three children, already mentioned, 
that proved fatal in three and eleven hours respectively, the 
mucous membrane of the mouth, pharynx, and oesophagus was 
found, in several places, softened, white, and could be easily 
detached by the handle of the scalpel. The mucous surface of 
the stomach and bowels exhibited patches of acute inflamma- 
tion, and here and there of partial erosion; at these places, its 
color was of a deep brown, or of an eschar-like hue. On the 
inner surface of the left ventricle of the heart, in the elder 
child, there were observed two patches of distinct ecchymosis, 
caused by the effusion of blood between the investing serous 
membrane and the muscular tissue. In the younger child, also, 
a similar appearance, but less distinctly marked, was found. 
No other appearances are mentioned in the description of these 
cases. 
In a case related by Dr. H. Williams (Am. Jour. Med. Sen? 
Jan., 1851, p. 79), in which thirty grains of the poison proved 
fatal, to an adult, on the third day, the following appearances 
were observed, twenty-five hours after death. The stomach 
was contracted, for the extent of about two inches, at its mid- 
dle portion, into the form of a dumb-bell. It contained a small 
quantity of bright yellow fluid, having the consistency of thm 
gruel. Its larger and smaller curvatures presented patches of 
dotted injection, of a bright crimson tint; and the mucous 
membrane was a little softened in the neighborhood of the most 
vivid red patches. Patches of beautifully arborescent vascu- 
larity were also observed at intervals along the whole extent of 
the small intestines; the large intestines were healthy. The 
bladder was contracted, and contained about a drachm of turbid 
urine. The other organs of the body were healthy. CHEMICAL PROPERTIES. 
327 
Chemical Properties. 
General Chemical Nature.—Corrosive sublimate crystal- 
lises, without water of crystallisation, in the form of colorless, 
transparent, rhombic prisms. Its specific gravity has been vari- 
ously stated at from 5*2 to 6'5. It has an exceedingly styptic, 
nauseous, metallic, and persistent taste. When heated to a 
temperature of 509° F., it fuses to a colorless liquid, which boils 
at about 568°, evolving an extremely acrid and poisonous vapor. 
If the vapor be received upon a cold surface, it frequently con- 
denses in the form of white crystalline needles. 
Corrosive sublimate is readily decomposed by the fixed alka- 
les, forming a chloride of the alkali and oxide of mercury. 
sulphuric acid fails to decompose or dissolve it, but it is 
somewhat soluble, without decomposition, in nitric and hydro- 
efdoric acids. When in aqueous solution, it is readily decom- 
posed and precipitated by various vegetable and animal prin- 
such as albumen, fibrin, casein, gluten, and tannic acid. 
once the utility of these substances, as antidotes, in poisoning 
AP this salt. 
Solubility' 1. In Water.—The solubility of corrosive subli- 
mate in water, at the ordinary temperature, has been variously 
abated at from nine to twenty parts of the fluid. According to 
?Ur own experiments, when the pure, powdered crystallised salt 
digested with ten times its weight of pure distilled water at a 
£ Porature of about 60°, with occasional agitation, for twenty- 
Ul hours, the solution then filtered, and the filtrate cautiously 
vaporated to dryness, it leaves a residue indicating that one 
lait of the salt had dissolved in 13'30 times its weight of the 
Hnid. & 
tin CCording to most observers, the salt is soluble in less than 
•t .Ge bines its weight of boiling water. From these statements, 
*s obvious that the quantity of the poison that may be taken 
1,1 solution by water, will in a great measure depend upon 
e temperature of the latter. 
. Alcohol.—When the powdered salt is agitated for some 
U esi at the ordinary temperature, with two parts of alcohol 328 
MERCURY. 
of specific gravity o'Boo (=9B per cent.), the solution filtered, 
and evaporated to dryness, the residue indicates that one part 
of the poison had dissolved in 2-47 parts of the liquid. 
On digesting the powdered salt with five parts of common 
whisky, for twenty-four hours, at the ordinary temperature, with 
frequent agitation, one part of the former required fifteen parts 
of the latter for solution. 
3. In Absolute Ether.—When powdered corrosive sublimate 
is digested, with frequent agitation, for twenty-four hours, with 
five parts of absolute ether, at a temperature of about 60°, one 
part of the salt dissolves in B’B parts of the menstruum. The 
salt is much more freely soluble in ordinary commercial ether, 
this liquid usually taking up about one-third of its weight of 
the poison. 
By taking advantage of the solubility of corrosive sublimate 
in ether, the salt may be separated from its aqueous solution, 
or from organic mixtures. If one grain of the mercury com- 
pound be dissolved in one hundred grains of pure water, and 
the solution agitated for several minutes with an equal volume 
of commercial ether, the latter withdraws from the water o*6'/ 
of a grain of the salt. According to M, Karls, the presence of 
camphor very much increases the solvent power of both ether 
and alcohol for corrosive sublimate. 
4. In Chloroform.—Corrosive sublimate is only very spar- 
ingly soluble in chloroform. When the powdered salt is occa- 
sionally agitated during twenty-four hours with twenty parts of 
this liquid, at the ordinary temperature, one part of the salt 
requires seventeen hundred parts of the fluid for solution. 
Of Solid Corrosive Sublimate. 
In its solid state, corrosive sublimate may be identified by a 
variety of reactions. 
1. When a small portion of the salt is moistened with a drop 
of a solution of iodide of potassium, it assumes a bright scarlet 
color, due to the formation of iodide of mercury, which is sol- 
uble to a colorless solution in excess of the potassium com- 
pound. This reaction is extremely delicate, and peculiar to the REACTIONS OF CORROSIVE SUBLIMATE. 
329 
pioto-coinbinations of mercury. The residue obtained from the 
evaporation of one grain of water containing the I,oooth part of 
a grain of corrosive sublimate, when moistened with the reagent, 
acquires a fine scarlet color; the residue from the 10,000 th of 
a grain, assumes a distinct yellow hue, and soon dissolves. 
-• If a drop of a strong solution of iodide of potassium be 
placed on a piece of bright copper, and a small quantity of cor- 
iosive sublimate added, the latter undergoes decomposition and 
Copper becomes stained with a deposit of metallic mercury, 
when rubbed with a soft substance, as the end of the 
ager, assumes a bright silvery appearance. This reaction will 
Manifest itself with the Least visible quantity of the mercurial 
p°mpound. The dried stain is readily dissipated by heat. If, 
111 this experiment, the iodide of potassium solution be substi- 
tuted by a drop of hydrochloric acid, the same metallic deposit 
takes place, and the reaction is equally delicate. 
°* When corrosive sublimate is moistened with a few drops 
a solution of protochloride of tin, it slowly assumes a grey 
c°l°r, and finally becomes nearly black, from the separation of 
Metallic mercury. In this reaction, the mercurial compound 
lGkls up the whole of its chlorine to the tin, converting the 
atter into bichloride of tin. 
I- If the salt be treated with a few drops of a solution of 
• * nir<d of ammonium, it quickly acquires a yellow color, which 
ph a me chariges to black, due to the formation of sul- 
-111 et of mercury. This transition of color is peculiar to proto- 
-olabinations of mercury. 
of '.J' ien touched with a strong solution of caustic potash or 
Co it immediately assumes a yellow or brownish-yellow 
r W hue to the production of protoxide of mercury. This 
serves to distinguish corrosive sublimate from calomel, 
sul; *S Slackened by the reagent, due to the formation of 
a ■‘°xide of mercury. Calomel is also blackened by caustic 
°nia, whereas the color of corrosive sublimate remains un- 
paged. 
in IGn a smah quantity of corrosive sublimate is heated 
in lehnction-tube, it volatilises unchanged, and recondenses 
e cooler portion of the tube, usually in the form of groups 330 
MERCURY. 
of crystals of the forms illustrated in Plate V, fig. 2. The ex- 
act forms of these crystals, however, will depend in a great 
measure upon the quantity of the salt employed: the most per- 
fect crystals are obtained by using only a very minute portion 
of the salt; when a comparatively large quantity is employed, 
the sublimate is in the form of a dense crystalline mass, desti- 
tute of any distinct crystals. 
In applying this test, the analyst should bear in mind that 
salts of ammonia, oxalic acid, and arsenious acid, will also, like 
corrosive sublimate and certain other compounds of mercury? 
completely volatilise with the production of a white sublimate. 
The sublimate from arsenious acid, however, is in the form of 
octahedral crystals, whereas that from corrosive sublimate is 
never in the octahedral form j moreover, the former substance 
does not fuse before volatilising. The sublimates from oxalic 
acid and salts of ammonia, may closely resemble that from the 
mercurial compound, but the latter is readily distinguished from 
these, as well as from all other volatile white powders, in that 
when touched with a solution of iodide of potassium, it assumes 
a bright scarlet color. 
7. When a small quantity of perfectly dry corrosive subli- 
mate is intimately mixed with several times its volume 
recently ignited carbonate of soda, and the mixture heated m a 
reduction-tube, the heat being very gradually increased, it yields 
a globular sublimate of metallic mercury; at the same time, an 
equivalent quantity of chloride of sodium is formed and remain8 
in the residue. The reaction, in this case, is expressed as f°l' 
lows : HgCl + NaO, C02 - NaCl +Hg+ 0 + C02. This reaction 
will manifest itself with the least visible quantity of the corro- 
sive salt, at least if the operation be conducted in a very narrow 
or contracted tube ; it must be remembered, however, that the 
production of the metallic sublimate is common to all the com- 
pounds of mercury. 
When the sublimate thus obtained is examined under a l°n 
power of the microscope, it will be found to consist of minute? 
opake, spherical globules, which under incident light have an 
exceedingly brilliant, metallic luster. These characters read- 
ily distinguish the mercurial from all other sublimates. The AMMONIA TEST. 
331 
Presence of the chlorine in the chloride of sodium, resulting from 
the decomposition of the corrosive sublimate, may be shown, by 
dissolving the saline residue in a little warm water, acidulating 
the solution with nitric acid, and then adding a little nitrate of 
sdver, when the chlorine will be thrown down as white chloride 
°f silver, which is insoluble in nitric acid but readily soluble in 
aitnnonia. Similar results would be obtained if the substance 
submitted to examination was calomelj but the insolubility of 
|he latter in water, readily distinguishes it from corrosive sub- 
[llate. Before resorting to this method of reduction, in the 
Examination of a suspected substance, the operator should sat- 
!sf> himself that the carbonate of soda about to be employed, 
ls Perfectly free from chlorine. 
Of Solutions of Corrosive Sublimate. 
Pure aqueous solutions of corrosive sublimate are colorless, 
aud when not very dilute, feebly redden litmus-paper. The 
ffUse°us metallic taste of the salt is well marked, even in very 
ouy diluted solutions. On cooling, hot concentrated solutions 
OAv down the excess of the salt in its crystalline state. When 
l°p of a tolerably strong solution is allowed to evaporate 
the residue usually consists of long, transparent, 
} stalline needles and prisms; but from more dilute solutions, 
1S llsually in the form of a confused crystalline film. The 
} sballisaqi011 of the salt is readily interfered with by the pres- 
°h organic matter. 
n the following investigations, in regard to the chemical 
tio aVlor °h solutions of corrosive sublimate, pure aqueous solu- 
fr nS. the salt were employed. The fractions indicate the 
Uutional part of a grain of the anhydrous salt present in one 
re£ 11 °h the liquid; and the results, unless otherwise stated, 
1 to the behavior of one grain of the solution. 
1. Ammonia. 
a ammonia produces in solutions of corrosive sublimate, 
nt°, Aocculent precipitate of the double chloride and amide 332 
MERCURY. 
of mercury (HgCl, HgNH2). The precipitate is soluble in large 
excess of the precipitant, and readily soluble in the mineral 
acids ; it is also soluble in some of the salts of ammonia, but 
insoluble in chloride of ammonium. 
1. yoo grain of corrosive sublimate, in one grain of water, 
yields with the reagent, a very abundant precipitate. If 
the mercurial solution be exposed to the vapor of ammo- 
nia, it yields the same reaction. 
2. TVYoTj grain, yields a quite good deposit. 
3. 576lou grain, yields a quite satisfactory reaction, by either 
ammonia or its vapor. 
4. TovVoo grain : a quite perceptible turbidity. 
This reagent also produces white precipitates in solutions of 
various other substances, beside proto-combinations of mercury* 
But if the mercurial precipitate be dried and heated, it readily 
volatilises without residue, in which respect it differs from all 
other metallic precipitates produced by the reagent. When 
heated with a solution of caustic potash, the precipitate is de- 
composed, with the production of yellow oxide of mercury* 
The precipitate is also decomposed by protochloride of tin, with 
the separation of metallic mercury. 
2. Potash and Soda. 
The fixed caustic alkalies, when added in not sufficiellt 
quantity to effect complete decomposition, throw down frolll 
quite strong solutions of corrosive sublimate, reddish-broMn 
amorphous precipitates, consisting of a compound of protoxide 
of mercury and the undecomposed chloride of the metal; hid 
when the reagent is added in excess, the precipitate has a y 
low color, and consists alone of the protoxide of mercury. The 
precipitate is insoluble in excess of the precipitant, but readily 
soluble in free acids. 
1. -5-5-0 grain of corrosive sublimate, yields a rather copied 
2. y-gro’ grain, yields only a slight cloudiness. 
The production of a reddish-brown precipitate, which he 
comes yellow upon the further addition of the alkaline reage^b 
reddish-brown or yellow deposit. lODIDE OF POTASSIUM TEST. 
333 
Ls peculiar to tlie per-combinations of mercury. The only other 
Petals that yield yellow precipitates with the reagent, are the 
xare substances platinum and uranium: the precipitate from the 
Tiner of these is usually in the form of octahedral crystals ; 
ut the precipitate from the latter, like that from mercurial 
impounds, is amorphous and insoluble in excess of the pre- 
cipitant. 
When the precipitated protoxide of mercury is collected, 
Iled, and strongly heated in a reduction-tube, it undergoes 
composition, with the evolution of free oxygen gas and the 
P1 eduction of a globular sublimate of metallic mercury. This 
faction will serve for the identification of the merest trace of 
e Mercurial precipitate. The presence of the chlorine of the 
c°U'osive sublimate, in the liquid from which the mercury was 
Precipitated, may be shown, by acidulating the solution with 
acid, and then adding nitrate of silver, when it will yield 
a white precipitate of chloride of silver. 
I he protocarbonates of the fixed alkalies, when added in lim- 
lt;ed quantity, throw down from one grain of a 100 th solution of 
c°D'osive sublimate, a quite good, yellowish precipitate; when 
I . excess of the reagent is employed, the precipitate has a 
Dck-red color. A similar quantity of a 500 th solution of the 
a yields only a slight turbidity. 
3. lodide of Potassium. 
a reagent produces in solutions of corrosive sublimate, 
scarlet, amorphous precipitate of iodide of mercury 
which is readily soluble in excess of the precipitant, as 
as in large excess of the mercurial solution. At first, the 
Clpitate has frequently a yellow color, but it quickly becomes 
} ' °t, except if only in minute quantity, when the yellow color 
tp Permanent. The iodide of mercury is also soluble in 
tp a kahne chlorides, and in alcohol, but only slowly soluble in 
re^. mineral acids; strong nitric and sulphuric acids 
l 7 decompose it, with the elimination of iodine, 
o 100 Srain of the salt, yields a copious, scarlet precipitate. 
Fool) grain: a reddish-yellow deposit. 334 
MERCURY. 
3. o .foTj grain, yields, with a very minute quantity of the re- 
agent, a quite satisfactory, yellow precipitate. 
The production of a scarlet precipitate by this reagent, is 
peculiar to solutions of persalts of mercury. The iodide of 
mercury, when washed, dried, and heated in a reduction-tube, 
volatilises unchanged, and recondenses in the form of a yellow, 
partly crystalline sublimate, the color of which slowly changes 
to scarlet. When the dried precipitate is intimately mixed 
with recently ignited carbonate of soda and heated in a reduc- 
tion-tube, it yields a sublimate of metallic mercury. 
4. Sulphuretted Hydrogen. 
When somewhat concentrated neutral or acidulated solutions 
of corrosive sublimate are treated with a relatively small quan- 
tity of sulphuretted hydrogen gas or of sulphuret of ammonium, 
they yield a precipitate, which, at least when the mixture is 
agitated, has a pure white color, and consists of the protosul- 
phuret of mercury and undecomposed corrosive sublimate. On 
the further addition of the reagent, the precipitate acquires a 
yellow, then a brown color, and finally becomes black, when if 
consists alone of the sulphuret of mercury. From more dilute 
solutions, the precipitate has at first a brownish color. 
The precipitated sulphuret of mercury is insoluble in nitric 
and hydrochloric acids, even on the application of heat; but it 
is readily decomposed and dissolved by cold nitro-hydrochlorie 
acid, with the separation of free sulphur, and the formation of 
protochloride of mercury and more or less sulphate of mercur}, 
the latter compound being derived from the oxidation of sonic 
of the sulphur. It is insoluble in the caustic alkalies, and n1 
the alkaline sulphurets. 
The following results, in regard to the reactions of this 
test, refer to the behavior of ten grains of the corrosive sub- 
limate solution, when acidulated with hydrochloric acid and 
subjected to the action of a slow stream of the washed su' 
phuretted gas. 
1. 100 th solution (=jL - grain of HgCl), yields an immediate, 
brownish precipitate, which soon assumes a dark brom1 SULPHURETTED HYDROGEN TEST. 
335 
color, and ultimately becomes black, the final precipitate 
being quite copious. 
IjOOOth solution, yields a yellowish-brown, brown, then a 
rather copious, black precipitate. 
10,000 th solution: the liquid immediately assumes a brown- 
ish color, then small brownish flakes separate, and after a 
little time, there is a good, brownish deposit. 
* 25,000 th solution: almost immediately the liquid assumes a 
yellowish color, and in a few minutes, very small, brown- 
ish flakes appear, which after some time subside to a very 
distinct deposit. 
°0?000th solution: very soon the fluid becomes turbid, and 
after standing some time, throws down a just perceptible, 
yellowish precipitate. 
* 100,000 th solution, .when saturated with the gas and allowed 
to stand several hours, undergoes no well-marked change. 
13ic progressive change of color from white to black, of the 
Precipitate j)roduced by this reagent, is peculiar to solutions of 
Pci salts of mercury. But this change, as shown above, is well 
Ularkcd only in comparatively strong solutions of the mercurial 
Sa 15 mid, the production of a black or brownish precipitate is 
llot in itself characteristic of mercury, since there are several 
‘ther metals that yield similar results, even from acidulated 
,s°lotions. 
Ihe sulphuret of mercury differs from all other black precip- 
Jates, produced under like conditions, in that when thoroughly 
lle3, and heated in a reduction-tube, it completely volatilises, 
residue or decomposition, and yields a black sublimate, 
aving a metallic appearance. Again, when mixed with anhy- 
°Us carbonate of soda, and heated in a reduction-tube, it 
j. ergoes decomposition with the production of a globular sub- 
j of metallic mercury. Either of these methods, but the 
ei is preferable, will serve for the identification of very 
ute traces of the mercurial compound. 
tlie liquid from which the mercury was precipitated by 
dr Su^P^ur reagent, was not purposely acidulated with hy- 
v?i^oric acid, previous to the application of the reagent, it 
serve for the detection of the chlorine of the corrosive 336 
MERCURY. 
sublimate, which element now exists as free hydrochloric acid. 
For this purpose, the filtered liquid is gently heated until the 
odor of the sulphuretted hydrogen has entirely disappeared, and 
then treated with a solution of nitrate of silver. 
5. Chloride of Tin. 
When a limited quantity of protochloride of tin is added to 
solutions of corrosive sublimate, the latter, giving up a portion 
of its chlorine to the tin, is reduced to subchloride of mercury? 
or calomel, which falls as a white precipitate, the reaction being: 
2 HgCl + SnCl = SnCl2 + Hg2CI. In the presence of an excess 
of the reagent, the mercury is entirely deprived of its chlorine 
and separates as a dark grey precipitate of exceedingly minute 
globules of the metal. The reaction in this case is: HgCl T 
SnCl = SnCl2 + Hg. The separation and subsidence of the me- 
tallic precipitate is much facilitated by heating the mixture with 
a little hydrochloric acid; if the clear supernatant liquid be 
then decanted, and the residue again heated with a little fresh 
hydrochloric acid, the finely divided mercury will unite into 
larger globules : the hydrochloric acid employed in this opera- 
tion, should be perfectly free from nitric acid; otherwise, the 
metallic globules may disappear, being dissolved. This tost 
may be conveniently applied in a watch-glass. 
1. yxitt grain of corrosive sublimate, in one grain of water? 
yields with the reagent a rather copious precipitate, which 
at first is white, but quickly changes to a grey color, and 
then becomes almost black. 
2. r.cnru grain, yields much the same results as 1 
3. j-;u~o~o grain : a quite good precipitate. 
4. YoTcnro grain, yields a quite distinct reaction. 
The production of metallic globules by this test, is, of course? 
peculiar to solutions of mercury. When the precipitate is pres- 
ent in only minute quantity, its globular nature may still be 
readily recognised by means of a hand-lens or a low power 
the microscope. If the precipitate be stirred with a small piece 
of bright copper-foil, the latter receives a coating of metalbc 
mercury, which when rubbed by a soft body, assumes a bright COPPER TEST. 
silvery appearance. In this manner, especially by the aid of a 
d*°P of hydrochloric acid and a gentle heat, the true nature of 
a mercurial deposit that will not furnish satisfactory globules, 
lllay sometimes be readily determined. 
It is important to bear in mind, in the application of this 
test, that the reaction of protochloride of tin is interfered with 
01 entirely prevented, by the presence of alkaline chlorates, 
and also of free nitric acid. 
6. Copper Test. 
When a small slip of bright copper-foil is placed in a normal 
s°lution of corrosive sublimate, the latter is decomposed with 
le deposition of metallic mercury upon the copper. The deli- 
C.acy of this reaction is much increased by acidulating the solu- 
n with hydrochloric acid, and also by heat. The deposited 
Mercury, when separated from normal solutions of the salt, has 
Usually a dark grey color; whilst, when from acidulated solu- 
ns> it has generally a bright silvery appearance: its exact 
aPpearance, however, will depend much upon the thickness of 
le deposit, which in its turn, will, of course, depend upon the 
Wl s°lu^on an(l the size of the copper-foil employed. 
hi'1(311 deposit has a dull color, it immediately acquires a 
soffit, mlrror-like appearance, on being rubbed with a piece of 
v°od or any similar substance, 
TK j 
irie same metallic deposit will, of course, make its appear- 
0f h’- W^en a drop of the mercury solution is placed on a jnece 
uSht copper plate. Under these circumstances, it has been 
**** to touch the copper, through the mercurial solution, 
pos’ ,a neod^e °I zinc. This somewhat facilitates the decom- 
cai ,lon mercurial compound, but at the same time, it 
glii^es Ihe separated mercury to be distributed over a greater 
the d being deposited upon the immersed end of 
I kon a smaH piece of the coated copper-foil is carefully 
he + 6C 7 dried at a moderate temperature, in a water-bath, and 
YqJ 0... m a narrow, perfectly dry reduction-tube, the mercury 
1 Ses and recondenses in the cooler portion of the tube, 
22 338 
MERCURY. 
forming a mist-like sublimate. Under a low power of the mi" 
croscope, this sublimate will be found to consist of innumerable 
spherical globules, which are opake to transmitted light, and 
present a bright silvery appearance, when viewed under inci- 
dent light. These characters readily distinguish the mercurial 
from all other sublimates. 
In the following investigations, in regard to the limit of this 
test, one grain of the mercurial solution, placed in a thin watch- 
glass, was acidulated with hydrochloric acid, and the mixture 
heated with a small fragment of the copper-foil. 
1. two grain of corrosive sublimate, imparts to the copper an 
immediate luster, and very soon the deposit becomes com- 
paratively thick. This reaction takes place about equally 
well without the presence of the free acid or the aid of 
heat. The copper employed should measure about yth by 
Ygfh of an inch in extent. When the washed and dried 
coated copper is heated in a narrow reduction-tube, h 
yields a very good, globular sublimate, many of the glob- 
ules measuring the 100 th of an inch in diameter. 
2. rruou grain: when the copper employed measures about t^1 
by of an inch, in extent, it immediately assumes a 
silvery appearance, and in a little time, receives a 
coating. Similar results are obtained without the aid of 
heat. Without either the free acid or heat, the deposd 
begins to form in a very little time 5 by heat alone, llß' 
mediately. The coated copper, when heated in a small 
reduction-tube, yields a very satisfactory globular sub- 
limate. 
3. grain: when the acidulated liquid is heated with a 
slip of copper measuring about by -2J-0-th of an m 
in extent, the mercurial deposit manifests itself immedi- 
ately, and very soon becomes satisfactory. If the coate 
copper be heated in a very narrow reduction-tube, it yield3 
a sublimate which is quite perceptible to the naked eyc?_ 
and which, under the microscope, is found to consist ° 
innumerable spherical globules. 
When deposits but little smaller than that just 
are heated in a reduction-tube of the ordinary form, even COPPER TEST. 
339 
Very narrow bore, the results are by no means uniform. Very 
Uniform results, however, may be obtained in the following 
banner. A quite thin and perfectly clean tube, of about the 
fOtli of an inch in diameter, is drawn out into a small capil- 
laiy neck, as shown in Fig. 11, A. The coated copper is then 
urtroduced, through the wider 
portion of the cooled tube, to 
*le point c, the neck of the 
tube moistened with water or 
"rupped with wet cotton, and 
le wider end very carefully 
l^sed shut, by a small blow- 
?*Pe flame, when the fusion 
18 slowly advanced to the copper, as illustrated in B. The 
pupillary end of the tube may now be fused shut. When the 
thus prepared, is wiped and examined under the micro- 
Sc°pe, the mercurial sublimate will be found at about the point 
Jj’ forming a narrow ring of well-defined globules. This method 
t ° Possesses the advantage of allowing the higher powers of 
e Uiicroscope to be applied, since these tubes may readily be 
11( pared with walls not exceeding the 200 th of an inch in thick- 
U-ss. The tube, containing the sublimate, may be reserved for 
Ure reference; after long periods, however, the sublimate 
tit eilora^es somewhat, and may even, if only in minute quan- 
V entirely disappear. 
2 VoWo grain: if the acidulated solution be heated, and as the 
evaporates its place supplied with pure water, the 
Tubes for Sublimation of Mercury. Natural size. 
c°pper in a little time presents a silvery appearance, and 
before long acquires a very decided, grey coating. When 
ibe coated copper is heated in a tube of the above form, 
yields a sublimate visible to the unaided eye, and which, 
Under an amplification of about seventy-five diameters, is 
found to consist of a ring of well-defined globules. In a 
uurnber of instances, over one hundred globules, varying 
iu size from the I,oooth to the 10,000 th of an inch in 
•arneter, were counted in a single field of the objective; 
niany of the globules measured over the 2,333 d of an inch 
111 diameter. 340 
MERCURY. 
5. grain: when the slip of copper employed measures 
only about yoth by -jVth of an inch in extent, the results 
obtained are very similar to those described under 4. 
6. riroVoY grain: the copper, after continued heating and re- 
newal of the evaporated liquid by water, acquires a quite 
distinct metallic tarnish, and when heated in a tube, °* 
the above form, yields a very satisfactory globular subli- 
mate. In some few instances, over one hundred globules 
were obtained, several of which, singly, measured over the 
1,750 th of an inch in diameter; the greater number of 
the globules, however, were quite small: none less than 
thd 10,000 th of an inch in diameter were counted. 111 a 
7 • A 
majority of the experiments made, the sublimate contained 
about fifty well-defined globules, most of which were usu- 
ally in a single field of a j|ds inch object-glass. So far as 
the evidence of the presence of mercury is concerned, this 
quantity of corrosive sublimate, when manipulated in the 
above manner, will yield just as satisfactory results as 
much larger quantity, the only difference being in the ab- 
solute number and size of the globules obtained. 
7. 5 o o!oVTS grain: the copper, even after prolonged heating, un- 
dergoes but little change in appearance. But when washed, 
dried, and heated in a tube, as many as twenty satisfac' 
tory mercurial globules were obtained, the largest of which 
measured about the 3,000 th of an inch in diameter; fhe 
diameter of most of them, however, varied from the 5,000t 
to the 10,000 th part of an inch. Most of the sublimate8 
obtained, contained from five to ten globules measuring 01 
exceeding the 5,000 th of an inch in diameter. 
For the identification of these mercurial globules, an amph 
fication of about seventy-five diameters is generally the m°s* 
useful. Under this power, a globule measuring the 3,000 
part of an inch in diameter, is very readily identified: such a 
globule, if a perfect sphere, would weigh only about the 
000 th part of a grain. So also, under this power, globules 
the 5,000 th of an inch in diameter, are very distinct and qul^e 
satisfactory: a globule of this size would weigh about 
70,000,000 th of a grain. And, even, when of the 7,000 th 0 COPPER TEST. 
341 
ail inch, their spherical nature may still be determined with 
considerable certainty: such a globule would weigh only about 
\ e 190,000,000 th part of a grain. But, under this amplifica- 
b°n, globules of only the 10,000 th of an inch in diameter, ap- 
PeTr as mere opake points, under transmitted light. Under an 
aaq>lification of about two hundred and fifty, a globule of the 
. boooth of an inch in diameter, may be satisfactorily deterra- 
med; and even when of only the 15,000 th of an inch, their spher- 
lcal outline may still be recognised with considerable certainty. 
account of the curvature of the glass tube, a Ith inch 
. JJect~glass, or an amplification of about two hundred and fifty, 
abont the highest power, that can be satisfactorily employed 
01 these identifications. When upon a flat surface, the true 
ature of globules much smaller than any of those mentioned 
ob.-, can be readily determined. Thus, with a |th inch 
o Jective, a globule, or u artificial star,” measuring only the 
WOth of an inch in diameter, and weighing about the 9,000,- 
;000th of a grain, will present the characters of sphericity 
aild °Pacity, and reflect incident light. It need hardly be ob- 
-olved, that it is not intended to imply, that quantities of mer- 
-P 111 themselves no greater than these, can be recovered 
bITI a solution and reproduced in the globular form. From the 
fa °Ve exPeiamenfs7 it would appear, that even under the most 
£Ol able conditions, the least quantity of corrosive sublimate 
. °m the mercury can thus be reproduced, is about the 
)000th or at least the 500,000 th part of a grain, 
t may be remarked, that in the above experiments, the 
as 100 is to 135‘5. It may also be added, that from these 
v I nments, it would appear that mercury is not as readily 
all 1 continued heating with boiling water, as is usu- 
of This view is also borne out by the experiments 
*Gsenius (Quantitative Analysis, p. 641). 
ol>c|. le tost noAv under consideration, has an advantage over 
qp lnaiA liquid tests, in that it is not as readily affected by 
c^ri^1|>ru Thus, ten grains of a 100,000 th solution of the mer- 
the ' Compound, will yield after a time, even upon renewal of 
evaP°rated liquid, very nearly as good results as one grain 342 
MERCURY. 
of a 10,000tli solution. Beyond a certain limit, however, this, 
like all other tests, will entirely fail to act. Another advantage 
possessed by this test, is that while being applied to a solution, 
the latter may be concentrated to almost any extent. 
Fallacies.—The mere fact of a metallic deposit being formed 
upon the copper, in the application of this test, is not in itself 
positive evidence of the presence of mercury, especially if the 
solution be acidulated and heated, since arsenic, antimony, sib 
ver, bismuth, platinum, palladium, and some few other metals 
are deposited under similar conditions. Of these various metals? 
however, the only ones that like mercury have a white silvery 
appearance, are silver and bismuth. Moreover, the only ones 
which like that metal, will deposit from cold solutions? are silver, 
platinum, and palladium. When, therefore, the deposition takes 
place from a cold solution, and has a bright silvery luster, or 
acquires it by friction, the deposit is most probably mercury ? 
but it might be silver. 
Of the various metals that might thus be deposited, even 
from heated acidulated solutions, the only ones that will vola- 
tilise and yield a sublimate, when the coated copper is heated 
in a reduction-tube, are mercury, arsenic, and antimony. But 
the spherical nature, as well as the opacity of the globules un- 
der transmitted light, and their bright silvery luster under inci- 
dent light, of the mercurial sublimate, readily distinguish rt 
from the octahedral crystalline sublimate produced by arsenic? 
and from the amorphous deposit occasioned by antimony. 
Metallic zinc, bismuth, cadmium, tin, silver, nickel, iron? 
lead, arsenic, and antimony, will also, like copper, decompose 
solutions of corrosive sublimate, with the formation of a coating 
of metallic mercury upon the applied metal. But neither of 
these metals have, for this purpose, any advantage over me- 
tallic copper, and in most instances the reaction is very much 
less delicate than when that metal is employed. 
So also, if the acidulated mercurial solution be placed in a 
small platinum or gold dish and the metal touched, through 
the solution, with a thin wire of zinc, iron, tin, or any other 
of the above-named metals, the salt undergoes decomposition? NITRATE OF SILVER TEST. 
343 
by galvanic action, the mercury being deposited chiefly upon the 
platinum or gold, but partly upon the other metal. Similar 
resnlts may be obtained, by applying a small slip of gold or 
platinum-foil to a corresponding slip of tin, zinc or iron, or to a 
Slnall cylinder of either of these metals, and immersing the com- 
bination in the acidulated mercurial solution. Some of these 
galvanic combinations are extremely delicate in their reactions; 
but they are not as well adapted for the detection of very minute 
flnantities of the poison as the method by copper alone, as be- 
lore described. 
7. Nitrate of Silver. 
This reagent decomposes neutral and acidulated solutions of 
c°iTosive sublimate, with the production of a white, amorphous 
Precipitate of chloride of silver (Ag Cl), which is insoluble in 
nih’ic acid. In its pure state, chloride of silver is very readily 
s°hible in ammonia, but as precipitated from the mercurial 
s°lntion, which itself yields a precipitate with ammonia, it is 
s°hible with difficulty in that alkali, and, unless very large 
excess of the alkali be added, is soon replaced by a white, 
deposit. 
1 7 
ioi grain of corrosive sublimate, in one grain of water, 
0 yields a very copious, white, curdy precipitate. 
iTrrs grain, yields a quite good precipitate, which, in the 
g mixture, dissolves with difficulty in ammonia. 
i'votto grain: a good deposit, which quickly disappears on 
the addition of ammonia. 
C s'oTo'o'o grain, yields a quite fair precipitate, 
g* grain: a very satisfactory turbidity. 
grain, yields a perceptible cloudiness. 
This reagent is simply for the purpose of detecting the 
Presence of the chlorine of the corrosive sublimate. The reac- 
-11 °f the reagent, is, of course, common to solutions of all 
it l 6 cb^orides and of free hydrochloric acid. If, however, 
e shown, by any of the other tests, that the solution also 
11 a*lls mercury, then it follows, providing the solution is not 
P c°mplex mixture, that the metal existed as corrosive sub- 
since this is its only soluble chloride. 344 
MERCURY. 
Other Reagents.—The mercury, from solutions of corro- 
sive sublimate, may be precipitated, in a state of combination, 
by several reagents other than those already described, but the 
reactions of these are much less delicate and characteristic, 
than those already considered. A few of these tests, however, 
may be very briefly mentioned. 
Ferrocyanide of potassium produces in solutions of the mer- 
curial compound, a dirty-white precipitate, which is soluble m 
excess of the precipitant. One grain of a 100 th solution of 
the salt, yields a very copious precipitate; and a similar quan- 
tity of a I,oooth solution, a quite good deposit. This is about 
the limit of the reaction of the test, for one grain of the solution. 
Ferricyanide of potassium throws down from aqueous solu- 
tions of the salt, a greenish-yellow, amorphous precipitate, which 
is insoluble in excess of the precipitant. One grain of a I,oooth 
solution of the mercurial compound, yields a quite good precip- 
itate; a similar quantity of a 5,000 th solution, yields only a 
slight turbidity. 
Protochromate of potash produces in quite strong solutions of 
the salt, a greenish-yellow precipitate; but the Bichromate of 
potash, occasions no visible reaction. 
Separation from Organic Mixtures. 
Since corrosive sublimate is readily precipitated, with more 
or less decomposition, by various animal and vegetable princi- 
ples, much of the poison, when added to mixtures of this kind, 
may be present in a form insoluble in water. Under these 
circumstances, however, sufficient of the mercury to be detected 
by the ordinary reagents will usually remain in solution, even 
in quite complex mixtures, and after standing for long periods. 
We find, that the solid coagulum resulting from the precipitation 
of the poison with albumen, which is one of the most insoluble 
compounds of this kind, when washed and dried, even to a 
horny mass, still yields up some of the mercurial compound on 
digestion with even cold distilled water; more of it to hot water, 
and still more, when boiled with water acidulated with hydro- 
chloric acid. RECOVERY FROM ORGANIC MIXTURES. 
345 
Suspected Solutions.—Any precipitate or mechanically sus- 
pended matter present, is separated from the suspected solution 
by a filter, and examined for any solid particles of the poison, 
then washed with warm water, and reserved for future examina- 
tion, if necessary. A portion of the clear liquid may then he 
acidulated with hydrochloric acid and boiled with a small slip 
°f bright copper-foil. If the copper quickly receives a metallic 
coating, it is removed from the liquid, and other and larger 
slips of the metal consecutively added, as long as they acquire 
a deposit. If the deposit thus obtained consists of mercury, it 
usually present a greyish-white appearance, and acquire a 
bright silvery luster when, gently rubbed with the finger, or any 
°ther soft body. The coated copper is then washed in alcohol 
0r ether, dried at a moderate temperature, one or more of the 
slips heated in an appropriate reduction-tube, and any sub- 
ulate obtained, examined by a loav power of the microscope. 
If the method now described, yields positive results, these 
may be confirmed, by examining other portions of the suspected 
yfiuid, by some of the other tests for the poison; this, however, 
ls not really necessary, at least so far as the presence of mer- 
cury 
is concerned. A portion of the liquid should be concen- 
k a.ted to a small volume, and allowed to stand in a cool place 
. r some hours, or longer if necessary, in order that the poison, 
present, may separate in its crystalline state. Any crystals 
118 obtained, after being carefully washed, are dissolved in a 
Slnall quantity of water, and a portion of the solution tested for 
c lorine, by nitrate of silver. 
Should the copper test, after prolonged heating and concen- 
. atlon of the liquid, fail to reveal the presence of mercury, it 
' Tute certain that the other tests for that metal would also 
ta:i 
le former. Under these circumstances, any organic solids 
from the suspected liquid, by filtration, are boiled for 
°at ten minutes with pure water, or better still, so far as 
? recovery of mercury is concerned, with water strongly 
with hydrochloric acid; the cooled liquid is then 
er°d, and the filtrate examined by the copper test, in the 
auner above described. It is obvious, that the employment 346 
MERCURY. 
of hydrochloric acid, in the preparation of the liquid, will, m 
the event of the detection of mercury, preclude the possibility 
of proving’ that the metal existed as a chloride, at least so far 
as the liquid under examination is concerned. 
Another method for the recovery of corrosive sublimate, 
from organic liquids, is to violently agitate the concentrated 
liquid, for some minutes, in a small bottle or a stout test-tube, 
with about twice its volume of pure commercial ether, in which, 
as we have already seen, the salt is freely soluble. When the 
liquids have completely separated, which will usually require a 
repose of only a few minutes, the ethereal fluid is carefully 
decanted into a watch-glass, and allowed to evaporate sponta- 
neously. Any saline residue thus obtained, is examined in the 
usual manner, a portion of it being first examined by some of 
the tests for the poison in its solid state. In the application of 
this method, it should be borne in mind, that ether does not 
extract the whole of the salt from its aqueous solutions. 
Vomited matters.—The matters ejected from the stomach 
may be examined in the same manner as just described, for 
suspected solutions. If an antidote, such as white of 
egg or 
gluten, were administered, the organic solids of the vomited 
matters may require long boiling with water strongly acidulated 
with hydrochloric acid, for the complete separation of the poison. 
Contents of the Stomach.—As corrosive sublimate is readily 
soluble, it is not often found in its solid state in the stomach*, 
however, this examination should not be omitted. The mass ig 
then stirred with sufficient water to make it quite liquid, the 
mixture gently heated for some time on a water-bath, the cooled 
liquid filtered, and the solids on the filter well washed with 
pure water, the washings being collected with the first filtrate- 
The filter, with its contents, should be reserved. The 
liquid is then concentrated to an appropriate volume, and, 
necessary, again filtered. 
A portion of the filtrate, thus obtained, is acidulated willl 
hydrochloric acid, and boiled with a very small slip of bright 
copper-foil. If this fails to receive a metallic coating, the ap- 
plication of the heat should be continued until the liquid 10 
evaporated to near dryness, before concluding that the poison RECOVERY FROM ORGANIC MIXTURES. 
347 
18 entirely absent. On the other hand, if the copper quickly 
receives a metallic deposit, it is removed from the liquid, and 
°ther slips of the metal added, as long as they become coated. 
The mercurial deposit, as already pointed out, is readily distin- 
guished from that produced by arsenic, antimony, and most 
°ther metals that are thus deposited, by its bright silvery 
aPpearance, at least when rubbed. The coated copper is thor- 
°ughly washed in alcohol or ether, dried, then heated in a 
reduction-tube, and any sublimate thus obtained examined by 
the microscope. 
Another portion of the filtrate may be acidulated with hydro- 
chloric acid, and treated with excess of a solution of proto- 
ehloride of tin, when, if it yields a dark grey precipitate, the 
ruixture is gently heated until the precipitate has completely 
subsided • the supernatant fluid is then decanted, the residue 
hashed with hot water, then boiled with a little water strongly 
aci(lulated with pure hydrochloric acid, which will cause any 
finely divided mercury present to collect into comparatively 
aige globules. It must be remembered that various organic 
solutions yield with the tin reagent, a white precipitate, which 
may 
more or less conceal the color of the mercurial deposit. 
. nuer these circumstances, the precipitate is boiled for some 
tllne with a strong solution of caustic potash, which will dis- 
s°lve the organic matter, leaving the mercury in the form of a 
§reyish-black powder. This is then boiled with a little diluted 
acid, in the manner just described. 
> u portion of the filtrate be acidulated with hydrochloric 
acid and treated with sulphuretted hydrogen gas, any of the 
present will give rise to sulphuret of mercury, which 
be thrown down as a black precipitate, at least if excess 
tfie reagent has been employed. After the precipitate has 
c°mpletely subsided, it may be collected on a filter, washed, 
then dried. Its mercurial nature may be established, by 
it with several times its volume of recently ignited 
aikonate of soda, and heating the mixture in a reduction-tube, 
®u it will undergo decomposition with the production of a 
0 ular sublimate of metallic mercury, readily identified by 
emis of the microscope. 348 
MERCURY. 
The positive reaction of either of the foregoing tests, would, 
of course, simply indicate the presence of the mercury of the 
corrosive sublimate. For the purpose of showing the presence 
of the chlorine, it is best to agitate a portion of the filtrate with 
ether, in the manner already directed, then allow the ethereal 
solution to evaporate spontaneously, dissolve the residue in a 
small quantity of warm water, and treat the solution with nitrate 
of silver. As the alkaline chlorides are insoluble in ether, the 
detection of chlorine under these circumstances, would not be 
open to the objection that would hold if the silver reagent were 
applied directly to the original filtrate; especially will this objec- 
tion be guarded against, if the ethereal liquid, on evaporation, 
leave the poison in its crystalline state. 
Should the methods already given fail to reveal the presence 
of mercury, in the filtrate, then the organic solids left upon the 
filter may be examined. For this purpose, the mass is trans- 
ferred to a porcelain dish, the solids cut into small pieces, and 
boiled for about twenty minutes with pure water, the mixture 
being frequently stirred by means of a glass rod. When the 
mixture has cooled, the liquid portion is separated by a filter, 
the filtrate concentrated to a small volume, and then examined 
in the manner before directed, for the first filtrate. Instead of 
boiling the organic solids with pure water, they may be boiled 
with water containing hydrochloric acid, until they are entirely 
disintegrated. If, however, this method be employed, the pres- 
ence of the chlorine of the corrosive sublimate could not be 
established. 
Another method for the examination of the above organic 
solids, is to boil the mass with a somewhat concentrated solution 
of caustic potash, until the solids are entirely decomposed, and 
then treat the mixture with a solution of protochloride of tin, 
the heat being continued for some little time after the addition 
of the tin reagent. Any dark grey precipitate thus obtained, 
is carefully collected, washed, and examined in the manner 
already described. 
From the Tissues.—lf there has been a failure to detect 
corrosive sublimate under one or other of the conditions non 
described, it will no longer be possible to show the presence of SEPARATION FROM THE TISSUES. 
349 
the poison as a whole; but the presence of the absorbed mer- 
cury may be shown, in some of the soft tissues of the body, 
the recovery of the absorbed metal, various methods have 
been advised. The finely divided tissue, as about ten ounces 
°f the liver, may be made into a thin paste with water con- 
taining about one-sixth of its volume of pure hydrochloric acid, 
and the whole heated at about the boiling temperature, until the 
organic solids are completely disintegrated, which will usually 
require about two hours. The mass is then allowed to cool, 
transferred to a linen strainer, the strained liquid filtered, and 
then concentrated to a comparatively small volume. A portion 
0f the liquid may now be heated to the boiling temperature, 
ar|d examined by the copper test, employing at first only a 
very minute slip of the metal. In applying this test, it should 
remembered that the copper, after prolonged heating, may 
acquire a very distinct stain or tarnish, even in the absence of 
Mercury or of any other metal. Before heating the copper in 
a reduction-tube, it should be very thoroughly washed, first in 
M ater containing a little ammonia. Should the first portion of 
%aid examined, fail to reveal the presence of mercury, then 
another and larger portion or even the whole of the remaining 
nqmd, should be examined in a similar manner. 
, The copper test will serve to recover very minute quantities 
mercury from very complex organic liquids. A portion of a 
ninan liver, free from mercury, was boiled with diluted hy- 
lochloric acid, in the manner just described, and the liquid 
plained. To one hundred grain-measures of the strained fluid, 
Xe I,oooth part of a grain of corrosive sublimate was added— 
le poison then being under a dilution of 100,000 times its 
Weight of the organic liquid—and the mixture boiled with a 
Very small slip of bright copper-foil. After a little time, the 
pepper received a very distinct metallic stain, and when washed, 
Xlcd, and heated in a small reduction-tube, yielded a sublimate, 
llch> under the microscope, was found to contain over one 
ndred characteristic globules of mercury, 
j. Should the examination of the first portion of the above 
(iUld indicate the presence of mercury, and it be desired to 
1111 sue the investigation, another portion may be treated with 350 
MERCURY. 
excess of protochloride of tin, and gently warmed, until the 
precipitate has completely deposited. The precipitate is then 
collected, washed, and boiled in a porcelain evaporating dish 
with a solution of caustic potash, until the organic matter is 
dissolved and the residue assumes a dark grey color. The clear 
supernatant liquid is then decanted, and the residue repeatedly 
washed with hot water, then boiled with hydrochloric acid, 
which will cause any finely divided mercury present, if entirely 
free from foreign matter, to coalesce into globules. 
Another, and in some cases preferable method for breaking 
up the animal tissues, is by means of hydrochloric acid and 
chlorate of potash, in the manner described for the recovery of 
absorbed arsenic. The finely divided tissue is treated with 
about one-fourth of its weight of pure concentrated hydrochloric 
acid, and the whole made into a thin paste, by the addition of 
water. The mixture is then heated to about the boiling tem- 
perature, and small quantities of powdered chlorate of potash 
occasionally added, until the mass becomes perfectly homogene- 
ous, after which it is kept at a gentle heat, until the odor of 
chlorine has entirely disappeared. The mixture is now allowed 
to cool, the liquid filtered, and the solid matters on the filter 
well washed with hot water. The filtrate may now be partially 
neutralised with pure carbonate of soda, and concentrated, until 
its volume is about five times that of the hydrochloric acid em- 
ployed in the destruction of the organic matter. 
The liquid thus obtained, after filtration if necessary, ig 
exposed for several hours to a slow stream of sulphuretted hy- 
drogen gas, then gently heated, and allowed to stand in a mod- 
erately warm place for about fifteen hours. Any mercury 
present, will now be in the precipitate, in the form of the black 
sulphuret, together with more or less organic matter, the color 
of which may disguise that of the mercurial compound. The 
precipitate is collected upon a small filter, well washed, and 
then transferred to a porcelain dish, treated with a proportion- 
ate quantity of concentrated hydrochloric acid, and pure nitric 
acid added drop by drop, until complete solution has taken place. 
By this treatment, with the mixed acids, the mercury of the 
mercurial sulphuret, will be dissolved to protochloride of the FAILURE TO DETECT. 
351 
ttietal, while the sulphur will be eliminated as a yellow adherent 
mass, which, as fast as it forms, should be removed, by means 
a glass rod. On now cautiously evaporating the solution to 
dryness on a water-bath, the chloride of mercury will be left as 
a white crystalline mass; if the eliminated sulphur was not 
leinoved from the mixture, the residue may consist largely o± 
the sulphate of mercury. 
A portion of the saline residue, thus obtained, may be tested 
f°r the poison in its solid state, and another portion dissolved in 
a small quantity of water, and the solution examined by the 
c°pper test. If the addition of water produces an insoluble 
} ellow sulphate of mercury, its solution may be readily effected 
by the addition of a drop or two of hydrochloric acid. 
From the Urine.—About twelve ounces of the urine are 
strongly acidulated with hydrochloric acid, evaporated to a small 
volume, filtered, the filtrate boiled with a small slip of bright 
c°Pper-foil, and the latter washed, dried, and examined in the 
llsual manner. Another method for the examination of this 
®llfl, is to concentrate it to near dryness, and- then destroy the 
olganic matter by means of hydrochloric acid and chlorate of 
Potash, in the manner described for the recovery of the poison 
ortl the tissues. If the first of these methods be adopted and 
ere is a failure to detect the metal, any solids separated by 
Nation should be examined. 
Hr. Thudichum remarks (Pathology of the Urine, p. 408), 
Jjlat in all cases, where the urine contains mercury, there is at 
same time a peculiar albuminous substance present in it, 
Uch with nitric acid yields a faint reaction of albumen. A 
stance is also present, having the reactions of sugar. In 
®°nie cases of mercurialism, he adds, the metal only appeared 
fke urine at intervals, even where the symptoms had under- 
§°He no remission. 
Failure to detect the Poison.—lt has not unfrequently hap- 
pened, in acute corrosive sublimate poisoning, that there was a 
Ul'e to detect the poison in any part of the dead body. In 
Case quoted by Dr. Beck (Med. Jur., ii, p. 638), in which a 
tq rrian had poisoned herself with this substance, not a trace of 
poison was found either in the matters vomited during life, 352 
MERCURY. 
or in the contents of the stomach after death. So, also, in a 
case cited by Wharton and Stifle (Med. Jur., p. 538), none of 
the poison was detected in the stomach and intestines of a young 
man who had taken three drachms of corrosive sublimate, and 
died from its effects on the sixth day. In another instance, 
recorded by Dr. Taylor (On Poisons, p. 471), in which two 
drachms were swallowed, and death occurred on the fourth day? 
a chemical examination of the stomach, blood, and tissues failed 
to reveal the presence of mercury. 
According to the observations of I. L. Orflla, absorbed mer- 
cury is eliminated from the system chiefly by means of the 
kidneys. In examining the urine of patients treated with mer- 
curial preparations, he found the metal five days after it had 
ceased to be taken, but in eight days it was no longer discov- 
ered. In experiments upon dogs, he found the metal in the 
tissue of the stomach and liver of some of the animals, as late 
as the eighteenth day, but in others, similarly treated, it had 
entirely disappeared. (Orfila’s Toxicologic, 1852, i, p. 680.) 
When mercury remains in the body at the time of death, 
it, like arsenic, may be recovered after very long periods. 111 
a case of corrosive sublimate poisoning, which we examined 
several years since, and in which death occurred on the fourth 
day, the metal was readily detected in the stomach and liver oi 
the body, after it had been buried nine months: none of the 
other organs were chemically examined. It need hardly be 
remarked, that, since mercurial preparations are so frequently 
taken medicinally, the detection of minute traces of the metal 
in the dead body, would not in itself be any evidence that it 
was the cause of death. 
Quantitative Analysis.—The quantity of corrosive subh' 
mate present in a solution of the salt, may be readily estimated 
by precipitating the metal as sulphuret of mercury. For this 
purpose, the solution, acidulated with hydrochloric acid, is satu- 
rated with a slow stream of washed sulphuretted hydrogen gaS? 
after which it is allowed to stand in a moderately warm place, 
until the precipitate has completely subsided; the precipitate is 
then collected on a small filter of known weight, washed with QUANTITATIVE ANALYSIS 
353 
Pure water until the washings no longer have an acid reaction, 
-j , O O 
'V'led on a water-bath at 212° F., and weighed. One hundred 
parts by weight, of the dried sulphuret of mercury, correspond 
11G ■Bl parts of anhydrous corrosive sublimate. 
If in the application of the tin test, a known quantity of the 
Mercurial solution was employed, any globules of metallic mer- 
CllrJ obtained, may be carefully washed, dried, and weighed. 
lle hundred parts of the pure metal, represent 135*5 parts of 
Coi’rosive sublimate. 354 
LEAD 
CHAPTER YII. 
LEAD, COPPER, ZINC. 
Section I. Lead 
History and Chemical Nature.—Lead is one of tlic elementary 
metals. Its symbol is Pb; its combining equivalent 103*57 j 
and its density 11*44. It is found in nature associated with 
several other elements, but it occurs principally as sulphuret of 
lead, or galena. Lead has a bluish-grey color and strong me- 
tallic luster ,* it is quite soft, being easily scratched by the 
finger-nail, and leaves a well-known mark upon white paper* 
It is very malleable, and fuses at about 620° F. 
In its pure state, lead is unacted upon by pure water. But 
if air be present in the liquid, or its surface be freely exposed 
to the action of the atmosphere, the metal rapidly becomes cor- 
roded, and gives rise to oxide of lead, which partly unites with 
water and partly with carbonic acid, forming a hydrated oxY' 
carbonate of lead. This compound partly deposits upon the 
lead as silky scales or falls as a precipitate, while a portion re- 
mains mechanically suspended in the liquid; at the same time? 
some little of the compound becomes dissolved. When, how- 
ever, the water holds in solution certain salts, such as the 
7 7 
carbonates, sulphates or the phosphates, an insoluble crust 01 
lead-salt slowly deposits upon the metal and protects it frolll 
further action, and thus none of the lead is dissolved. On the 
other hand, the presence of chlorides and of nitrates, increase 
the corrosive action of water. 
Lead is readily soluble in diluted nitric acid, especially upo** 
the application of heat, with the formation of nitrate of l°a 
and the evolution of binoxide of nitrogen. Cold diluted siJ' 
phuric acid fails to dissolve it, but the hot concentrated ad 
dissolves it to sulphate of lead, with the evolution of sulphur°uS PHYSIOLOGICAL EFFECTS. 
355 
acid gas. Hydrochloric acid, even under the application of heat, 
has hut little action upon the metal. Heated on charcoal before 
I'he hlow-pipe flame, it gives rise to a yellow or brownish incrust- 
ation of oxide of lead. 
Physiological Effects.—In its metallic state, lead seems to be 
lllei't. But all the compounds of the metal that are soluble in 
ater or in the animal juices, are more or less poisonous. Acute 
poisoning by the preparations of lead has been of rare occur- 
ence, and has chiefly been the result of accident. 
Of the salts of lead, the acetate, or sugar of lead, is one of 
the most active, and has more frequently been taken as a poi- 
s°n than any of the other compounds. This salt, however, is 
poisonous only when taken in large quantity. Van Swieten 
Mentions an instance in which it was given to the amount of a 
(h'achrn daily for ten days before it caused any material symp- 
t°m. (Christison, On Poisons, p. 430.) Cases are not wanting, 
°Wever, in which it produced speedy and violent symptoms, 
ail<l even death. 
Acetate of Lead 
Symptoms.—When an overdose of acetate of lead is swal- 
the patient usually experiences at first a nauseous me- 
taste in the mouth, with a sense of constriction or burning 
eat in the fauces and epigastrium. These effects are followed, 
B°oner or later, by severe gastric and abdominal pains, which 
ai e generally relieved, but sometimes increased by pressure ; 
B°ifietimes the pain is constant, at others intermittent. There 
8 also nausea, and sometimes frequent vomiting of a yellowish 
01 blackish liquid ; in some instances, the vomiting has been 
Veiy shght. The thirst is frequently very urgent; the skin 
hut sometimes hot, and generally covered by a clammy 
Aspiration; the countenance anxious; the strength greatly 
Pestrated; the pulse slow and feeble, but often accelerated. 
some instances there has been severe and even bloody purg- 
eiag either no discharges or the matters passed being hard, dry 
11 black, and their discharge attended with pain. Sometimes 356 
LEAD 
the limbs become affected with spasms, and a sense of constric- 
tion. The urine is usually diminished in quantity. The intel- 
lect generally remains clear. 
It is well known that the frequently repeated introduction 
of even very minute quantities of any of the preparations of 
lead into the system, may after a time induce serious symptoms. 
Under these circumstances, the patient experiences general de- 
pression, loss of appetite, a metallic taste in the mouth, and 
generally great thirst. The throat becomes dry, the breath 
fetid, the countenance dull and anxious, the skin dry and of a 
dull yellow color, the bowels constipated, and the urine gener- 
ally diminished. At the same time, a blue line forms along the 
margins of the gums • and there is more or less uneasiness or 
pain in the abdomen. As the case advances, the pain in the 
abdomen becomes very severe, and more or less constant: the 
walls of this cavity are generally hard and depressed. These 
effects are frequently followed by sharp pains in the extremi- 
ties, muscular emaciation and paralysis. 
In a case recently reported by Dr. G. A. Kunkler, the 
external application of white-lead to a scalded surface, as a 
dressing, produced unmistakable symptoms of lead colic—acute 
abdominal pain, retraction of the umbilicus, constipation, and 
slight discoloration of the gums. (Brit, and For. Med.-Ohm 
Rev., Oct., 1857, p. 525.) 
When Fatal.—ln a case quoted by Dr. Beck, a soldier who 
swallowed an unknown quantity of acetate of lead in solution; 
was soon seized with the most violent symptoms, indicative of 
gastric inflammation, and died in great agony at the end of 
three days. (Med. Jur., i, 690.) Dr. Taylor refers to two 
cases in which Goulard’s extract—which is a solution of the 
subacetate of lead—was taken in unknown quantity by two 
children, aged respectively four and six years, and they both 
died within thirty-six hours. The Symptoms were at first vio- 
lent vomiting and purging: in one case they resembled tho»e 
of Asiatic cholera. (Op. cit., p. 482.) In a case mentioned 
by Dr. Christison (On Poisons, p, 430), the same preparation 
of lead was taken in unknown quantity by a soldier. The fh’st 
symptoms could not be ascertained, but on the second day? ANTIDOTES. 
357 
was affected with loss of appetite, paleness, costiveness, and 
Excessive debility; on the third day, he had severe colic, draw- 
lng in of the abdomen, loss of voice, cold sweats, locked jaw, 
and violent convulsions, and expired before the evening of the 
saine day. 
Fatal Quantity.—ln the few fatal cases of acute poisoning 
this substance that have occurred, the quantity taken could 
n°t be accurately determined. Instances are reported in which 
doses of about an ounce were taken without producing any very 
s°nous results. On the other hand, a case is quoted by Dr. 
C'liristison, in which two doses of a drachm each taken by a 
lriarb with an interval of- several hours between the doses, pro- 
duced acute pain in the abdomen, bilious vomiting, loss of 
spoech, delirium, profuse sweating, and slow pulse; with the 
aid of treatment, the patient recovered. 
Treatment.—ln acute poisoning by the acetate of lead, the 
sf°mach should be immediately emptied by the administration 
an emetic of sulphate of zinc; and its action followed by 
arge draughts of milk containing white of egg. Various chem- 
lcal antidotes have been proposed. Among these the most use- 
dd is sulphuric acid in the form of a solution of sulphate of 
Magnesia or of soda. Either of these salts would decompose 
le lead compound with the formation of the insoluble and inert 
Sldphate of lead. The alkaline sulphurets have also been rec- 
ommended. They would give rise to the insoluble sulphuret of 
act. These salts, however, are in themselves poisonous in 
' oe doses, and their use as antidotes has not been as success- 
as upon chemical grounds might have been expected. The 
I C rated sesquisulphuret of iron has been strongly recommended 
M. Bouchardat; and its efficacy has been recently confirmed 
. a Case reported by M. Lepage. As this compound is inert, 
111 ay be administered in large quantity. The alkaline carbon- 
‘ Ts and bicarbonates are inadmissible, as they would give rise 
the carbonate of lead, which is equally poisonous with the 
acetate of the metal. 
■q Tqst-mortem Appearances.—ln the case already cited from 
/’ Teck, the mucous membrane of the stomach was found 
laded in several places, particularly near the pylorus; and 358 
LEAD 
the oesophagus, stomach, duodenum, mesentery, liver, and spleen 
were in a state of high inflammation. In the two cases men- 
tioned by Dr. Taylor, the mucous membrane of the stomach 
was found of a grey color, but otherwise perfectly healthy ; and 
the intestines were much contracted. In the fatal case cited by 
Dr. Christison, the lower end of the oesophagus, the whole 
stomach and duodenum, part of the jejunum, and the ascending 
and transverse colon, were found much inflamed; and the vil- 
lous coat of the stomach appeared as if macerated. 
It is necessary to bear in mind, that acetate of lead has caused 
death without leaving any well-marked morbid appearance in the 
body. 
Chemical Properties. 
General Chemical Nature.—Acetate of lead, as usually 
found in the shops, is in the form of white, crystalline masses, 
which have a density of about 2-6, a slight, vinegar-like odor, 
and a sweetish, astringent taste. In its crystalline state, this 
salt consists of one equivalent of the protoxide of lead, one of 
acetic acid, and three equivalents of water (PbO, C 4H303, 3 Ag) ? 
it crystallises in four-sided prisms. When the crystals are ex- 
posed to dry air, they slightly effloresce, and after a time 
become partially converted into the carbonate of lead, from the 
absorption of carbonic acid from the atmosphere. When mod- 
erately heated, they fuse and give off their water of crystal- 
lisation j at higher temperatures, the salt undergoes complete 
decomposition, leaving a black residue consisting of a mixture 
of charcoal and metallic lead. 
Solubility. 1. In tvater.—When finely powdered crystallised 
acetate of lead is agitated for a few minutes with its own weight 
of water, at a temperature of 60° F., and the liquid quickly 
filtered, crystals of the salt immediately begin to separate from 
the filtrate; if this mixture be allowed to evaporate spontane- 
ously, it leaves a crystalline residue, indicating that the filtered 
fluid originally held in solution one part of the salt in I‘d-1 
parts of the liquid. 
When the powdered salt is agitated for a few minutes with 
an equal weight of water at a temperature of 60° F., and the SPECIAL CHEMICAL PROPERTIES. 
359 
fixture allowed to stand at about the same temperature for 
forty-eight hours, and the liquid then filtered, the filtrate con- 
tains only one part of the salt in 2*67 parts of water. 
From these experiments, it is obvious that the mere act of 
agitation very much increases the solubility of this salt in water. 
This circumstance may, in part at least, account for the dis- 
Crepant statements of observers in regard to the solubility of 
the salt. 
2. In Alcohol.—When large excess of the pulverised salt is 
agitated for a few minutes with pure alcohol of 97 per cent., 
ari(f the solution quickly filtered, the filtrate contains one part 
°f the salt in twenty parts of the liquid. But, if after agitating 
fhe mixture for a few minutes, it be allowed to stand quietly 
°r twenty-four hours, and the liquid then filtered, the filtrate 
c°ntains only one part of the salt in about sixty-five parts of 
*he menstruum. 
The more dilute the alcohol, other conditions being equal, 
ae greater will be the quantity of the salt that it will dissolve. 
3. In Ether.—Absolute ether, under any circumstance, fails 
t° dissolve an appreciable trace of the salt. 
Special Chemical Properties.—When acetate of lead, in 
solid state, is moistened with a solution of iodide of potas- 
it assumes a bright yellow color, due to the formation of 
of lead. The least visible quantity of the salt will ex- 
this reaction. Thus a residue containing only the I,oooth 
hail of a grain of oxide of lead, will yield a very satisfactory 
Jl*ght yellow coloration; and even the 10,000 th of a grain, 
deposited at one point, will assume a distinct yellow hue. 
le iodide of lead thus produced, is slowly soluble in large ex- 
Cess of the reagent. 
cfi a portion of the salt be introduced into a drop of 
louiate of potash solution, it also assumes a bright yellow 
0 % chromate of lead being formed. Crushing the crystal, 
itates the formation of the yellow compound, 
j When gradually heated on a piece of porcelain, acetate of 
ad fuses to a clear liquid, boils, and then becomes reduced to 
’ anhydrous mass; if the heat be continued, the mass 
fuses, then becomes dry and charred, and slowly assumes 360 
LEAD 
a yellowish or reddish-brown color. This residue consists of a 
mixture, in variable proportions, of different oxides of lead. 
Almost the least visible crystal of the salt, when thus treated, 
leaves a brownish residue, apparently several times greater than 
the crystal employed. The carbonate of lead, when treated m 
this manner, does not fuse 5 but it is slowly decomposed with 
the production of a similar reddish-brown residue. 
Heated upon a piece of charcoal in the inner blow-pipe 
flame, acetate of lead fuses, then undergoes decomposition 
with the production of bright, malleable globules of metallic 
lead, and the formation of a yellow incrustation of oxide of 
lead. The carbonate of lead, under these circumstances, yields 
at first a brownish mass, which soon furnishes bright, metallic 
globules. 
When acetate of lead is placed in a small quantity of ses- 
quichloride of iron solution, it slowly dissolves to a fine red 
solution of acetate of sesquioxide of iron (Fe2o3, 3 C 4H303). 
the salt be heated in a test-tube with concentrated sulphuric 
acid, it undergoes decomposition with the evolution of pungent 
vapors of acetic acid. When heated with a mixture of equal 
volumes of alcohol and sulphuric acid, it evolves acetic ether, 
readily recognised by its peculiar, aromatic odor. These reac- 
tions are simply due to the acetic acid of the lead-salt, and are 
common to all acetates. 
Pure aqueous solutions of acetate of lead, are colorless, odor- 
less, and have a sweetish, styptic taste, and, if not too dilute? 
a feebly acid reaction. When a solution of this kind is allowed 
to evaporate spontaneously, the salt is left in the form of white? 
crystalline needles. 
In the following examinations, in regard to the behavior of 
reagents with solutions of lead, the pure crystallised acetate 
was dissolved in water very slightly acidulated with acetic acid. 
The fractions employed, indicate the fractional part of a granl 
of the protoxide of lead (PbO) in solution in one grain of the 
liquid. Except when otherwise indicated, the results refer to 
the behavior of one grain of the solution. One pax*t of the 
protoxide of lead, represents 1 *696 parts of crystallised acetate 
of lead. SULPHURETTED HYDROGEN TEST. 
361 
1. Sulphuretted Hydrogen. 
This reagent, either in its gaseous state or in the form of 
an alkaline sulphuret, throws down from neutral, acidulated, 
aild alkaline solutions containing lead, a black, amorphous pre- 
cipitate of sulphuret of lead (PbS), which is insoluble in the 
caustic alkalies and in the diluted mineral acids. Hot con- 
centrated hydrochloric acid dissolves the precipitate, with the 
evolution of sulphuretted hydrogen and the formation of chlo- 
l'ide of lead, which, unless the quantity be very minute, sep- 
arates as the liquid cools in the form of beautiful crystalline 
plates. 
The precipitate is readily decomposed by hot nitric acid, 
the formation of nitrate of lead and the separation of free 
salphur; if the acid be concentrated and the heat continued, 
6m separated sulphur becomes oxidised into sulphuric acid, 
displacing the nitric acid, unites with the lead, forming 
sHphate of lead. The sulphate of lead thus formed, gen- 
erally separates in the form of a white, granular powder, but 
in the form of small, brilliant, crystalline plates; 
however, the quantity of sulphate of lead produced be only 
Srtlall, it may remain in solution in any excess of nitric acid 
Present. 
In examining the limit of the reaction of this reagent, a 
6ow stream of the washed sulphuretted gas was passed into ten 
drains of the lead solution, contained in a small test-tube. 
• 100 th solution of oxide of lead (= grain PbO), yields an 
immediate, copious, black deposit. When the precipitate 
is dissolved in the mixture, by excess of hydrochloric 
acid, it yields a white precipitate of crystalline needles of 
chloride of lead. 
IjOOOth solution, yields an immediate precipitate. When a 
solution of this strength is exposed to the vapor of sulphu- 
retted hydrogen, its surface becomes covered with a black 
0 pellicle of the lead-sulphuret. 
10,000 th solution: the first bubble of the reagent produces 
a deep brown coloration; and a few bubbles produce a 362 
LEAD 
deep brown turbidity. After saturating the solution with 
the reagent, and allowing it to stand an hour, a very sat- 
4. 50,000 th solution: after a few moments, the liquid assumes 
isfactory, black deposit separates. 
a distinct brown color, and very soon presents a brown 
turbidity ; after a few hours, distinct brownish flakes sep- 
5. 100,000 th solution: after some minutes, the liquid assumes a 
distinct brownish tint, and soon afterwards becomes turbid; 
arate. 
after some few hours, the brownish color deepens, but no 
deposit separates. 
7. 250,000 th solution: after several minutes, the liquid assumes 
a just perceptible cloudiness, with a faint brownish tint, 
which is only distinctly observed when compared with a 
clear solution, and best seen by looking through the liquid 
The formation of the precipitate, from very dilute solu- 
tions, is much facilitated by heating the mixture. The deli- 
cacy of the reaction of this test has been variously stated. 
Thus, Pfaff placed the limit of the brown coloration, at one 
part of lead oxide, in the form of nitrate, in 100,000 parts 
of liquid | Lassaigne at 200,000; and Harting at 350,000 parts. 
As, however, neither of these observers state the amount 
of the solution operated upon, these discrepancies are readily 
explained. 
from the top. 
Fallacies.—The production of a black precipitate by this 
reagent is common to solutions of several other metals, besides 
lead. The true nature of the lead precipitate may be estab- 
lished, by dissolving it, by the aid of heat, in diluted nitric acid 
containing just sufficient of the acid to effect decomposition, and 
then testing the solution with either iodide of potassium, chro' 
mate of potash, or diluted sulphuric acid; or, after filtration, the 
nitric acid solution may be evaporated to dryness, and the resi- 
due examined by any of the tests already mentioned, for oxide 
of lead when in its solid state. 
. . f 
When strongly heated in a reduction-tube, sulphuret 0 
lead is converted into a hard, brittle mass, but fails to yi 
a sublimate. SULPHURIC ACID TEST. 
363 
2. Sulphuric Acid. 
This acid and its soluble salts throw down from solutions of 
salts of lead a heavy, white precipitate of sulphate of lead 
\ b(j, S03), which is soluble in large excess of the fixed alka- 
es? and in some of the salts of ammonia, but very sparingly 
soluble in diluted nitric and hydrochloric acids. Strong nitric 
acid dissolves it in limited quantity to a clear solution. Con- 
Ceutrated hydrochloric acid dissolves it rather readily, especially 
P°n the application of heat, yielding crystals of chloride of 
ea6., as the mixture cools. 
From very dilute solutions of salts of lead, the precipitated 
Slllphate does not separate until after some time: it then de- 
posits in the form of small granules. Solutions of the alkaline 
Caibonates and bicarbonates convert sulphate of lead, even at 
binary temperatures, into carbonate of lead; the solutions of 
e alkaline carbonates, but not those of the bicarbonates, dis- 
e some of the lead compound in this process (H. Rose). 
loin an alkaline solution of sulphate of lead, the metal is pre- 
cipitated by sulphuretted hydrogen, as sulphuret of lead. 
Too- grain of oxide of lead, in one grain of liquid, yields 
With a drop of dilute sulphuric acid, a copious precipitate, 
which partly consists of crystalline needles. If the drop 
of reagent be allowed to slowly flow into the lead solution, 
the precipitate generally consists of a mass of crystalline 
9 Reedies, Plate V, fig. 3. 
iToinj grain, yields a good precipitate, consisting principally 
g of needles and granules. 
Trio grain: an immediate, granular precipitate, and in a 
little time, a quite fair deposit. 
grain: after a few moments, a cloudiness appears, 
aßcl in a little time, there is a very satisfactory, granular 
g deposit. 
grain, yields after a few moments, a slight cloudiness, 
a*id after a little time, a satisfactory, granular precipitate. 
sulphate of potash be employed as the reagent, it pro- 
es the same results as the above. 364 
LEAD 
Free sulphuric acid, as well as soluble sulphates, also pro- 
duce white precipitates in solutions of baryta and strontia. 
The sulphate of lead, however, is distinguished from that of 
either of these metals, in that when moistened with sulphuret 
of ammonium, it is turned black, due to the formation of sul- 
phuret of lead. When sulphate of lead is intimately mixed 
with carbonate of soda and heated before the blow-pipe flame, 
on a charcoal support, it yields globules of metallic lead. 
3. Hydrochloric Acid. 
Hydrochloric acid and its soluble salts occasion in somewhat 
strong solutions of salts of lead, a white precipitate of chloride 
of lead (Pb Cl), which is less soluble in diluted hydrochloric 
and nitric acids than in pure water. When excess of chloride 
of lead is digested, at the ordinary temperature, with puf? 
water for forty-eight hours, one part of the salt dissolves ill 
110 parts of the liquid j it is much more soluble in hot water• 
It is readily soluble in concentrated hydrochloric acid. Chloride 
of lead bears a strong heat without decomposition; but at high6l 
temperatures, with a free supply of air, it is partially decoim 
posed with the evolution of chlorine, and leaves a residue com 
sisting of a mixture of oxide and chloride of lead. 
1. x<To grain of oxide of lead, in one grain of water, yields; 
with free hydrochloric acid, a copious, white, crystalhm3 
precipitate, Plate V, fig. 4. 
2. xwo grain: in a very little time, a very fair deposit of 
granules and crystalline needles. 
3. r.iro'o grain, yields after some minutes, a quite satisfactd} 
deposit of granules, needles, and prisms. 
The results under 2 and 3 are obtained only when excess 
of hydrochloric acid is employed. 
This reagent, as well as soluble chlorides, also produce whfie 
precipitates in solutions of silver and of salts of the suboxid0 
of mercury. The chlorides of silver and mercury, howevd; 
are always thrown down in the amorphous form. The pIC 
cipitated chloride of lead is insoluble, and unchanged in coloh 
by caustic ammonia j whereas the silver precipitate is readfl} lODIDE OF POTASSIUM TEST. 
365 
Soluble in that alkali, whilst the mercury compound is turned 
ack. The action of ammonia, therefore, readily serves to 
istinguish between the chlorides of these three metals. More- 
°7er? the chloride of lead is readily soluble, especially by the 
"lld of heat, in large excess of water, whereas, on the other 
. c ll(b the silver and mercury compounds are wholly insoluble 
111 this liquid. 
4. lodide of Potassium. 
This reagent produces in solutions of salts of lead, a bright 
} ellow precipitate of iodide of lead (Pb I), which is readily 
. u^'e to a clear solution, in caustic potash, but almost wholly 
even in very large excess of the precipitant; under 
action of ammonia, it slowly assumes a white color. It 
B°tves to a clear solution in strong hydrochloric acid; nitric 
acirl q* & J 7 . 
. 1 dissolves it to nitrate of lead. Heated before the blow- 
-1 lPe on charcoal, it turns reddish-yellow, then becomes brown- 
-8 b and finally volatilises. 
lodide of lead is but sparingly soluble in cold water, but at 
as*3 ng temperature, it dissolves more freely, and separates, 
* le 6quid cools, in beautiful, six-sided laminse. We have 
ncu that when excess of the well-washed salt is digested in 
te 6 Waler? with frequent agitation for twenty-four hours, at a 
j w Perature ranging from Go° to 70° F., one part dissolves in 
7WB parts of the fluid. It is, however, much less soluble in 
llle solution of iodide of potassium. This reagent, there- 
-0 7 Pr°duces a copious precipitate from a pure saturated aque- 
e Solation of the iodide of lead; even in the presence of slight 
j 1> 8s °I the reagent, a precipitate will form, when the lead- 
of Xt]e es n°l f°rm more than the 10,000 th part by weight 
s°lntion. The precipitate from a I,oooth solution of 
lrqxte °I lead, does not usually entirely dissolve by heating the 
]_ |Ue to the boiling temperature. 
x“° Srain of oxide of lead, in one grain of water, yields a 
c°pious, bright yellow precipitate, which is usually partly 
2 pmrular and crystalline. 
I'°o's grain, yields a very good deposit. 366 
LEAD 
3. 2,T0"0 grain, yields a quite good precipitate, which readily 
dissolves by heating the mixture to the boiling tempera- 
ture, and again separates, as the liquid cools, in brilliant, 
golden-yellow, six-sided plates, Plate V, tig. 5. 
4. vrooo grain: a very fair deposit. 
5. TO7WO grain, yields an immediate, yellow precipitate, which 
6. yotWo grain, yields, with a very small quantity of the re- 
agent, after a little time, a quite satisfactory deposit of 
granules and small plates. 
soon becomes a fair deposit. 
The production, by this reagent, of a yellow precipitate, 
which is soluble in boiling water, and separates as the mixture 
cools, in the form of six-sided plates, is characteristic of lead. 
5. Chromate of Fotash. 
Chromate and bichromate of potash throw down from solu- 
tions of salts of lead, a bright yellow, amorphous precipitate of 
chromate of lead (PbO, Cr 0:5), which is insoluble in acetic 
acid, and only sparingly soluble in diluted nitric acid, but 
readily soluble in caustic ]3otash. Hydrochloric acid slowly 
changes it to white chloride of lead; it is blackened by sulphu- 
ret of ammonium. 
1. ycTo grain of oxide of lead, yields a copious precipitate. 
2. i7Yo"o grain: a very good deposit. 
3. totWo grain, yields a quite good, greenish-yellow precipitate* 
4. tO7WO grain, yields an immediate cloudiness, and in a f6^ 
minutes, a very satisfactory, greenish deposit. 
5. TFoVoo grain, yields after a little time, a greenish turbidity* 
The formation of the deposit from dilute solutions, is facili- 
tated by heating the mixture. 
Chromate of potash produces in dilute neutral solutions of 
salts of copper a yellowish precipitate, which after a tuuc 
assumes a reddish-brown color, and which, unlike the chromate 
of lead, is readily soluble in acetic acid. The precipitate fr°nl 
somewhat strong solutions of copper, has at once a reddish-browu 
color. Bichromate of potash produces no precipitate from eveu 
concentrated solutions of salts of copper. REACTIONS WITH THE ALKALIES. 
367 
6. Potash and Ammonia. 
The caustic alkalies produce in solutions of salts of lead, a 
de precipitate, consisting chiefly of the hydrated oxide of 
acb which is readily soluble in large excess of the fixed alka- 
s’ msoluble in ammonia, and but sparingly soluble in nitrate 
ammonia. The precipitate is readily soluble in nitric acid; 
changed to chloride of lead by hydrochloric acid. Upon 
e addition of sulphuretted hydrogen or sulphuret of ammonium, 
le precipitate is changed to black sulphuret of lead. 
From solutions of acetate of lead, ammonia causes only a 
Partial precipitate, due to the formation of tribasic acetate of 
-j6ad PbO; C 4H303), which remains in solution. 
low grain of oxide of lead, yields with either of the fixed 
9 alkalies, a copious, white, amorphous deposit. 
TToow grain: a very good precipitate, which is readily solu- 
o Pie in excess of the precipitant. 
ioTcRTo grain, yields with a very small quantity of the re- 
agent, a very satisfactory deposit. 
These reagents also produce white precipitates with solutions 
several other metals, which in some instances, as with bis- 
and tin, are, like the lead deposit, blackened by sulphuret 
ammonium. When, however, the dried lead precipitate is 
it^ on charcoal before the reducing flame of the blow-pipe, 
_ eaves malleable metallic globules, which are characteristic of 
thls metal. 
7. Alkaline Carbonates, 
alkaline carbonates occasion in solutions qf salts of lead, 
amorpP°us precipitate of carbonate of lead, together 
Kiore or less hydrated oxide of the metal. The precipitate 
r ITl°st wholly insoluble in excess of the precipitant, but 
riel 1 So^n^e in nitric and acetic acids, and changed to chlo- 
i 6 Fad by hydrochloric acid; it is also readily soluble in 
j excess of the fixed caustic alkalies. 
10 o' grain of oxide of lead, in one grain of water, yields a 
c°pious precipitate. 368 
LEAD 
2. itoVo grain: a very good deposit. 
3. yoToee grain: a very satisfactory precipitate. 
4. 3-07W0 grain, yields within a few minutes, a quite distinct 
cloudiness. 
These reagents also produce white precipitates in solutions 
of many other metals. But, from all these precipitates, the lead 
compound is readily distinguished by its behavior before the 
blow-pipe flame. 
8. Oxalate of Ammonia. 
Oxalate of ammonia produces in neutral solutions of salts ol 
lead, a white precipitate of oxalate of lead, which soon becomes 
crystalline. The precipitate is readily soluble in nitric acid? 
but insoluble in acetic acid, and blackened by sulphuret ol 
ammonium. 
1. yeot grain of oxide of lead, yields a copious precipitate? 
which soon changes to a mass of long, crystalline needles- 
2- ytoVu grain, yields a very good deposit, which soon changes 
to granules and groups of needles. 
3- Yo'.ttotj grain, yields an immediate cloudiness, and after a 
little time a quite distinct deposit. 
4- ystWo grain, yields after some minutes, a quite satisfactory 
turbidity. 
When the oxalate of lead is heated before the blow-pipe 011 
a charcoal support, it yields globules of metallic lead. 
9. Zinc Test. 
When a drop of a solution of acetate of lead is placed in a 
watch-glass, and a fragment of bright zinc added, the lead coni' 
pound is slowly decomposed with the deposition of metallic lead 
upon the zinc, in the form of a brush-like, crystalline deposit’ 
If the lead solution be placed upon a piece of bright coppel? 
and the metal touched through the drop with a needle of zinc? 
the lead deposits partly on the zinc and partly on the coppel? 
as a strongly adhering, grey deposit, over the space occupy 
by the drop. SEPARATION FROM ORGANIC MIXTURES. 
369 
* To~o grain of oxide of lead, when placed in a watch-glass 
and treated as just stated, yields a quite large, brush-like 
o deposit. 
iToWo grain: the zinc immediately darkens, and in a little 
time, receives a quite satisfactory deposit. 
A solution of tin yields with a fragment of zinc, a brush- 
-1?:e deposit of metallic tin, which sometimes very closely re- 
sembles that produced under similar conditions by lead. 
Ferro cyanide of potassium produces in solutions of salts of 
ac* a white amorphous precipitate of ferrocyanide of lead 
'' 2 Cy3), which is -slowly soluble in large excess of nitric 
and changed to chloride of lead by hydrochloric acid, 
grain of a I,oooth solution of oxide of lead, yields with 
lls reagent, a quite good precipitate; and the same quantity of 
a solution, gives after a little time, a quite satisfactory 
cleposit. 
erricyanide of potassium throws down from solutions of 
a®etate of lead a dirty yellow precipitate, which is soluble in 
nitlic acid, decomposed by hydrochloric acid, and blackened by 
*VWet of ammonium. With one grain of a I,oooth solution 
d °Xl(^e Ike reagent produces a quite good, amorphous 
P°sit j one grain of a 10,000 th solution, yields after a few 
lrmtes, a quite satisfactory, granular precipitate, 
iix lese reagents produce somewhat similar precipitates 
solutions of several other metals. 
Separation from Organic Mixtures. 
s i ®llsPected Solutions.—Various kinds of animal and vegetable 
Wd aiIC6S more or less decompose and precipitate acetate of 
si ’ vken in solution; but most of these precipitates are readily 
p U 6*n diluted nitric acid. When a mixture of this kind is 
ac- entod for examination, it should be acidulated with nitric 
qjt heated for some time, then allowed to cool, the liquid 
P .eied> and the solids upon the filter washed, the washings 
collected with the original filtrate, and the solids reserved. 
e filtrate, after concentration if necessary, is then saturated 
24 370 
LEAD 
with sulphuretted hydrogen gas, and the mixture allowed to 
stand in a moderately warm place for some time; any precipl' 
tate thus produced, is collected on a small filter, washed, and 
while still moist, washed from the filter into a test-tube or any 
convenient vessel, by means of a jet of water from a wash- 
bottle. 
When the precipitate has completely subsided, most of the 
supernatant fluid is decanted, and the solid residue dissolved, 
by the aid of a gentle heat, in* the least possible quantity of 
nitric acid, added drop by drop. By this means, any sulphnret 
of lead present will be converted into nitrate of lead, while the 
sulphur set free will remain unoxidised. The mixture is now 
diluted somewhat with pure water, the liquid filtered, and a 
portion of the filtrate tested with a solution of chromate of 
potash. Other portions of the filtrate may be examined by any 
of the other tests already pointed out. 
The sulphuret of lead precipitated from the I,oooth of a 
grain of oxide of lead, when diffused in ten grains of watei 
and heated with one drop of nitric acid, yields a clear soln- 
tion, which gives with reagents about the same reactions as a 
10,000 th solution of lead-oxide. If large excess of nitric acid 
has been used for dissolving the sulphuret of lead, the filtered 
liquid should be carefully neutralised by pure caustic potash, 
before the application of any of the tests. 
It would rarely, if ever, happen with organic mixtures 0 
this kind containing lead, that the metal would entirely escapc 
solution in diluted nitric acid. If, however, there has been a 
failure to detect the metal, by the above method, the solid3 
obtained by filtration from the original mixture, may be boiled 
for some time with water containing about one-sixth of its voh 
ume of nitric acid, the solution filtered, the filtrate evaporate 
to dryness, and the residue incinerated. This residue is treate 
with a little nitric acid, the solution diluted with a small qnan 
tity of water, then filtered, and the filtrate neutralised and teste 
in the ordinary manner. 
Contents of the Stomach.—These, after the addition of wate 
if necessary, may be acidulated with nitric acid, and examine 
in the manner just described for suspected solutions. SEPARATION FROM THE TISSUES. 
If an alkaline sulphate had been administered as an anti- 
dote, the poison may be in the form of insoluble sulphate of lead. 
Under these circumstances, the contents of the stomach should 
e carefully examined, and any white powder found, collected 
aricl washed, then boiled with a strong solution of pure caustic 
P°tash, and the lead precipitated by sulphuretted hydrogen. 
any sulphate of lead obtained, may be placed in a wide test- 
Inbe and agitated occasionally for several hours with a strong 
s°liition of bicarbonate of soda, the clear liquid decanted and the 
operation repeated with a fresh portion of the soda solution. 
}r this means, the lead-sulphate will be converted into insoluble 
carbonate of lead. This is washed, then dissolved in a little 
acetic acid or in very dilute nitric acid, and the solution tested. 
According to the observations of Ortila, in acute poisoning 
y the salts of lead, the villous coat of the stomach frequently 
Plesents numerous white points which contain lead, and which 
aie Slackened by sulphuretted hydrogen. 
j. From the Tissues.—The solid organ, such as a portion of the 
Ter> is cut into small pieces, and boiled in a porcelain dish 
1 citric acid, diluted with about four parts of water, until the 
IXture becomes homogeneous. When the mixture has cooled, 
liquid is filtered, the filtrate evaporated to dryness, the resi- 
-0 Moistened with nitric acid, again evaporated to dryness, 
ancl the heat continued until all vapors cease to be evolved and 
f x’esidue becomes a carbonaceous mass. The mass thus ob- 
. llGcb is pulverised and boiled with a small quantity of strong 
tlJtlic acid, the mixture diluted with water, the solution filtered, 
le filtrate evaporated to dryness, and the residue dissolved in 
small quantity of Avater slightly acidulated with nitric acid. 
, 18 s°lution, after filtration if necessary, is saturated Avith sul- 
llr®tted hydrogen gas, and allowed to stand until the precipi- 
e has completely subsided. Any sulphuret of lead thus 
i P°Slted, is collected on a small filter, washed, then suspended 
j a small quantity of Avater and dissolved, by the aid of heat, 
*be least possible quantity of nitric acid, and the solution 
<;t ln the usual manner. 
. / 16 (luantity of sulphuret of lead, precipitated by the 
P fretted gas, is too minute to be separated from the filter, 372 
LEAD 
the filter or that portion of it containing the deposit, may be 
heated with sufficient dilute nitric acid to dissolve the precipi" 
tate 5 the solution is then filtered, neutralised, and tested. 
From the observations of several experimentalists, it appears 
that absorbed lead is very slowly eliminated from the system- 
Orfila states (Toxicologic, i, p. 858), that when dogs were given 
about eight grains of acetate of lead daily for one month, the 
metal was found in the liver and brain of the animals when 
killed one hundred and four days after they had ceased to take 
the poison. According to this observer, the metal is eliminated 
from the body principally with the urine. 
From the Urine.—Fifteen or twenty ounces of the urine? 
acidulated with nitric acid, may be evaporated to dryness, the 
residue carbonised by nitric acid, and the carbonaceous mass 
treated in the manner just described for the separation of the 
metal from the tissues. By following this method, we detected 
the metal in notable quantity in the urine almost daily for about 
two weeks, in two instances of severe chronic lead-poisoning? 
resulting from the use of water collected in a leaden cistern- 
Of eight persons who used this Avater, only tAvo of them AATere 
affected by it, and these the elder members of the family. 
Kletzinsky proposes, after rendering the urine alkaline b} 
caustic potash, to add about two per cent, of its weight of 
nitrate of potash and evaporate to dryness. The residue 
then exposed to a dull red heat, whereby the AAdiole of the oi' 
ganic matter is destroyed. The cooled mass is poAvdered and 
boiled for some time Avith a half saturated solution of neutral 
tartrate of ammonia, to which some caustic ammonia has been 
added, the solution filtered, the filtrate acidulated Avith hydro' 
chloric acid, and then precipitated by sulphuretted hydrogen- 
The precipitate is alloAved twenty-four hours to subside, thell 
washed, redissolved in warm dilute nitric acid, the solution al- 
tered, neutralised, and tested in the usual manner. (Thudichum 
On the Urine, p. 406.) 
Quantitative Analysis. Lead may be very accurately 
estimated in the form of sulphuret of the metal. The solution? 
very slightly acidulated with nitric acid, is treated Avith a slou COPPER: CHEMICAL NATURE. 
373 
stream of washed sulphuretted hydrogen gas, as long as a pre- 
Clpitate is produced, and the mixture then allowed to stand in 
a Moderately warm place, until the precipitate has completely 
deposited. The precipitate is then collected on a filter of known 
height, washed, thoroughly dried on a water-bath, and weighed. 
hundred parts by weight of the dried sulphuret, correspond 
t° 93*81 parts of oxide of lead, or 158*87 parts of pure crys- 
tallised acetate of lead. 
When the lead exists in the form of sulphate, this may be 
hashed with water containing a little alcohol, dried at 212° F., 
and weighed. One hundred parts by weight of the dried sul- 
phate, correspond to one hundred and twenty-five parts of crys- 
tallised acetate of lead. 
Section ll.—Copper. 
History and Chemical Nature.—Copper is represented by 
.6 symbol Cu ; its combining equivalent is 31*68, and its spe- 
mfic gravity 8*95. This metal is frequently found in its uncom- 
Md state in nature; its most common ore is copper-pyrites, 
. llch consists of a mixture of the sulphurets of copper and 
!loru According to Walchner, copper is as widely distributed 
th na^Ure as i™. In some mineral waters it is said to exist to 
e extent of half a grain to the gallon of water. (See Liebig 
111 Popp’s Annual Report, vol. ii, p. 268.) It is also found in 
Sea-water and in sea-weeds. Sarzeau states that he found it in 
IXlute quantity in various vegetable substances, such as coffee, 
wheat, and flour; and several observers state, that they 
ected traces of it in the blood and various organs of the 
a thy human body. On the other hand, equally reliable ob- 
-61 vers have failed to detect a trace of the metal, either in 
rhcles of ordinary food, or in the healthy human body. 
Copper, in its uncombined state, is a rather hard, quite 
a§h, ductile metal, of a peculiar red color, and a somewhat 
fZ*** fracturej its fusing point, according to Daniell, is about 
’ OF, When exposed to moist air, it slowly absorbs oxy- 
bGll ailcl carbonic acid, with the formation of a green coating of 374 
COPPER. 
subcarbonate of copper, known also as natural verdigris. Illl' 
mersed in pure water, copper undergoes little or no change j 
but in water containing common salt, it slowly becomes covered 
with a layer of oxychloride of the metal. In water containing 
an organic acid, as vinegar, or when certain kinds of fatty mat- 
ters are present, the metal is more readily acted upon. Nitric 
acid rapidly dissolves it, with the evolution of binoxide of nitro- 
gen and the formation of nitrate of oxide of copper. Cold sul- 
phuric acid has no direct action upon the metal; but the hot 
acid readily dissolves it, with the evolution of sulphurous acid 
gas, to sulphate of copper. Hydrochloric acid, even at the 
boiling temperature, fails to act upon the metal. 
Combinations.—Copper readily unites with most of the metal- 
loids. With oxygen, it unites in two proportions, forming the 
protoxide (CuO), and the suboxide (Cu2o), the former of which 
has a black, and the latter a red color. In its hydrated state, 
the protoxide has a blue color; the color of the hydrated sub- 
oxide is yellow. The protoxide of copper readily unites with 
acids forming salts, which in their hydrated state have either a 
blue or green color, and several of which are freely soluble n1 
water. The suboxide forms but few salts, and these are exceed- 
ingly unstable. The most important compounds of copper, i*l 
regard to their medico-legal relations, are the sulphate, and the 
subacetate, or verdigris. 
Sulphate of copper, or blue vitriol, in its crystallised state, 
consists of one equivalent of protoxide of copper, one of sul- 
phuric acid, and five equivalents of water (CuO, S03, 5 A<f)’ 
In this state, it forms large, blue crystals, which have a nause- 
ous, metallic taste, and a density of 2*27. It is soluble in about 
four times its weight of water at the ordinary temperature, and 
in about two parts of boiling water: the solution has a blue 
color, and a distinctly acid reaction. At a temperature of about 
400°, the salt becomes anhydrous and crumbles to a nearly white 
powder; at a strong red heat, it undergoes decomposition, evolv- 
ing oxygen and sulphurous acid gas, and leaving a residue ° 
protoxide of copper. 
Verdigris, as found in the shops, is a mixture in variable 
proportions of the lower acetates of copper, having either a bin0 PHYSIOLOGICAL EFFECTS. 
375 
01 green color, and a disagreeable acetous odor. It is usually 
lllot with in the form of hard, irregular masses, but sometimes 
as a fine powder. Under the action of water, verdigris is only 
partly dissolved, a greenish residue of tribasic acetate of copper 
eing left. ]q *s completely soluble in water containing a little 
lee hydrochloric or nitric acid. Sulphuric acid readily decom- 
poses it, with the formation of sulphate of copper, and the 
e hnination of acetic acid. 
Physiological Effects.—When swallowed in its metallic state, 
popper seems to be entirely inert, at least so long as it retains 
nietallic form; should, however, the metal become oxidised, 
Within the alimentary canal, it may give rise to severe symp- 
toms. In a case, quoted by Dr. Beck, in which six copper 
penny-pieces were swallowed, and retained in the body for five 
} ears, no inconvenience was experienced, except the effects of 
|*lechanical obstruction. On the other hand, a case is related 
I hfr. Jackson, of Boston, in which a copper half-cent, swal- 
by a child, produced nausea and vomiting, with other 
niptoms of copper poisoning. 
j, 'The compounds of copper, when taken in large doses, or in 
equently repeated small doses, are all more or less poisonous. 
en some of the compounds that are insoluble in water, are 
of producing very active effects. The preparations of 
fiave been rarely administered for criminal purposes; 
Numerous instances are recorded of accidental poisoning by 
olae of them, resulting from the use of food prepared in cop- 
per vessels. 
®yMPtoms.—The usual effects produced by the preparations 
Y°Pper, when swallowed in poisonous quantity, are a coppery 
e m the mouth, nausea, a sense of burning heat in the mouth 
j-i 7 7 o 
taroat, eructations, severe headache, violent vomiting, with 
°*e 0r less purging, and acute pain throughout the stomach 
11 bowels. The pulse becomes small, frequent, and irregular; 
a c Ifiere may be great dizziness, difficulty of breathing, great 
g Yiety? cold sweats, extreme thirst, cramps in the extremities, 
antiness or entire suppression of urine, and death is sometimes 
by convulsions and insensibility. Among the symp- 
s occasionally present, is jaundice, which, according to Dr. 376 
COPPER. 
Christison, is never observed either in arsenical or corrosive 
sublimate poisoning. 
When taken in frequently repeated small doses, the prepara- 
tions of copper produce much the same symptoms as those just 
described. There is loss of appetite; a coppery taste in the 
mouth; nausea, with frequent efforts to vomit; violent head- 
ache ; irregular and frequent pulse ; hot skin ; impaired respira- 
tion ; great thirst; extreme debility ; sharp, shooting pains m 
the stomach, with tension and tenderness of the abdomen; fi’e' 
quent purging, the discharges being usually dark colored, and 
their passage attended with pain; and there is more or less 
alteration of the color of the skin. 
A not unfrequent cause of slow poisoning by copper, as 
already intimated, is the use of utensils of the metal for the 
preparation of food. The risk of contamination in these cases, 
is always much increased by the free action of the atmosphere, 
and by allowing the food to cool and remain in contact with the 
vessel. By employing bright vessels, and removing the food as 
soon as prepared, there is little danger in the use of the metal, 
for such purposes. 
Period when Fated.—The time at which death has taken 
place, in acute poisoning by copper, has been subject to con- 
siderable variation. In the case of a young lady, mentioned by 
Dr. Percival, death occurred on the ninth day. In this case, 
the poisoning resulted from the eating of pickles contaminated 
with copper. The symptoms were, sharp pains in the stomach, 
an eruption over the breast, general shooting pains, thirst, a 
small, frequent pulse, vomiting, hiccough, and purging: there 
was neither stupor nor convulsions. In a case related by 
two ounces of verdigris proved fatal in three days, to a woman- 
In another instance, quoted by Dr. Christison, a lady and her 
daughter wrere poisoned by sour-krout, which had been kept 
in a copper vessel. They were soon seized with pain 111 
the stomach, then nausea and vomiting, followed by purging? 
convulsions, and insensibility. The daughter died inttweeDe 
hours, and the mother an hour later. (On Poisons, p. 362-) 
A child, aged sixteen months, swallowed an unknown quantity 
of solid sulphate of copper, and died from its effects four houlS ANTIDOTES. 
377 
afterwards. This is, perhaps, the most rapidly fatal case yet 
Recorded. 
Fatal Quantity.—ln a case quoted by Dr. Beck, one ounce 
sulphate of copper, taken with suicidal intent, by a man aged 
Oity years, proved fatal within twelve hours. (Med. Jur., vol. 
ll> P* 667.) In another instance, seven drachms of the same 
salt, with three drachms of sulphate of iron, caused the death 
an adult, in three days. Dr. Percival states, that the most 
Vl°lent convulsions he ever witnessed, were produced in a young 
°man, by two drachms of blue vitriol: under appropriate 
treatment, she recovered. In a case cited by Dr. Taylor, half 
an ounce of verdigris ’ destroyed the life of a woman, in sixty 
°Urs; and in another, about twenty grains of the subchloride 
copper, caused the death of a child. (On Poisons, p. 524.) 
11 the other hand, in a case quoted by Dr. A. Stille (Mat. 
ed., vol. i? p. 825), in which an ounce of blue vitriol had 
oen swallowed with suicidal intent, complete recovery took 
t ace, although the patient refused to take an emetic. 
Treatment.—ln acute poisoning by any of the preparations 
. c°Pper, the vomiting should be encouraged by the free ad- 
ministration of demulcent liquids; or the stomach may be emp- 
al|C 111621118 of the stomach-pump. As a chemical antidote, 
mnen in large excess was strongly advised by Orfila. The 
lte °f egg should be freely given, and its exhibition followed 
large draughts of tepid water. An excess of albumen read- 
-OjT decomposes the soluble salts of copper, with the formation 
kuminate of copper, which is said to be but sparingly sol- 
e m the juices of the stomach, 
tii CCording to recent experiments by Dr. Schrader, of Got- 
milk is equally efficient with albumen, as an antidote. 
le caseate of copper thus produced, should be speedily re- 
q etl from the stomach, by vomiting. (Amer. Jour. Med. Sci., 
T855, p. 540.) M. Duval strongly advised the use of 
k ’ Tut it is very questionable whether this substance can 
j le§arded as an antidote : it might, however, be administered 
connection with albumen or milk. 
tid lllollS the other substances that have been proposed as an- 
°t°s, may be mentioned ferrocyanide of potassium, iron filings, 378 
COPPER. 
calcined magnesia, and hydrated sulphuret of iron. The em- 
ployment of the alkaline sulphurets, and also of vinegar, would 
be inadmissible. 
Post-mortem Appearances.—The morbid appearances, ill 
poisoning by the preparations of copper, are usually confined to 
the alimentary canal. In acute cases, the inside of the stomach 
and of the intestines not unfrequently present a bluish or green- 
ish appearance, due to the presence of the poisonous compound. 
It should be remembered, however, as first pointed out by 
Orfila, that a somewhat similar appearance may result from the 
presence of altered bile. The lining membrane of the stomach 
is usually inflamed and softened; and in some few instances it 
presented an ulcerated, and even gangrenous appearance. Sim- 
ilar appearances have been found in the intestines ; in some few 
cases, the intestines were found perforated, and their contents 
had partially escaped into the cavity of the abdomen. 
In the fatal case cited by Dr. Beck, the oesophagus was 
found of a livid-red color, and the stomach of a bluish hue? 
which could be removed by washing; under this, the mucous 
membrane was of a deep red color. The intestinal tube, through' 
out fits whole extent, was highly inflamed. In the case before 
referred to, in which seven drachms of the sulphate of copper> 
together with three drachms of green vitriol, had been taken? 
the mucous membrane throughout the stomach and intestines 
was found in a perfectly healthy condition. 
Chemical Properties. 
In the solid state. The general chemical nature and 
properties of the sulphate and subacetates of copper, or verdi- 
gris, have already been pointed out. The nitrate of coppel 
has a beautiful blue color, and is freely soluble in water. 
carbonates of the metal have either a blue or green color; these 
salts are insoluble in water, but readily soluble in diluted acids? 
with effervescence. With chlorine, the metal unites in two p1’0' 
portions, forming the subchloride and the protochloride; 
former of which is white and insoluble, while the latter has a 
green color, and is readily soluble. SULPHURETTED HYDROGEN TEST. 
379 
The property of forming* blue and green compounds is some- 
what peculiar to copper; yet some of the preparations of a few 
°ther metals have one or the other of these colors. Thus, some 
the compounds of nickel, sesquioxide of chromium, and pro- 
vide of uranium are green, while some of the salts of cobalt 
j.|'e blue. Copper, however, is the only one of these metals 
llkely to be met with in medico-legal investigations, and is 
1 eadily distinguished from the others in that when its salts are 
Moistened with a diluted acid and placed in contact with a piece 
° bright iron or steel, they impart to the iron a coating of me- 
lc copper, readily recognised by its peculiar red color. 
Salts of copper, when heated in the inner blow-pipe flame, 
lapart a beautiful green coloration to the outer flame. When 
with dry carbonate of soda or cyanide of potassium and 
on a charcoal support, in the reducing blow-pipe flame, 
ey yield red particles of metallic copper. 
b>F Solutions of Copper. The soluble salts of copper 
their color to solutions, even when highly diluted. 
*be case of the sulphate, the blue color is quite perceptible 
its a^ns °b a solution containing only the I,oooth part of 
w eight of oxide of copper; the same quantity of a 5,000 th 
tp !°n> exbibits a slight bluish tint. In larger quantities of 
e liquid, the color of this salt is quite perceptible, in solutions 
0£ 1 moi'e dilute than those just mentioned. Solutions of salts 
c°pper, when not too dilute, slightly redden blue litmus- 
-1 1 5 they have an astringent, metallic taste, and when evap- 
spontaneously, leave the salt in its crystalline state. 
11 toe following investigations of the different tests for cop- 
’ when in solution, pure aqueous solutions of the sulphate 
i(Je 6 eruPl°yed. The fractions indicate the quantity of protox- 
p COPPer (CuO) present in one grain of the solution. One 
°l* the protoxide corresponds to 3*142 parts of pure crys- 
lsed sulphate of copper. 
1. Sulphuretted Hydrogen. 
dowSUlphuretted hydrogen gas and the alkaline sulphurets throw 
11 fioni solutions of salts of copper, even in the presence of 380 
COPPER. 
a free acid, a precipitate of sulphuret of copper (CuS), which 
as first produced has a brown color, but sooner or later becomeS 
brownish or greenish-black. The precipitate is slightly soluble 
in large excess of sulphuret of ammonium, but insoluble in the 
fixed alkaline sulphurets, and in the caustic alkalies. It is only 
sparingly soluble in cold concentrated nitric acid; but upon the 
application of heat, even when the acid is somewhat dilute, 1 
readily dissolves, forming a blue solution of the nitrate, with 
more or less sulphate of copper. It is slowly dissolved by hot 
concentrated hydrochloric acid, with the formation of subchlo' 
ride of copper; concentrated sulphuric acid has but little action 
upon it in the cold, but it is decomposed by the hot acid. 111 
its dry state, sulphuret of copper has a greenish-black coloi j 
when exposed to moist air, it slowly absorbs oxygen, and be- 
comes converted into sulphate of copper. 
In examining the limit of this test, ten grains of the coppcl 
solution were submitted to a slow stream of the washed sulphu' 
retted gas. 
1. 100 th solution of oxide of copper (= -jV grain CuO), yield3 
an immediate, deep brown precipitate, which soon becomes 
brownish-black. After standing some time, the precipha^e 
entirely separates as a copious, black deposit, leaving 
solution perfectly colorless. 
2. I,oooth solution, yields at first a brown mixture, from wmc 
after a time, a brownish-black deposit separates, leavm» 
the liquid of a brownish color. After standing some homn7 
the liquid becomes colorless, and the deposit acquireB 
greenish-black color. 
3. 5,000 th solution: the solution immediately assumes a bro^11 
color, and soon becomes turbid 5 after several hours, 
quite fair, greenish-black deposit separates. 
4. 10,000 th solution: the liquid immediately acquires a bronn 
ish color, which soon deepensj after the mixture 
stood about twenty-four hours, it yields a greenish-brn" 
deposit. 
5. 25,000 th solution : the liquid immediately assumes a yell°A 
brown color, which soon changes to brown; in 
four hours, a satisfactory, light brown deposit has form6 AMMONIA TEST. 
381 
000 th solution: almost immediately the liquid assumes 
a yellowish color, and soon becomes brownish-yellow 5 in 
twenty-four hours, quite perceptible brownish flakes have 
separated, and the liquid has a brownish color. 
100,000 th solution: after several minutes, the liquid acquires 
a faint yellowish color, which soon becomes quite distinct 5 
111 twenty-four hours, it has a faint brownish hue, but there 
18 uo precipitate. 
This reagent also produces brownish precipitates with sev- 
eial other metals, but most of these are extremely rare and 
v°uld never be met with in medico-legal investigations. The 
ftsition of color observed in the sulphuret of copper is some- 
clt peculiar to this substance, especially when the metal is 
Present in quite notable quantity. When the sulphuret of cop- 
f.er *s Moistened with hydrochloric acid and touched for a little 
° wbb a bright sewing needle, the latter becomes coated 
1 liable copper, of its peculiar color. The true nature of 
precipitate may also be established by dissolving it, by the 
°f heat, in a little nitric acid, evaporating the solution to 
yaess, dissolving the residue in a little water, and testing the 
ion with ammonia or ferrocyanide of potassium, in the 
aarier described hereafter. 
Either nickel, chromium, uranium, nor cobalt—metals which 
Mil C°bPer have the property of forming green or blue salts— 
y!eld a precipitate from acid or neutral solutions, when 
eated with sulphuretted hydrogen gas. 
2. Ammonia. 
T] •. 
0 ms reagent produces in solutions of salts of copper a blue 
to f!enish'blue, amorphous precipitate, which is readily soluble, 
dill1 00b blue solution, in excess of the precipitant. With very 
cj • Cupreous solutions, the reagent may fail to produce a pre- 
is ‘ a y but the liquid immediately assumes a blue color, which 
eadily destroyed upon the addition of a free acid. 
10 0 §rain of oxide of copper, in one grain of fluid, yields a 
Copious precipitate, which with excess of the reagent dis- 
s°bves to an intensely blue solution. 382 
COPPER. 
2. rrcro“o grain, yields a bine, flocculent deposit, which readily 
dissolves in excess, forming a distinctly bine liquid. 
3. t,wo~o grain, with a very minute quantity of the reagenb 
yields a very distinct precipitate : this precipitate is best 
obtained by exposing the copper solution to the vapor of 
ammonia; when the precipitate is dissolved in excess of 
the reagent, the mixture has a just perceptible blue tint- 
dr. r075i)“0 grain, when exposed to the vapor of ammonia, yields 
a distinct precipitate, which when dissolved in excess ot 
the precipitant, forms an apparently colorless liquid. Ten 
grains of the solution, have a quite distinct blue color* 
This blue color is quite obvious in much more dilute solu- 
tions, when larger quantities of the liquid are examined* 
Normal solutions of salts of nickel, yield with ammonia a 
partial precipitate of green, hydrated oxide of nickel, which 
readily soluble in excess of the reagent, forming a deep hlne 
solution. Cobalt yields with the reagent, a blue precipitate? 
which dissolves in excess of the precipitant, forming a reddish- 
brown liquid. Sesquioxide of chromium solutions yield a bluish- 
green deposit, slightly soluble in excess of the reagent, with the 
formation of a pink solution. Salts of uranium yield with the 
reagent, a yellow precipitate, which is insoluble in excess 0 
the precipitant. 
3. Potash and Soda. 
The fixed caustic alkalies throw down from solutions of salt® 
of copper, a blue amorphous precipitate of hydrated oxide o 
copper (CuO, HO), which is insoluble in excess of the precip1 
taut, but readily soluble in acids, even acetic acid. On boilnb? 
the mixture containing an excess of the reagent, the precipitate 
speedily becomes anhydrous and of a black color; this change 
is slowly effected even at ordinary temperatures. 
•The reaction of these reagents is much modified by the 
presence of certain organic substances. Thus, in a solution 
the sulphate of copper containing grape-sugar, the precip^9'*'6 
is readily soluble in excess of the precipitant, forming a deep 
blue solution, from which the whole of the copper is thro' FERROCYANIDE OF POTASSIUM TEST. 
383 
°Wn by boiling, in the form of a yelloiv or red powder of the 
Suboxide of copper. In the presence of tartaric acid, the re- 
aSent may fail to produce a precipitate, even upon boiling the 
fixture. 
Teh grain of oxide of copper, in one grain of water, yields 
0 a copious, blue, gelatinous deposit. 
Trowo grain: a very good, flocculent precipitate. 
T,'(ToT) grain, yields, in a very little time, a slight, flocculent 
precipitate, which soon becomes a quite fair deposit. 
ToToiro grain: after a little time, a just perceptible cloudi- 
ness, and soon a quite distinct, flaky deposit. 
3-hese reagents also produce a blue precipitate in solutions 
salts of cobalt, which is insoluble in excess of the reagent; 
u when this mixture is boiled, the precipitate is changed into 
1 °wnish or reddish deposit. Solutions of the sesquioxide of 
°niium yield with the reagent a bluish-green precipitate, 
jCadily soluble in excess of the precipitant, forming a greenish 
flnid, from which, by continued boiling, the whole of the chro- 
-IUIII is reprecipitated, as green, hydrated sesquioxide of the 
These are the only two metals which yield with these 
. pnts precipitates, the color of which might be confounded 
1 that of the copper precipitate, 
tio ar^ona^e °f potash and of soda occasion in aqueous solu- 
°f cupreous salts, a greenish-blue, amorphous precipitate 
} crated subcarbonate of copper, which is sparingly soluble, 
a bluish liquid, in excess of the precipitant. If an excess of 
P leagent be added and the mixture boiled, the precipitate 
j- C.ottles converted into anhydrous black oxide of copper. The 
th 1 le reacti°n °f these reagents, is the same as that of 
bxed caustic alkalies. 
4. Ferrocyanide of Potassium. 
reagent throws down from somewhat strong solutions of 
c S , Copper, a reddish-brown, amorphous precipitate of ferro- 
th0 111(^e COPPer (Cu2 FeCy3), which is insoluble in excess of 
in(>.j^le(bpitant, and in acetic and hydrochloric acids, but spar- 
Soluble in ammonia to a bluish-green liquid, from which 384 
COPPER. 
it is reprecipitated by excess of acetic acid. From more di u 6 
solutions, the reagent produces a purple precipitate; while bom 
still more dilute solutions, it fails to produce a precipitate, u 
the mixture assumes a reddish color. 
1. y4o" gram of oxide of copper, yields a copious, reddish-brown? 
gelatinous precipitate. 
O A i. 1 * *1 /~\ aTI 
2. T7o“o“o grain; an immediate purple precipitate, which s 
becomes a quite good, reddish-brown deposit. 
3. grain: a reddish, flocculent turbidity. 
4. 25.V00 grain, yields a slight cloudiness; when viewed o\er 
white paper, the mixture exhibits a distinct reddish c 0 01 
When five grains of a 100,000 th solution are treated wit i a 
small quantity of the reagent, the mixture presents a quite lS 
tinct reddish color. This color is readily observed even in m°re 
dilute solutions, when larger quantities are examined. 
Ferrocyanide of potassium, also produces in 
persalts of uranium, a precipitate very similar in color to n 
of the ferrocyanide of copper. But the uranium precipitate is 
changed to a yellow compound upon the addition of excess 
ammonia; whereas, as before stated, the ferrocyanide of coppcl 
is soluble to a limited extent in excess of this alkali, yielding a 
bluish-green liquid. Moreover, solutions of copper are rea . f 
distinguished from those of uranium, by their behavior w 
sulphuretted hydrogen, and ammonia, as already pointed ou 
Copper and uranium are the only metals that yield reddish 
brown precipitates with ferrocyanide of potassium. 
The reaction of this reagent, with solutions of cupreous sa 
is much modified by the presence of even minute quantities 
iron, with which it produces a blue precipitate. 
5. Iron Test. 
When a piece of bright iron or steel is immersed in a so u 
tion of a salt of copper, it sooner or later decomposes the sa 
and receives a coating of metallic copper, having the chara 
teristic color of the metal; at the same time, a salt of 11 
/ ' lS 
containing the acid previously combined with the coppeb 
formed. This reaction, especially from dilute solutions, is nIU PLATINUM AND ZINC TEST. 
385 
facilitated by the presence of a little free sulphuric or hydro- 
chloric acid. 
In examining the limit of this test, a single grain of the 
copper solution, placed in a watch-glass, was acidulated with 
sulphuric acid, and a small portion of a bright sewing needle 
introduced into the mixture; in the very dilute solutions, the 
length of the needle did not exceed the -jV of an inch. It is 
obvious, that the thickness of the deposit from a given quantity 
of copper, and consequently the delicacy of the test, will de- 
pend very much upon the extent of surface over which the 
metal is distributed. 
!• Tinr grain of oxide of copper, yields a very fine coating. 
2. TTcTou grain: in a little time, the needle acquires a very sat- 
isfactory deposit. 
x~o,ooo grain: in a few minutes, the needle presents a red- 
coating. 
4. airrsiro grain: after several minutes, the needle exhibits a 
dish tint, and in fifteen minutes, receives a satisfactory 
hour, becomes perfectly satisfactory. 
By allowing the needle to remain in the acidulated liquid 
for several hours, satisfactory deposits may be obtained from 
solutions much more dilute than the last-mentioned. The true 
color of very thin deposits, is best determined by the aid of a 
hand-lens. 
just perceptible reddish hue, which improves, and after an 
It need hardly be remarked that this reaction is peculiar to 
copper. The cupreous nature of the deposit may be shown, by 
dissolving out the iron, from the coated needle, with diluted 
sulphuric acid, and then dissolving the washed coating in a 
little nitric acid, evaporating the solution to dryness, redissolv- 
lng the residue in a few drops of water, and testing the liquid 
’"uth ferrocyanide of potassium. 
6. Platinum and Zinc Test. 
When a solution of a salt of copper is acidulated with hy- 
drochloric or sulphuric acid, and placed in a platinum dish, 
aild then a fragment of bright zinc placed in the liquid, the 
25 386 
COPPER. 
cupreous compound quickly undergoes decomposition with the 
deposition of a coating of metallic copper, of its peculiar color? 
upon the platinum covered by the liquid. 
1. y-,nr grain of oxide of copper, in one grain of fluid, when 
treated after this method, yields a very fine deposit. 
2. Triroo grain: after a few minutes, the platinum exhibits a 
very satisfactory coating. 
3. TroWo grain : after several minutes, there is a quite distinct 
deposit. 
This method will not serve for the detection of as minute 
quantities of copper as the iron test, since in its application the 
metal is distributed over a larger surface than when the iron- 
method is employed. If the washed deposit be moistened with 
a few drops of caustic ammonia, the liquid slowly acquires a 
blue color, due to the formation of a soluble compound of the 
metal. 
7. Arsenite of Potash. 
This reagent throws down from neutral solutions of salts ol 
copper, when not too dilute, a bright green precipitate of arsen- 
ite of copper (2 CuO ; As03), known also as Scheele’s green. 
This precipitate is readily soluble in ammonia and in free acids. 
1. Yiro grain of oxide of copper, in one grain of water, yields 
a copious precipitate. 
2. y.oWo grain: a quite good, yellowish-green deposit. 
3. i o :wo~o grain: after a little time, the mixture becomes decid- 
edly turbid; but the green color is not perceptible. With 
larger quantities of the solution, the reagent produces sat- 
isfactory results, even in much more dilute solutions. 
The production of a bright green precipitate by this reagent 
is quite characteristic of copper. However, solutions of salts 
of nickel yield with the reagent, a pale green deposit, which? 
like the copper precipitate, is readily soluble in ammonia and m 
acetic acid. 
8. Chromate of Potash. 
Protochromate of potash, when added in excess to somewhat 
strong solutions of salts of copper, produces a reddish-brown FERRICYANIDE OF POTASSIUM TEST. 
387 
precipitate of chromate of copper, which is readily soluble in 
ammonia, forming a beautiful green liquid; the precipitate is 
also soluble in acetic acid, and in excess of the copper solution. 
From more dilute solutions, the reagent throws down a yellow 
0r greenish-yellow deposit. 
F TTo grain of oxide of copper, in one grain of water, yields 
a very copious, reddish-brown, amorphous precipitate. 
F TTcfoo grain: a copious, yellow deposit, which soon assumes 
a greenish-yellow color. 
roTsiro grain, yields an immediate, bluish-yellow turbidity, 
and soon a quite satisfactory, greenish-yellow precipitate. 
F Torroo grain: after several minutes, a quite perceptible tur- 
bidity. 
Bichromate of potash fails to produce a precipitate, even in 
concentrated solutions of salts of copper. 
9. Ferricyanide of Potassium. 
Normal solutions of salts of copper, yield with this reagent, 
a brownish-yellow or greenish-yellow amorphous precipitate of 
ferricyanide of copper, which is insoluble in acetic acid, but is 
readily soluble in ammonia, forming a beautiful green fluid. 
F Tiro grain of oxide of copjmr, yields a copious, brownish- 
yellow precipitate. 
*■'* TToiro grain: a very good deposit. 
F svwoo grain: a rather good, greenish-yellow precipitate. 
F Totsito grain, yields a greenish turbidity. 
The production of a brownish or greenish-yellow precipitate 
this reagent, is common to solutions of several other metals, 
besides copper. 
10. lodide of Potassium. 
This reagent produces in solutions of salts of copper a yel- 
°w or brownish-yellow precipitate, which soon changes to a 
1 ownish or yellowish-white deposit of subiodide of copper 
\Fu2I) • at the same time, iodine is set free, and dissolves in 
anT excess of the reagent present. The precipitate is insoluble 388 
COPPER. 
in acetic acid, but is readily soluble to a deep blue solution, m 
ammonia. 
1. grain of oxide of copper, yields a copious, brownish- 
yellow precipitate, which soon acquires a yellowish-white 
color. 
2. grain: a quite good deposit. 
3. rrcnro grain: the liquid assumes a yellow color, then be- 
comes turbid, and after a short time, throws down small 
granules. 
4. i 0.000 grain: after a little time, the mixture acquires a yel- 
low color, then becomes turbid. 
The production by this reagent of a brownish or yellowish 
precipitate, which is readily soluble in ammonia to a deep blue 
solution, is quite peculiar to solutions of copper. 
Detection of the Acid.—The tests now considered, would, 
of course, only serve for the detection of the metal of the cu- 
preous compound, and would not indicate the acid with which 
it was combined. The presence of sulphuric, hydrochloric, or 
nitric acid, when combined with the metal, could be shown m 
the manner already described, under the special consideration 
of these acids. 
The presence of acetic acid, as in the case of verdigris? 
could be shown by boiling the cupreous salt with a small quan- 
tity of a mixture of about equal volumes of strong sulphuric 
acid and alcohol, when acetic-ether of its characteristic odor 
would be evolved. 
Separation from Organic Mixtures. 
Suspected Solutions.—The soluble salts of copper are more 
or less decomposed, with the precipitation of oxide of the metal 
in combination with organic matter, by various animal and vege- 
table principles. A portion of the clear liquid, after concentra- 
tion if deemed best, may be slightly acidulated with sulphuric 
acid, and a portion of a bright sewing needle placed in the 
mixture, the immersion being continued for several hours 1 
necessary. Any metallic deposit thus obtained, may be washe 
and confirmed, by dissolving the needle in diluted sulphuric SEPARATION FROM ORGANIC MIXTURES. 
389 
Amd, and afterwards the washed coating in nitric acid, in the 
Planner already described, when considering the iron test. 
In the application of this test, it should be borne in mind 
that the needle may after a time, even in the absence of cop- 
per, present a reddish appearance, due to the formation of a 
coating of oxide of iron. A deposit of this kind, however, may 
be readily distinguished from that produced by copper, even in 
most instances by examining it with a hand-lens. Should the 
mon test reveal the presence of copper, other portions of the 
liquid may be examined by some of the other tests for the 
metal. Most of these tests, however, have their action readily 
interfered with by the presence of organic matter. 
Should the liquid presented for examination be mixed with 
much solid organic matter, the mixture, after the addition of 
water if necessary, may be gently heated for some time, and a 
portion of the filtered liquid then examined in the manner be- 
fore described. Should there be a failure to thus detect the 
poison, there would be little doubt of its entire absence. Yet, 
the solids separated from the liquid by filtration, may be boiled 
for about fifteen minutes with water containing a little hydro- 
chloric acid, and the solution thus obtained be examined either 
by the iron test or by sulphuretted hydrogen gas. 
Contents of the Stomach.—These are carefully transferred to 
a clean, porcelain dish, and the inside of the stomach well 
scraped, the scrapings being added to the matters in the dish. 
The contents of the dish, after the addition of water if neces- 
Sary, are strongly acidulated with hydrochloric acid, and gently 
boiled until the organic solids are well broken up. The cooled 
bquid is then filtered, the filtrate somewhat concentrated, again 
filtered, and then exposed to a slow stream of sulphuretted 
hydrogen gas, as long as a precipitate is produced, by which 
any copper present will be thrown down as sulphuret of the 
metal. When the precipitate has completely subsided, it is col- 
lected on a filter, washed, and then dissolved, by the aid of 
bejit, in a small quantity of diluted nitric acid. On now treat- 
mg the solution with a drop or two of sulphuric acid and cau- 
tiously evaporating it to dryness, the metal, if present, will be 
feft as blue sulphate of copper. The residue thus obtained, is 390 
COPPER. 
dissolved in a small quantity of warm water, and the filtered 
solution examined for copper by the ordinary reagents, espe- 
cially by the iron and ammonia tests. 
Should the precipitate produced by sulphuretted hydrogen 
be small in quantity and apparently contain much organic mat- 
ter, the residue obtained after solution in nitric acid and evap- 
oration, is moistened with concentrated nitric acid and heated 
until the organic matter is entirely destroyed. The dry mass 
is then treated with a little diluted nitric acid, the liquid ex- 
pelled by a moderate heat, the residue dissolved in a little pure 
water, and the solution tested. 
From the Tissues.—For the purpose of examining any of 
the soft tissues of the body, for absorbed copper, the organ, as 
a portion of the liver, cut into small pieces, is made into a 
paste with pure nitric acid diluted with three or four volumes 
of water, and the mixture gently boiled, with the occasional 
addition of small quantities of powdered chlorate of potash, 
until the whole becomes perfectly homogeneous. It is then 
diluted with water, allowed to cool, and the filtered liquid evap- 
orated to dryness. The residue thus obtained, placed in a thin 
porcelain capsule, is covered with concentrated nitric acid, a 
little chlorate of potash added, and the liquid evaporated by a 
moderate heat; the heat is then increased and continued until 
the organic matter is entirely destroyed, when the mass will as- 
sume a nearly white color. On boiling this residue in nitric 
acid containing a little water, any copper present, together with 
the small quantity of iron which is usually present in the tis- 
sues, will be taken up in a soluble form. This solution is care- 
fully evaporated to dryness, to expel the excess of nitric acid, 
the residue dissolved in a little warm water, and tested in the 
usual manner. Should the solution contain iron, any copper 
present may be separated from that metal by acidulating the 
liquid with hydrochloric acid and treating it with sulphuretted 
hydrogen, when the copper will be thrown down as sulphuret 
of the metal, while the iron will remain in a soluble form; the 
precipitated sulphuret of copper is then collected on a filter, 
washed, dissolved in a little nitric acid, and the solution exam- 
ined in the manner already indicated. QUANTITATIVE ANALYSIS. 
391 
Another method for the separation of iron, when present in 
a liquid with copper, is to treat the solution with excess of am- 
monia, when the former metal will be precipitated as hydrated 
sesquioxide of ii’on, while the copper will remain in solution, 
forming a deep blue liquid. After removing the iron precipi- 
tate by a filter, a portion of the filtrate may be slightly acidu- 
lated with acetic acid, and tested with a solution of ferrocyanide 
of potassium. 
In a recent case of poisoning by the sulphate of copper, M. 
Malagutti readily detected the metal in a portion of the liver 
of the deceased; arid also, in about two ounces of the urine. 
(Jour, de Chim. Med., Avril, 1862, p. 209.) In experiments 
on animals, in regard to the elimination of the salts of copper, 
I. L, Orfila administered small quantities of the sulphate, mixed 
with food, to dogs, for fifteen days, and found the metal in the 
liver, tissue of the stomach, and in the lungs, sixty days after 
it had been administered. But the metal was found in the urine 
for only a few days after it had ceased to be taken ; and even 
in some instances, it was not detected after the lapse of twenty- 
four hours. (Orfila’s Toxicologic, i, p. 791.) 
From the Urine.—About five ounces of the urine are evap- 
orated to dryness, and the organic matter of the residue de- 
stroyed by means of concentrated nitric acid and chlorate of 
potash, and subsequent incineration. The ash thus obtained, 
which will generally contain a small trace of iron, is dissolved 
in hot diluted nitric acid, and the liquid evaporated. Any 
nitrate of copper present in the residue, is then dissolved in a 
small quantity of water, and the solution examined in the usual 
manner. 
In six cases of non-fatal poisoning by salts of copper, col- 
lected by M, Kletzinsky, the metal was found in the urine as 
long as the patients experienced any active symptoms. When 
these ceased, the metal disappeared from the urine; but it con- 
tinued to be discharged with the fasces. (Thudichum, Pathology 
of the Urine, p. 409.) 
Quantitative Analysis.—Copper is usually estimated as 
protoxide of the metal. The solution is heated to about the 392 
ZINC 
boiling temperature, and a solution of caustic potash or soda 
added as long as a precipitate is produced, after which the 
heat is continued for some minutes. When the mixture has 
cooled and the supernatant liquid become perfectly clear, the 
precipitate is collected on a filter of known ash, washed with 
warm water, and dried. It is then, as far as practicable, sep- 
arated from the filter, strongly ignited in an equipoised platinum 
capsule, and the ash of the filter, which has been burned sep- 
arately, added to the ignited mass; the whole is then allowed 
to cool, and quickly weighed. When the quantity of precipi- 
tate is small, it may be ignited along with the filter. 
Should the alkaline liquid separated by filtration from the 
precipitated oxide of copper, have a blue color, it is boiled 
with a little grape-sugar, when any copper still present will be 
thrown down as suboxide of the metal; this is collected, washed, 
moistened with nitric acid, the liquid evaporated, and the resi- 
due ignited, when the copper will remain as protoxide of the 
metal. One hundred parts by weight of anhydrous protoxide 
of copper, represent 314*21 parts of pure crystallised sulphate 
of copper; or, in other words, the crystallised sulphate contains 
31*825 per cent, of the anhydrous oxide. 
Section lll.—Zinc. 
History and Chemical Nature.—The symbol for zinc is Zn, 
its combining equivalent 32*53, and its specific gravity about 7. 
Zinc is found in nature under several forms of combination, but 
only in the inorganic kingdom. It is a bluish-white metal hav- 
ing a bright metallic luster; very brittle, and when fractured, 
exhibits a crystalline structure. It fuses, according to Daniell, 
at 773° F., and at a red heat is volatilised, being dissipated in 
the form of a colorless vapor, which in the presence of air, 
takes fire and burns with a white flame, forming oxide of zinc 
(ZnO). When heated on a charcoal support before the reduc- 
ing blow-pipe flame, it fuses, then burns, evolving dense white 
fumes, and coating the charcoal with a yellow incrustation, 
which on cooling becomes white. SULPHATE OF ZINC. 
393 
Exposed to the air, at ordinary temperatures, zinc becomes 
covered with a grey coating of basic carbonate of zinc. The 
metal is readily dissolved by nitric acid, with the formation of 
nitrate of oxide of zinc, and evolution of either protoxide or 
binoxide of nitrogen, the nature of the evolved gas depending 
upon the strength of the acid employed. It is also readily sol- 
uble in diluted sulphuric and hydrochloric acids, with the for- 
mation of a salt of zinc, and the evolution of hydrogen gas. 
As found in commerce, metallic zinc is liable to be contami- 
nated with carbon, arsenic, sulphur, antimony, iron, lead, and 
cadmium. 
The only salifiable oxide of zinc, is the protoxide. This 
forms a white, amorphous powder, which at elevated tempera- 
tures, has a lemon-yellow color. The salts of zinc, unless they 
contain a colored acid, are colorless. They are for the most 
part readily soluble in water, and their normal solutions have a 
slightly acid reaction. When intimately mixed with carbonate 
of soda, and heated before the blow-pipe on a charcoal support, 
the salts of zinc are readily decomposed, with the formation of 
an incrustation, over the charcoal, of oxide of zinc. 
When taken into the stomach, metallic zinc is destitute of 
poisonous properties, at least so long as it retains its metallic 
state; but all the preparations of this metal are more or less 
poisonous ; they are, however, less active than the compounds 
of lead and copper. The continued inhalation of the oxide of 
zinc, has, in several instances, given rise to serious symptoms. 
(London Chem. Graz., vol. viii, p. 362.) The only salts of zinc 
requiring notice in this connection, are the sulphate and chlo- 
ride. Poisoning by these salts has been of rare occurrence, and 
has been chiefly the result of accident. 
Sulphate of zinc, or white vitriol (ZnO, S03, HO, 6 Aq), as 
usually found in the shops, is in the form of small, colorless, 
prismatic crystals, which have a strong, astringent, metallic 
taste, and are slightly efflorescent in dry air. At 212° F., the 
crystallised salt gives up six equivalents of water, and at about 
400° becomes anhydrous ; at a bright red heat, it is entirely 
decomposed, leaving a residue of oxide of zinc. It is soluble 
in about two and a half times its weight of water, at ordinary 394 
ZINC 
temperatures; and in less than its own weight of boiling water. 
It is insoluble in alcohol, ether, and chloroform. 
Chloride of zinc (ZnCl), is readily obtained bj dissolving 
zinc in diluted hydrochloric acid, and evaporating the solution 
to dryness. In its anhydrous state, it forms a soft, white, very 
deliquescent solid, which is readily fusible, and volatilises un- 
changed at a strong red heat, condensing sometimes in the form 
of colorless, crystalline needles. It is soluble in water in all 
proportions, and also soluble in alcohol and ether. The liquid 
known in the shops under the name of u Sir Win. Burnett’s 
disinfecting fluid,” is a solution of this salt, containing about 
two hundred grains of the anhydrous salt in each fluid ounce. 
Several instances of poisoning by this liquid have been reported. 
Symptoms.—Sulphate of zinc has frequently been adminis- 
tered in doses of several grains daily for long periods, without 
producing any ill effects. Dr. Babington even gave, in one 
instance, thirty-six grains of the salt, three times a day for 
three weeks, without any noxious symptom having appeared. 
When, however, the salt is swallowed in doses of several 
drachms or more, it may produce very speedy and violent 
symptoms, and even death. The usual symptoms are, an as- 
tringent taste in the mouth, a sense of constriction and burning 
in the throat and fauces, nausea, violent vomiting, intense pain 
in the stomach and bowels, frequent purging, small and frequent 
pulse, great anxiety, and coldness of the extremities. The 
intellect usually remains clear. 
A robust woman, aged twenty-five years, swallowed, by 
mistake for Epsom salt, a solution containing an ounce and a 
half of sulphate of zinc. She instantly vomited, and then be- 
came affected with almost incessant retching and purging for 
half an hour, which continued afterwards, at short intervals, for 
three hours. There was also a small and frequent pulse, ex- 
treme prostration, great anxiety, coldness of the body, violent 
pain in the abdomen and limbs, with a sense of burning in the 
throat and stomach, and death ensued in thirteen hours and a 
half after the poison had been taken. A sister of this woman, 
aged thirty-five years, took at the same time a similar dose of 
the poison, but after several days of severe illness she finally PHYSIOLOGICAL EFFECTS. 
395 
recovered. In this instance, the vomiting was delayed for fif- 
teen minutes, and there was no purging for ten hours ; the other 
symptoms much resembled those of her sister, except the burn- 
ing sensation in the throat, which was absent. (Amer. Jour. 
Med. Sci., July, 1849, p. 279; from Brit, and For. Med.-Chir. 
Rev., April, 1849.) 
A case of suspected slow poisoning by the sulphates of zinc 
and iron, has been recently reported by Dr. Wm. Herapath 
(London Chem. News, June 16, 1865, p. 288). The symptoms 
were a sense of burning heat in the stomach, fauces, and gullet, 
coppery taste in the mouth, great thirst and nausea after eating 
and drinking, followed by vomiting after from half an hour to 
an hour. After death, the stomach was found considerably 
inflamed in the cardiac portion, and its inner surface was in a 
blistered state; the intestines were but slightly inflamed. Traces 
of sulphates of zinc and iron were found in the vomited mat- 
ters, and also in the contents of the lower intestines; but in 
the contents of the stomach and duodenum, only sulphate of 
iron was found. 
In poisoning by solutions of the chloride of zinc, the symp- 
toms are much the same as those caused by the sulphate. There 
is an immediate burning sensation in the throat, burning pain 
in the stomach, nausea, violent vomiting, purging, cold perspi- 
rations, great anxiety, and feeble pulse. In some instances, 
the vomited matters are streaked with blood, owing to the local 
action of the poison upon the throat and neighboring parts. 
In a case of poisoning by Burnett’s disinfecting fluid, re- 
ported by Dr. Letheby, the patient, a child fifteen months old, 
was seized with extreme prostration, and died in a comatose 
condition, ten hours after taking the dose. In a case communi- 
cated to Dr. Taylor, a woman, aged twenty-eight years, swal- 
lowed an ounce of this fluid, and died from its effects four 
hours afterwards. This is, perhaps, the most rapidly fatal case 
of poisoning by zinc yet recorded. A woman, forty years of 
age, swallowed a quantity of Burnett’s fluid, in mistake for a 
glass of gin. It remained on the stomach only about ten min- 
utes, when it was ejected by vomiting. A burning sensation 
was experienced in the throat and chest for two or three days ; 396 
ZINC 
this was succeeded by an inability of the stomach to retain 
food, and death ensued at the expiration of fourteen weeks, 
apparently from simple prostration, due to want of nourishment. 
(Amer. Jour. Med. Sci., Jan,, 1860, p. 190.) In an instance re- 
ported by Dr. Stratton, of Montreal, a man, aged fifty-four years, 
drank about a wine-glassful of a dense solution of chloride of 
zinc, containing, as prepared, four hundred grains of the salt, 
and entirely recovered from its effects; not, however, without 
experiencing very severe symptoms for several days. 
As metallic sine is more or less acted upon by certain arti- 
cles of food, especially such as contain free organic acids or 
fatty matters, its use for culinary operations, is not altogether 
free from danger. In an instance in which we were consulted, in 
1860, a family, consisting of eight persons, suffered with symp- 
toms of zinc poisoning, occasioned by the use of apple-butter 
prepared with cider, which had been concentrated on a gal- 
vanised iron pan. On chemical examination, the concentrated 
cider was found to contain I*l4 grains of oxide of zinc, in each 
fluid ounce. 
Treatment.—This is much the same as in poisoning by 
salts of lead and copper. No chemical antidote is known. The 
efforts of the stomach should be assisted by the free adminis- 
tration of mild demulcent drinks. The free exhibition of a 
mixture of milk and hydrate of magnesia, and, also, of decoc- 
tions of the vegetable astringents, have been recommended. In 
poisoning by the chloride of zinc, a solution of bicarbonate of 
soda, followed by large draughts of any bland liquid, has been 
advised. Opium may be found useful to allay the subsequent 
irritation. 
Post-mortem Appearances.—ln the case, already cited, in 
which an ounce and a half of the sulphate of zinc proved fatal 
in thirteen hours and a half, the following appearances were 
observed, forty hours after death: great lividity of the external 
surface of the body; congestion of the brain and its mem- 
branes ; a congested state of the lungs; flaccid condition of the 
heart, the right cavities being filled with black, thick blood; 
the inner surface of the stomach was covered with a yellowish, 
pultaceous matter, on the removal of which a uniform yellow, 397 
CHEMICAL PROPERTIES. 
ochrous color was observed, except towards the great curvature, 
where it became reddish; there was also a gelatiniform ramol- 
lissement of the mucous membrane of the stomach, exposing, 
in some parts, the submucous cellular tissue. The small intes- 
tines were somewhat injected, and contained yellowish matters. 
In another case, the stomach was very vascular, spots of ecchy- 
mosis being observable, and near the pylorus, slight ulceration. 
The brain and its membranes were much congested, and the 
pleura contained a large quantity of sanguinolent fluid. (Amer. 
Jour. Med. Sci., July, 1849, p. 280.) In a case, quoted by 
Dr. A. StilD (Mat. Med., vol. ii, p. 33C), which proved fatal on 
the fifth day, after a wineglassful of a concentrated solution of 
sulphate of zinc had been taken, the only morbid appearances 
detected, were patches of inflammation of the mucous mem- 
brane of the pyloric end of the stomach and of the duodenum. 
In Dr. Letheby’s case of poisoning by UurneWs disinfecting 
fluid, before cited, twenty-two hours after death, the mucous 
membrane of the mouth, fauces, and oesophagus, was found of 
a white color and opake. The stomach was hard and leathery, 
and contained about an ounce and a half of liquid resembling 
curds and whey, in which chloride of zinc was afterwards found. 
The inner surface of the stomach had a highly acid reaction, 
was corrugated, opake, and tinged of a dark leaden hue j this 
appearance ceased abruptly at the pylorus. The lungs and 
kidneys were congested. In the case of poisoning by this fluid 
in which death did not occur until the lapse of fourteen weeks, 
the stomach was found so much contracted as to contain only 
four ounces of fluid, and completely perforated in two places by 
ulcers, one being near the cardiac and the other near the py- 
loric orifice. There was no decided peritonitis, but the whole 
of the serous membrane had a slightly greasy feel when touched, 
as if there were some exudation on its surface. 
Chemical Properties. 
Ix the Solid State.—When a few crystals of the sulphate 
of zinc, placed in a watch-glass, are treated with a drop or two 
of a solution of protochromate of potash, they acquire a yellow 398 
ZINC 
color, and soon become converted into a mass of small yellow 
granules. This reaction, although perhaps not entirely peculiar, 
readily serves to distinguish the least visible crystal of the zinc- 
salt from the sulphate of magnesia, or Epsom salt, for which it 
has in several instances been fatally mistaken, and which, when 
treated in a similar manner, slowly dissolves. 
If a small portion of sulphate of zinc be heated on a char- 
coal support in the inner blow-pipe flame, it quickly fuses in 
its water of crystallisation, and leaves a residue which is slowly 
consumed, covering the charcoal in part with a yellow incrus- 
tation of oxide of zinc, which on cooling becomes white. If 
the unconsumed residue, or the incrustation, be moistened with 
a solution of nitrate of cobalt, and then heated in the outer 
flame of the blow-pipe, the mass on cooling acquires a green 
color. These reactions are peculiar to compounds of zinc, and 
will serve for the identification of very minute quantities of the 
metal. It is usually best, however, before applying the blow- 
pipe heat, to mix the zinc compound with carbonate of soda. 
Of Solutions of Zinc.—Pure aqueous solutions of sulphate 
of zinc are colorless, have a styptic, metallic taste, and slightly 
redden litmus-pajaer. When a drop of the solution is allowed 
to evaporate spontaneously, the salt is left in the form of 
slender, prismatic crystals. As found in the shops, sulphate 
of zinc is usually contaminated with iron, and sometimes con- 
tains other impurities, which more or less modify its chemical 
reactions. 
In ascertaining the limit of the reactions of the different 
reagents for zinc, pure aqueous solutions of the sulphate were 
employed. The fractions indicate the fractional part of a grain 
of oxide of zinc (ZnO), present in one grain of the solution. 
The results, unless otherwise stated, refer to the behavior of one 
grain of the solution. One part of the oxide represents 3*54 
parts of pure crystallised sulphate of zinc. 
1. Sulphuretted Hydrogen. 
Sulphuretted hydrogen gas throws down from neutral and 
alkaline solutions of salts of zinc a white, amorphous precipitate SULPHURETTED HYDROGEN TEST. 
399 
of hydrated sulphuret of zinc (ZnS, HO), which is insoluble 
in the caustic alkalies, alkaline sulphurets, and in acetic acid, 
but very readily soluble in the stronger mineral acids. In solu- 
tions containing either free sulphuric, hydrochloric, or nitric 
acid, the reagent fails to produce a precipitate. Even in strong 
solutions of the normal salts of these acids, the reagent throws 
down only a portion of the zinc ; but from solutions containing 
only about one per cent, or less of these salts, the precipitation 
is complete. The separation of the precipitate, especially from 
very dilute solutions, is much facilitated by the application of a 
gentle heat. 
The following results refer to the behavior of ten grains of 
a normal solution of‘sulphate of zinc. 
1. 100 th solution of oxide of zinc (= yo grain ZnO), yields an 
immediate precipitate, and soon there is a copious, white 
deposit. 
2. I,oooth solution: a quite good precipitate. 
3. 10,000 th solution: in a very little time, the liquid becomes 
turbid, and after standing a few hours, yields a very 
satisfactory deposit. 
4. 25,000 th solution : after a little time, the mixture becomes 
turbid, and after a few hours, there is a quite distinct 
deposit 
5. 50,000 th solution: after a little time, the liquid becomes 
cloudy, and after about ten hours, a distinct, flaky deposit 
has formed. 
The production of a white precipitate by this reagent is 
characteristic of zinc, as this is the only metal the sulphuret of 
which has a white color. It should be remembered that the 
color of the precipitate may be much modified by the presence 
of even minute quantities of other metals. It must also be 
borne in mind, that solutions of sesquioxide of iron, may yield 
with sulphuretted hydrogen a white turbidity, due to the decom- 
position of the reagent with the separation of sulphur. 
Sulphuret of ammonium produces the same precipitate of 
sulphuret of zinc from neutral and alkaline solutions of salts of 
the metal. In this case, the precipitation is complete, even 
Irom concentrated normal solutions of any of the salts of the 400 
ZINC 
metal. This reagent, however, also produces in solutions of 
alumina a white precipitate of hydrated sesquioxide of alumina, 
with evolution of sulphuretted hydrogen gas. This precipitate 
is easily distinguished from the sulphuret of zinc, in being 
readily soluble in caustic potash. 
2. Potash and Ammonia 
The fixed caustic alkalies and ammonia throw down from 
normal solutions of salts of zinc, and also from acid solutions 
when excess of the reagent is added, a white precipitate of 
hydrated oxide of zinc (ZnO, HO), which is readily soluble in 
free acids, and in excess of the precijntant. From these alka- 
line solutions, the whole of the zinc is reprecipitated, as sul- 
phuret, by sulphuretted hydrogen gas. 
1. yihr grain of oxide of zinc, in one grain of water, yields a 
copious, gelatinous precipitate. 
2. TTohro grain: a quite good, flocculent precipitate, which readily 
disappears on the addition of slight excess of the reagent. 
3. totWo grain, yields with a very minute quantity of the re- 
These reagents also produce white precipitates in solutions 
of various other substances, beside zinc ; but from these pre- 
cipitates, the washed and dried oxide of zinc is readily distin- 
guished, by its behavior under the blow-pipe flame, as already 
pointed out. 
agent, a slight turbidity. 
The alkaline carbonates throw down from solutions of salts 
of zinc, a white precipitate of basic carbonate of the metal, 
which is insoluble in excess of the fixed alkaline carbonates, 
but soluble in excess of the carbonate and other salts of am- 
monia. The precipitate is also readily soluble in acids, even 
acetic acid, and in the caustic alkalies. The limit of the reac- 
tion of these reagents, is the same as that of the free alkalies. 
8. Ferrocyanide of Potassium. 
This reagent produces in solutions of salts of zinc a white, 
amorphous precipitate of ferrocyanide of zinc (Zn2 Cfy, 3 HO), FERRICYANIDE OF POTASSIUM TEST. 
401 
which is insoluble in acetic, nitric, sulphuric, and hydrochloric 
acids 5 also in ammonia, chloride of ammonium, and in excess 
of the precipitant. In the presence of excess of the precipitant, 
the precipitate acquires a greenish or greenish-blue color when 
acted upon by hydrochloric or nitric acid, due to the decom- 
position of the reagent. Ferrocyanide of zinc is readily soluble 
in caustic potash, to a colorless solution, from which it is repre- 
cipitated by an excess of hydrochloric acid. 
1. grain of oxide of zinc, in one grain of water, yields a 
very copious, gelatinous precipitate. 
2. y;wo grain: a quite good, flocculent deposit. 
3. heWo grain: in a very little time, the mixture becomes 
quite turbid. 
4. yt.oTjlj grain: after a few minutes, a very perceptible tur- 
bidity. 
This reagent also produces white precipitates in solutions of 
several other metals. Most of these precipitates, however, un- 
like that from zinc, are readily soluble in hydrochloric acid. 
4. Ferr icy ankle of Potassium. 
Ferricyanide of potassium occasions in solutions of salts of 
zinc a yellow, reddish-brown, or greenish, amorphous precipi- 
tate, the color depending upon the strength of the solution, 
and also, somewhat, upon the relative quantity of the reagent 
present. The precipitate is insoluble in acetic, hydrochloric, 
sulphuric, and nitric acids; but readily soluble to a clear solu- 
tion in potash, from which it is reprecipitated by hydrochloric 
and sulphuric acids. It is also soluble in ammonia, but in a 
very little time, the solution becomes turbid; from this solution, 
it is also reprecipitated by acids. 
1 • woo" grain of oxide of zinc, yields a copious, dirty-yellow 
precipitate, which very soon assumes a brownish color. 
2. rrifoo grain; a good, greenish-yellow deposit. 
4 • TTrroTn, grain: a very fair, greenish turbidity, and very soon 
a flocculent precipitate. 
4- ,2-570 00 grain: the mixture very soon becomes turbid, and in 
a little time, yields perceptible flakes. 
26 402 
ZINC 
The reaction of this reagent is common to solutions of sev- 
eral different metals. 
5. Oxalic Acid. 
Oxalic acid throws down from solutions of salts of zinc a 
white, granular or crystalline precipitate of oxalate of zinc 
(ZnO, C 203, 2 A<f)l which is insoluble in acetic acid, but readily 
soluble in the stronger mineral acids; it is also soluble in caus- 
tic ammonia, but almost insoluble in chloride of ammonium. 
The separation of the precipitate is much facilitated by a gentle 
heat; also by agitation of the mixture. 
1. inhr grain of oxide of zinc, in one grain of water, yields an 
immediate turbidity, and in a little time, a copious, gran- 
ular precipitate. 
2. r,Wo grain; in a little time, a distinct precipitate, and soon, 
a quite good deposit of granules and octahedral crystals, 
Plate V, fig. 6. 
3. T75~00 grain: after several minutes, small granules form 
along the margin of the drop, and in ten or fifteen min- 
utes, there is a very satisfactory, granular and octahedral 
deposit. 
Oxalic acid throws down white precipitates from solutions 
of salts of most of the metals, and in the case of lime, and also 
of strontia, the precipitate may have the same microscopic char- 
acters as the oxalate of zinc. The true nature of the zinc pre- 
cipitate, however, may be readily determined b}7 its behavior 
before the blow-pipe. 
6. Chromate of Potash. 
Protochromate of potash produces in solutions of sulphate ot 
zinc a bright yellow, amorphous precipitate, which, according 
to Thomson, consists of the subchromate of zinc. At ordinary 
temperatures, the precipitate is somewhat slow to form, even 
from strong solutions, but it separates immediately on the ap- 
plication of heat. It is insoluble in excess of the precipitant, 
but readily soluble in acetic acid, and in ammonia. PHOSPHATE OF SODA TEST. 
403 
1. Yoi) grain of oxide of zinc, yields, in tlic cold, an immediate 
cloudiness, and soon a copious, yellow precipitate. 
2. iToVo grain: an immediate turbidity, and soon a good, floc- 
culent deposit. 
3. rcVoT grain: after a little time, the mixture becomes quite 
turbid. 
This reagent produces similar yellow precipitates in solu- 
tions of several other metals. 
Bichromate of potash fails to produce a precipitate, even in 
concentrated normal solutions of salts of zinc. 
• 7. Phosphate of Soda. 
Common phosphate of soda throws down from solutions of 
salts of zinc a white precipitate of tribasic phosphate of zinc 
(3 ZnO ] P05), which is soluble in acids, even in acetic acid, 
also in potash and ammonia, but only sparingly soluble in 
chloride of ammonium. From strong solutions, the precipitate 
as first produced is gelatinous, whilst from dilute solutions it 
is flocculent; but after standing some time, it diminishes in 
volume and becomes converted, at least partially, into crystal- 
line plates: this change is produced immediately or in a very 
little time, by boiling the mixture. 
1. uru grain of oxide of zinc, yields a quite copious, gelatinous 
2. jtoWo grain: a good, flocculent deposit. 
precipitate. 
3- ruTcnnj grain: after some minutes, a quite distinct turbidity. 
The production of a white precipitate, by this reagent, is 
common to solutions of quite a number of the metals. 
Detection of the Acid.—The tests now considered, would, 
of course, only serve for the detection of the base of the zinc- 
salt. The presence of sulphuric acid, when combined with the 
metal, may be readily detected by acidulating the solution with 
nitric acid and treating it with chloride of barium, by which 
the sulphuric acid will be precipitated as white sulphate of 
baryta, which is insoluble in nitric acid. The presence of 
hydrochloric acid may be determined by treating the solution. 404 
ZINC 
acidulated with nitric acid, with nitrate of silver, when any 
chlorine present will he thrown down as chloride of silver, 
which is readily soluble in ammonia, but insoluble in diluted 
nitric acid. 
Separation from Organic Mixtures. 
Contents of the Stomach.—The same method of analysis is 
equally applicable for the examination of suspected articles of 
food, vomited matters, and the contents of the stomach. Salts 
of zinc are more or less decomposed and precipitated by albu- 
men, fibrin, casein, and certain other organic principles. When, 
therefore, the suspected mixture contains any solid matter, the 
whole, after the addition of water if thought best, should be 
acidulated with acetic acid and gently heated for some time, 
when any organic precipitate of zinc present will be dissolved. 
The solution thus obtained, is filtered, and the filtrate, after 
concentration if necessary, treated with sulphuret of ammonium 
as long as a precipitate is produced, after which it is gently 
warmed, to facilitate the complete separation of the precipitate. 
The precipitate is then collected on a filter, washed, and while 
still moist, digested with nitric acid, in which the zinc will 
dissolve, forming nitrate of the metal; at the same time, any 
iron present will be oxidised and dissolved as nitrate of sesqui- 
oxide of iron. The solution is now evaporated to dryness, to 
expel the excess of acid, the residue dissolved in a small 
quantity of distilled water, and the filtered liquid examined by 
the ordinary tests for zinc. 
Should the/solution contain iron, which is a frequent impur- 
ity in salts of zinc, the chemical reactions of the latter, as 
already pointed out, will be more or less modified. These 
metals may be separated by the addition of excess of caustic 
ammonia, which will precipitate the iron as hydrated sesqui- 
oxide, while the zinc will be redissolved and remain in solution. 
Should the iron exist as protoxide of the metal, before precipi- 
tating with ammonia, it must be converted into the sesquioxide, 
by boiling the mixture with a little nitric acid. After separa- 
ting the precipitated iron by a filter, the zinc in the ammoniacal QUANTITATIVE ANALYSIS. 
405 
filtrate may be precipitated by sulphuretted hydrogen gas; or, 
the solution may be exactly neutralised with acetic acid, and 
then tested in the ordinary manner. As this neutralisation 
would give rise to a salt of ammonia, in which the precipitates 
produced by many of the reagents for zinc are more or less 
soluble, if only a minute quantity of the metal be present, it 
is best to expel the excess of ammonia, by evaporating the 
solution to dryness, and then redissolve the residue in a small 
quantity of water containing a drop or two of acetic acid. 
From the Tissues.—Absorbed zinc may be recovered by 
boiling the finely divided tissue with nitric acid diluted with 
five or six volumes' of water, until the organic matter is com- 
pletely disintegrated. The mass is then transferred to a muslin 
strainer, the strained liquid evaporated to dryness, and the 
residue moistened with pure nitric acid, and heated until the 
organic matter is entirely destroyed. The dry mass thus ob- 
tained, is treated with water containing a little hydrochloric 
acid, the filtered liquid evaporated to dryness on a water-bath, 
the residue dissolved in pure water, and the solution treated with 
sulphuret of ammonium. Any precipitate thus obtained, is col- 
lected, washed, and examined in the manner before described. 
In several instances of poisoning by the salts of zinc, the 
metal was readily discovered in the blood and tissues after 
death, even in some cases after comparatively long periods. 
It need hardly be remarked that, when the metal is found in 
its absorbed state, it will be impossible from chemistry alone, 
to determine in what form it was originally taken. 
Quantitative Analysis.—Zinc is usually estimated in the 
form of oxide of the metal. For this purpose, the solution is 
heated to about ths boiling temperature, and treated with a 
somewhat dilute solution of carbonate of soda as long as a 
precipitate is produced, after which it is boiled for some min- 
utes. The precipitate is then allowed to subside, collected on 
a filter, washed with hot water, dried, and ignited. The whole 
of the zinc will now exist in the form of protoxide, one hund- 
red parts of which correspond to 354T3 parts of pure crystal- 
lised sulphate, or 167‘77 parts of anhydrous chloride of zinc. PART SECOND 
VEGETABLE POISONS VEGETABLE POISONS. 
INTRODUCTION. 
NATURE OF VEGETABLE POISONS GENERAL METHODS FOR RECOV- 
ERING THE ALKALOIDS FROM ORGANIC MIXTURES. 
The different poisonous plants owe their toxic properties to 
tLe presence of one or more proximate principles, some of 
which have not as yet been obtained in their isolated state. 
Most of these active principles have basic properties, and such, 
as a class, from their general chemical resemblance to the ordi- 
nary alkalies, have been named alkaloids, or vegetable al- 
kalies. A few others, in regard to their chemical nature, are 
neutral; while others still, have acid properties. In poisoning 
by these substances, the poison is usually taken in its more or 
less crude state; but in some instances, as in the case of 
strychnine, and morphine, it is not unfrequently taken in its 
pure form. The present consideration of this class of poisons, 
will be confined to such as contain principles, the nature of 
which, even when present only in minute quantity, can be fully 
established. 
The natural alkaloids always exist in the plants from which 
they are obtained, in the form of salts, which generally contain 
an organic acid peculiar to the plant in which the base is found. 
They all contain nitrogen, usually in the proportion of one 
equivalent, but sometimes two equivalents, combined with vari- 
ous proportions of carbon and hydrogen, sometimes alone, but 
generally with the addition of oxygen. They are naturally 
divided into two classes: the volatile, or liquid, and the fixed 
alkaloids. 410 
VEGETABLE POISONS; INTRODUCTION. 
The volatile alkaloids consist of carbon, hydrogen, and nitro- 
gen ; are liquid at ordinary temperatures; have a strong and 
peculiar odor; and pass over with the vapor of water, when 
their free aqueous solutions are distilled. On the other hand, 
the fixed alkaloids contain carbon, hydrogen, nitrogen, and ox- 
ygen ; are solid at ordinary temperatures; destitute of odor; 
and do not distill with the vapor of water. In their free state, 
most of the alkaloids are but sparingly soluble in water, but 
readily soluble in alcohol, ether, and chloroform. Their salts 
are, for the most part, soluble in water and in alcohol, but 
insoluble in ether, and chloroform. 
In their pure state, many of these substances may be identi- 
fied with as much certainty, and in as minute quantity, as most 
of the inorganic poisons; but their detection when present in 
complex mixtures, is generally much more difficult, requiring 
more care and delicacy of manipulation, and is attended with 
much greater loss of material, than the recovery of inorganic 
substances. Again, as the quantity of the alkaloids necessary 
to prove fatal, is usually very much less than that of inorganic 
poisons, the actual quantity of poison present in death from the 
former, is generally much less than that in poisoning by the 
latter. Moreover, since all organic poisons sooner or later un- 
dergo complete decomposition in the dead body, they can at 
most be detected after only very limited periods, at least in 
comparison with some of the metallic poisons. 
From these considerations, it is obvious that in poisoning by 
the vegetable alkalies, it may often happen that there will be a 
failure to detect the poison. Even when the poison is discov- 
ered, the amount recovered is frequently so minute as to ren- 
der it impossible to make a quantitative analysis. In many 
instances, the nearest approach that can be made as to the 
quantity recovered, is by observing the intensity of the reac- 
tions of the reagents applied, and comparing these with the 
reactions of known quantities of the poison. 
For the recovery and purification of the alkaloids, when 
mixed with foreign matters, several general methods have been 
proposed; but, as might be expected, these processes are not 
equally applicable for all the members of this class of poisons. RECOVERY BY METHOD OF STAS. 
411 
Some of these methods—most of which are based upon the 
principles first pointed out, in 1851, by M. Stas, of Brussels— 
will now be described, with some comments on. each. 
1. Method of Stas 
This method is much the same as that usually employed for 
extracting the alkaloids from the vegetables in which they oc- 
cur. It takes advantage of the fact that the acid salts of the 
alkaloids are soluble in water and in alcohol; and, that when a 
solution of this kind is decomposed by the addition of an excess 
of a fixed mineral alkali or its carbonate, and agitated with 
pure ether, this liquid will dissolve the liberated alkaloid. In 
the case of the volatile alkaloids, advantage is also taken of the 
insolubility of their acid salts in ether, to separate such organic 
impurities as are soluble in this liquid, by agitating the mixture 
with the fluid while the alkaloid is in the form of a salt. 
To apply this method, the suspected mixture, such as the 
contents of the stomach, is treated with about twice its weight 
of pure concentrated alcohol and from ten to thirty grains of 
tartaric or oxalic acid, and the whole heated in a flask to about 
160° F. If the substance under examination is one of the solid 
organs of the body, as the liver, heart or lungs, it is first cut 
into very small fragments and the mass moistened with strong 
alcohol, then strongly pressed, and the operation repeated with 
fresh portions of alcohol, until the soluble matters are entirely 
extracted; the mixed alcoholic fluids are then acidified with 
tartaric or oxalic acid, and heated in the manner just described. 
When the alcoholic mixture has entirely cooled, the fluid is 
filtered, the solids on the filter well washed with strong alcohol, 
and the mixed filtrates evaporated to near dryness at a temper- 
ature not exceeding 95° F., either in a strong current of air, 
or in vacuo over sulphuric acid. If during the evaporation, 
fatty or other insoluble matters separate, the concentrated fluid 
is filtered, the filter washed with alcohol, and the filtrate and 
washings evaporated as above, at a temperature not exceeding 
95°. The residue is then digested with cold absolute alcohol, 
the mixture filtered, the filter washed with alcohol, and the 412 
VEGETABLE POISONS: INTRODUCTION. 
mixed liquids evaporated at a low temperature to dryness. 
The residue thus obtained, is dissolved in a very small quan- 
tity of water, and the solution treated with slight excess of pow- 
dered bicarbonate of soda. The solution is now violently agi- 
tated, in a stout test-tube or a small flask, with four or five 
volumes of pure ether, the mixture allowed to repose, and then 
a small portion of the clear supernatant ether transferred to a 
watch-glass and allowed to evaporate spontaneously. 
If the transferred ether contained a liquid alkaloid, in not too 
minute quantity, it will now remain, in the watch-glass, as oily 
streaks, which, upon the application of a very gentle heat, col- 
lect into a drop and emit the peculiar pungent odor of the 
alkaloid (nicotine or conine), more or less masked by that of 
any animal matter present. If, however, a fixed alkaloid be 
present, there will be traces of a solid residue, destitute of any 
odor other than that of animal matter. 
.The alkaloid is liquid and volatile.—lf traces of a volatile 
alkaloid are thus discovered, the contents of the vessel, from 
which the small portion of ether was taken, are mixed with 
from fifteen to thirty grains of a strong solution of caustic pot- 
ash or soda, and the whole violently agitated; after repose, the 
clear ether is separated by means of a pipette, and the residue 
washed in a similar manner three or four times with fresh por- 
tions of ether. The mixed ethereal liquids are now agitated 
with a small quantity of water containing sufficient diluted sul- 
phuric acid to render the whole distinctly acid; the ether is 
then decanted, and the aqueous solution washed two or three 
times with fresh portions of ether. 
By this treatment, the aqueous solution will retain, in the 
form of sulphate, any volatile alkaloid present; while the de- 
canted ether will remove such foreign matters as are soluble in 
that liquid. As, however, the sulphate of conine is not alto- 
gether insoluble in ether, this fluid may contain a small quan- 
tity of that salt. 
The aqueous solution is now mixed with an excess of a 
concentrated solution of caustic potash or soda, and again 
agitated with three or four volumes of pure ether, which will 
dissolve the liberated alkaloid, and also any ammonia present. RECOVERY BY METHOD OF STAS. 
413 
The ether is then carefully decanted, the residue washed with 
a fresh portion of ether, the mixed ethers exposed to spon- 
taneous evaporation at a low temperature, and the last trace of 
ammonia, if present, removed by placing the dish, containing 
the residue, for a few moments in vacuo over strong sulphuric 
acid, when the alkaloid will be left in its pure state. The 
exact nature of the alkaloid is then determined by appropri- 
ate tests. 
The alkaloid is solid and fixed.—If the evaporation of the 
small portion of ether, taken from the mixture neutralised by 
bicarbonate of soda, does not indicate the presence of a volatile 
alkaloid, the original mixture is treated with twenty or thirty 
grains of a strong solution of potash or soda, and again violently 
agitated; when the liquids have separated, the clear ether is 
decanted, the residue thoroughly extracted with fresh portions 
of ether, and the united ethereal liquids allowed to evaporate 
spontaneously at a low temperature. The residue thus obtained, 
is sometimes in the solid form, but more frequently as a color- 
less milky liquid, in which are suspended small solid particles. 
It has usually a distinct alkaline reaction, and an offensive 
animal odor, which, however, is not pungent. 
The residue is now treated with a few drops of alcohol, and 
the liquid allowed to evaporate spontaneously. If this fails to 
furnish the alkaloid in its crystalline form, a few drops of water 
feebly acidulated with sulphuric acid, are added and gently 
rotated over the residue. This will convert the alkaloid into a 
sulphate of the base, which will dissolve ; while any fatty mat- 
ters present, will usually remain undissolved and adhere to the 
sides of the dish. The liquid is cautiously decanted or filtered, 
the residue washed with a few drops of acidulated water, and 
the mixed liquids evaporated to a small volume in vacuo, or 
under a receiver over strong sulphuric acid. The concentrated 
liquid is then rendered alkaline by a concentrated solution of 
pure carbonate of potash or of soda, and the mixture treated 
with absolute alcohol, which will dissolve the liberated alkaloid, 
while the sulphate of potash formed, together with any excess 
of carbonate of potash present, will remain undissolved. The 
alcoholic solution is carefully decanted or filtered, and exposed 414 
VEGETABLE POISONS: INTRODUCTION. 
to spontaneous evaporation, when the alkaloid will be left in its 
pure state. Its true nature is now determined by the appro- 
priate reagents. 
On applying the principles now described, M. Stas states 
that he has succeeded in isolating, when previously mixed with 
foreign matters, the following alkaloids; nicotine, conine, aniline, 
morphine, codeine, strychnine, brucine, veratrine, emetine, col- 
chicine, aconitine, atropine, and hyoscyamine. He has also 
thus extracted morphine from opium; strychnine and brucine 
from mix vomica; veratrine from extract of veratrum; emetine 
from extract of ipecacuanha; colchicine from tincture of colchi- 
cum; aconitine from an aqueous extract of aconite; hyoscy- 
amine from an old extract of henbane; and atropine from an 
old tincture of belladonna. (Chemical Gazette, London, 1852, 
p. 348, et seq.; from Bulletin de V Academic de Medecine de 
Belgique, vol. vi, No. 2.) 
In applying the above method, the operator should bear in 
mind that the different alkaloids differ greatly in regard to their 
solubility in ether, and, therefore, that the quantity of this fluid 
necessary for their complete extraction from aqueous or alkaline 
mixtures will vary, other things being equal, with the nature 
of the base. In all cases, the quantity of a given substance 
that ether or any similar liquid will separate from its aque- 
ous or alkaline solution—the quantities of the different liquids 
being equal—will be in the same ratio as the solubility of 
the substance in the former menstruum exceeds its solubility 
in the latter. 
For the extraction of most of the vegetable bases considered 
in the present treatise, the method of Stas is very applicable; 
but for others, it is only partially successful, or entirely fails, 
especially when the alkaloid is present in very complex mix- 
tures. Thus, solanine something over six thousand 
times its weight of ether for solution, and therefore the quantity 
of this liquid necessary for the extraction of even a small 
quantity of the alkaloid is so great that it at the same time 
dissolves so much foreign matter as to render the ethereal 
residue unfit for the application of special tests. The same DETECTION BY METHOD OF STAS. 
415 
difficulty is also experienced in the separation of morphine, 
which in its crystalline state requires nearly eight thousand 
times its weight of ether for solution, and is at the same time 
somewhat soluble in alkaline fluids. This difficulty is removed 
to a considerable extent, as first suggested by Poellnitz, by 
quickly agitating the aqueous or alkaline solution with ether 
and decanting this fluid before the morphine assumes the crys- 
talline form. Again, in the case of nicotine, large quantities 
and repeated agitations with ether are required for its complete 
separation from aqueous solutions; since, although the alkaloid 
is very soluble in ether, yet it is also freely soluble in water. 
In the special consideration of the different alkaloids, their exact 
solubility in water and ether, as well as in chloroform, will be 
pointed out. 
In the application of the above method for the detection of 
the fixed alkaloids, Professor Otto strongly advises (Detection 
of Poisons, p. 160) to pursue much the same coarse as that 
advised for the recovery of the volatile, or liquid bases. Thus, 
the organic mixture is treated with strong alcohol and oxalic or 
tartaric acid, and the whole gently heated; the cooled liquid is 
then filtered, the filtrate concentrated, the liquid again filtered, 
then evaporated to near dryness,, the residue extracted with 
absolute alcohol, the filtered extract evaporated to dryness, and 
the dry residue dissolved in a small quantity of water. All 
these operations are conducted in the same manner as before 
described. 
Instead of now treating the aqueous solution—which con- 
tains the alkaloid in the form of a salt—with bicarbonate of 
soda or the caustic alkali, it is agitated with pure ether, and 
the operation repeated as long as this liquid extracts any color- 
ing matter; it is then treated with excess of a mineral alkali, 
and again agitated with ether, which will now dissolve the 
liberated alkaloid, and leave it, upon spontaneous evaporation, 
in its nearly or altogether pure state, and not unfrequently in 
the crystalline form. 
Repeated experiments in our own hands, with several of the 
fixed alkaloids, have fully confirmed the advantages claimed by 
Professor Otto for this process. Even granting that the ether 416 
VEGETABLE POISONS: INTRODUCTION. 
takes up a trace of the alkaloidal salt, still, he remarks, this 
method deserves the preference, since a small quantity of the 
alkaloid, in a pure state, is infinitely more valuable for our 
purpose than a larger quantity in a state of impurity. 
2. Method of Rodgers and Gtrdwood. 
This process was recommended by its authors (London Lan- 
cet, June 28, 1856, p. 718) simply for the recovery of strych- 
nine, hut, with slight modifications, it is equally applicable for 
the detection of most of the alkaloids. In principle it is much 
the same as the method of Stas, only that chloroform instead of 
ether is used as the solvent of the liberated alkaloid. The 
details of this method are as .follows: 
The organic mixture, as the contents of the stomach, is 
treated with water acidulated with hydrochloric acid, and di- 
gested at a moderate heat, for about two hours; when the mass 
has cooled, the liquid is separated by means of a muslin strainer, 
then filtered, and evaporated to dryness over a water-bath. 
The residue thus obtained, is digested with strong alcohol con- 
taining a few drops of hydrochloric acid, the solution filtered, 
evaporated to dryness, and the residue extracted with distilled 
water. This aqueous solution is filtered, the filtrate supersat- 
urated with ammonia, and the mixture agitated with about half 
an ounce of chloroform. When the chloroform has completely 
subsided, it is transferred, by means of a pipette, to a small 
evaporating dish, and evaporated to dryness. This residue 
contains any strychnine present, together with more or less 
foreign matter. To destroy the latter, the residue is moistened 
with concentrated sulphuric acid and allowed to remain over a 
water-bath for at least half an hour; then treated with pure 
water, the mixture transferred to a test-tube, and when perfectly 
cool, treated with slight excess of ammonia, and again agitated 
with about half an ounce of chloroform. 
The chloroform solution thus obtained, usually contains the 
strychnine in a sufficiently pure state for special testing. If, 
however, a small portion of the liquid upon evaporation leaves 
a residue, which when moistened with concentrated sulphuric RECOVERY BY METHOD OF USLAR AND ERDMANN. 
417 
acid becomes charred, the whole of the chloroform is evapo- 
rated to dryness, and the residue charred with sulphuric acid, 
in the manner just described, then dissolved in pure water, and 
the solution, after the addition of ammonia, again agitated with 
chloroform. 
A small portion of the chloroform is now separated, by 
means of a small pipette, and several drops or more allowed to 
evaporate successively within as small a space as possible, in a 
white porcelain capsule. The residue thus obtained, is then 
tested in the ordinary manner. 
In case the liver, spleen, or kidneys are the subject of anal- 
ysis, the solid organ should be reduced to a state of pulp in a 
mortar, previous to digestion in acidulated water. In the case 
of the tissues, if recent, they should be cut into very small 
pieces, and triturated in a similar manner. 
As most of the alkaloids are much more freely soluble in 
chloroform than in ether, the former of these liquids is much 
better adapted than the latter, for the separation of these poi- 
sons from organic mixtures. In no case, however, have we 
found it necessary to resort to the use of concentrated sulphuric 
acid, as advised by Messrs. Rodgers and Girdwood, for the de- 
struction and separation of the foreign matter. 
3. Method of Uslar and Erdmann 
This process is founded on the fact that the free alkaloids 
are quite freely soluble in pure amylic alcohol; while, on the 
other hand, their chlorides are insoluble in this menstruum, and, 
therefore, the former are readily removed from their solution in 
this liquid, by shaking the mixture with water acidulated with 
hydrochloric acid. The manipulations according to this method, 
are the following : 
The suspected mixture, made if necessary into a thin paste 
with water, is slightly acidulated with hydrochloric acid, and 
digested for one or two hours at a temperature of about 160° F. 
It is then transferred to a linen cloth which has been previ- 
ously moistened with water, and when the liquid has passed, the 
27 418 
VEGETABLE POISONS: INTRODUCTION. 
residue exhausted with hof water acidulated with hydrochloric 
acid, and the combined liquids treated with slight excess of 
ammonia, after which they are concentrated, first over an open 
fire, then evaporated to dryness in a water-bath. The residue 
thus obtained, is extracted three or four times with hot araylic 
alcohol, and the united solutions filtered through paper, previ- 
ously moistened with the alcohol. The filtrate has usually a 
yellow color, and contains, besides the alkaloid, fatty and color- 
ing matters. To free it from the latter, the liquid is transferred 
to a cylindrical vessel, and violently agitated with several times 
its volume of nearly boiling water, acidulated with hydrochloric 
acid. By this operation the alkaloid is removed from its alco- 
holic solution, being taken up by the acidulated water, while 
the fat and coloring matter remain in the alcoholic liquid. 
This fluid is now removed by means of a caoutchouc-pipette, 
and the hot acid solution repeatedly extracted with fresh por- 
tions of arnylic alcohol, until the fatty and coloring matters are 
completely removed; after which the clear aqueous liquid is 
concentrated somewhat by evaporation, then supersaturated 
with ammonia, and the mixture well shaken with fresh, hot, 
arnylic alcohol. 
When the liquids have separated, the arnylic alcohol, which 
now contains the free alkaloid, is removed by means of a pi- 
pette, and the acid solution again extracted with a fresh portion 
of the hot alcohol. The mixed alcoholic liquids are then evap- 
orated to dryness on a water-bath, when the alkaloid will be 
left, often in a sufficiently pure state for special examination. 
Should it, however, still present a yellowish or brownish color, 
it is again dissolved in very dilute hydrochloric acid, the solu- 
tion agitated with a fresh portion of the hot alcohol, the latter 
liquid removed, and the aqueous solution treated with excess of 
ammonia, then shaken with hot arnylic alcohol, and this fluid 
separated and evaporated as before. 
The authors of this method cite a number of experiments in 
which, by it, they succeeded in recovering small quantities of 
morphine, narcotine, nicotine, conine, and strychnine, previ- 
ously added to quite complex organic mixtures. In one of these 
experiments, about the third of a grain of chloride of morphine RECOVERY BY METHOD OF GRAHAM AND HOFMANN. 
419 
was added to a calf’s stomach, and the latter exposed for a 
fortnight to the action of the sun and air; yet at the end of 
that time, although the mass had become thoroughly putrid, the 
alkaloid was recovered, and its presence indicated by the reac- 
tion of perchloride of iron. (Liebig’s Annalen, 1861, vol. 120.) 
As morphine is quite soluble in amylic alcohol, while it is 
almost insoluble both in ether and chloroform, the former of 
these liquids is very much better adapted than either of the 
latter for the separation of this base from organic mixtures. 
But, for the separation of alkaloids about equally soluble in 
these three liquids', we much prefer the use of ether or chloro- 
form to that of amylic alcohol, as the latter separates more 
slowly, than either of the others, from aqueous mixtures, and 
also requires a longer time for its evaporation. Moreover, as 
amylic alcohol requires a direct heat for its vaporization, any 
alkaloid present, is much less likely to be left in its crystalline 
state, than when it is deposited from ether or chloroform by 
spontaneous evaporation. Most of the alkaloids are more freely 
soluble in chloroform than in amylic alcohol. 
4. Process of Graham and Hofmann. 
This method was first advised by Professors Graham and 
Hofmann for the detection of strychnine, when present, in beer ; 
but it has since been extended, by other experimenters, to the 
separation of this and other alkaloids from other organic liquids. 
It takes advantage of the fact that when a solution of strych- 
nine is agitated with charcoal, the latter absorbs the poison, 
and yields it up to alcohol when boiled with this liquid. The 
following are the details of the process, as first employed by 
its authors. 
Two ounces of ivory-black, or animal charcoal, were shaken 
in half a gallon of beer to which half a grain of strychnine had 
been purposely added. After standing for about twelve hours, 
the liquid was found to be nearly deprived of all bitterness; 
the strychnine being absorbed by the charcoal. The liquid 
was now passed through a paper-filter, upon which the charcoal 420 
VEGETABLE POISONS: INTRODUCTION. 
containing the strychnine was collected and drained. The char- 
coal was then boiled for half an hour in eight ounces of ordinary 
spirits of wine, avoiding loss of alcohol by evaporation. 
The alcoholic liquid, thus obtained, which now contained the 
strychnine, was next filtered, and afterwards submitted to dis- 
tillation. A residual watery fluid was thus obtained, holding 
the strychnine in solution, but not sufficiently pure for the ap- 
plication of tests. This solution was rendered alkaline by a few 
drops of a solution of caustic potash, and then agitated with an 
ounce of pure ether. The ethereal liquid, when separated and 
allowed to evaporate spontaneously in a watch-glass, left the 
alkaloid in a state sufficiently pure for testing. (Quart. Jour. 
Chem. Soc., 1853, p. 178.) 
Upon repeating this method, we find that from complex or- 
ganic mixtures containing a very notable quantity of strychnine, 
the alkaloid is extracted by the charcoal in a very nearly pure 
condition, or at most requires only one agitation with ether or 
chloroform to complete its purification; but when only a very 
minute quantity of the poison is present, it either entirely 
escapes detection or is so contaminated with foreign matter as 
to require as many extractions with ether or chloroform, for its 
purification, as to separate it by either of these liquids directly 
from the prepared original mixture. In all cases, according to 
our experience, this method is attended with greater loss of 
material, than to prepare the mixture according to the process 
of Stas, and then extract by chloroform. 
5. Method by Dialysis. 
Professor T. Graham has recently shown that moist organic 
membranes possess the remarkable property of separating, when 
in solution, crystallisable substances from such as are uncrys- 
tallisable, the former readily passing through such membranes 
when surrounded by a liquid, whereas the latter entirely fail to 
thus pass or do so only very slowly. (Jour. Chem. Soc., 1862, 
p. 216.) The first of these classes, comprehending the crystal- 
lisable substances, he named crystalloids, the second colloids; RECOVERY BY DIALYSIS. 
421 
and to this method of separation, he applied the term dialysis. 
The most suitable substance for the dialytic septum, is the ma- 
terial known as parchment-paper, which is prepared by immers- 
ing unsized paper for a few moments in a cold mixture of two 
measures of sulphuric acid and one of water. 
For the application of this method, a light hoop of wood, 
or better, of sheet gutta percha, about two inches in depth and 
from five to ten inches in diameter, is covered with a piece of 
moistened parchment-paper, so as to form a sieve-like vessel 
(Fig. 12, a). The disc of paper used should exceed in diameter 
the hoop to be covered by three or 
four inches, so as- to rise well up the 
outside of the hoop, and it should be 
bound to the hoop by a string or by 
an elastic band, but it should not be 
firmly secured. The parchment-paper 
must be entirely free from rents or 
pores. Its soundness may be ascer- 
tained by sponging the upper surface 
with pure water, and then observing 
whether wet spots appear on the opposite side: in case they 
do, the defects may be remedied by applying liquid albumen, 
and then coagulating this by heat. The vessel thus prepared 
is called the dialyser. 
The liquid mixture to be examined is now poured into the 
dialyser, upon the surface of the parchment-paper, but only in 
such quantity as at most not to exceed about half an inch in 
depth. The vessel, with its contents, is then floated in a basin 
(b, Fig. 12) containing a quantity of pure water about four or 
five times greater than the volume of liquid in the dialyser. 
Any crystalloidal matter present, whether mineral or organic, 
will now begin to pass through the parchment-paper into the 
water in the larger vessel, and in twenty-four hours about two- 
thirds or more of it may be found in the outer liquid, or diffu- 
sate, as the latter is called. In most instances, the diffusion is 
much promoted by the application of a gentle heat. 
The diffusate is then concentrated, on a water-bath, to 
a small volume or evaporated to dryness, and the residue, if 
Graham’s Apparatus for the Appli- 
cation of Dialysis. 422 
VEGETABLE POISONS: INTRODUCTION. 
sufficiently pure, examined by appropriate reagents. If, how- 
ever, the residue is unfit for special testing, as will usually be 
the case, at least in the case of the alkaloids, it is further puri- 
fied by extraction with ether or chloroform, and then examined. 
In a number of experiments by this method, for the separa- 
tion of small quantities of different alkaloids from complex 
organic liquids, we were much disappointed in the results, they 
always falling far short of what we anticipated, especially in 
regard to the purity of the diffused alkaloid. 
Even when the diffusate contains a quite notable quantity 
of the poison, the amount of colloidal, or amorphous matter also 
present in the liquid, is not unfrequently such as to require for 
its removal as many operations and as much labor, as to extract 
the alkaloid at once from the original mixture by chloroform or 
ether, according to the methods previously considered. More- 
over, when only a minute quantity of the vegetable base is 
present in the mixture submitted to examination, as a portion 
of the poison always remains in the dialyser, it may entirely 
escape detection, even when the quantity present in the original 
mixture is sufficient to give satisfactory results by the chloro- 
form or ether method. 
These results closely accord with those obtained from simi- 
lar experiments by Dr. Harvey. (London Lancet, Jan. 3, 1863, 
p. 6.) Some quantitative experiments in regard to the merits 
of this method for the extraction of small quantities of strych- 
nine, will be detailed hereafter, in the special consideration of 
that alkaloid. 
From the fact, that in poisoning by metallic compounds the 
quantity present is generally much greater than in poisoning by 
vegetable substances, and, also, as the former usually diffuse 
somewhat more readily than the latter, through membranes, 
dialysis seems better adapted, in medico-legal examinations, for 
the detection of mineral than of organic poisons. NICOTINE. 
CHAPTER I. 
VOLATILE ALKALOIDS: NICOTINE, CONINE. 
Section I. Nicotine. (Tobacco.) 
History.—Nicotine, nicotina, or nicotia, is the active princi- 
ple of the common-tobacco plant, Nicotiana Tabacum, in which 
it occurs in combination with malic acid; it exists in the leaves, 
root, and seeds of the plant, and also in the smoke of tobacco. 
Nicotine is destitute of oxygen, its formula being or 
according to some observers, ClOH7N. Vauquelin, in 1809, was 
the first to attempt the separation of this active principle, and 
he succeeded in discovering some of the properties of some of 
its compounds, but failed to isolate the pure alkaloid. Posselt 
and Reimann, in 1828, were the first to separate the alkaloid; 
in 1842, Ortigosa analysed some of its compounds, and Barral 
analysed nicotine itself. (GrineliiTs Hand-book, vol. xiv, p. 220.) 
Preparation.—Nicotine may be prepared, as first proposed 
by M. Schloesing, in the following manner: Coarsely powdered 
tobacco is boiled with water, the cooled liquid strained through 
linen, then evaporated to the consistency of a syrup, and while 
hot agitated with twice its volume of alcohol of sp. gr. 0*837. 
After standing some time, the liquid portion of the mixture, 
which contains the whole of the vegetable base, is decanted 
from the black and almost solid deposit, then concentrated, and 
mixed, while still warm, with a solution of potash, by which 
the alkaloid will be set free. The cooled mixture is agitated 
with ether, which will dissolve the liberated base, together with 
some coloring matter. After repose, the ethereal liquid is de- 
canted and agitated with powdered oxalic acid, when, after a 
time, the oxalate of nicotine thus formed will subside as a 
syrupy mass. This, after the decantation of the ether, is 
washed with fresh ether, then rendered alkaline with potash and 424 
NICOTINE. 
again agitated with ether, which will now dissolve the alkaloid. 
The ethereal solution is transferred to a retort, the ether dis- 
tilled off, and the residue exposed for some hours, at a temper- 
ature of about 284° F., to a current of hydrogen gas, by which 
the last traces of ether, water, and ammonia will be separated; 
the heat is then increased to about 856° F., when the alkaloid 
will distill over pure and colorless. 
The proportion of nicotine varies greatly in different kinds 
of tobacco. According to Schloesing (Chem. Gaz., v, p. 48), 
some dried French samples contain from 7 to 8 per cent, of the 
alkaloid;■ Virginia and Kentucky, 6or 7 per cent.; while Mary- 
land and Havanna, only about 2 per cent., which is about the 
proportion found in ordinary snuff. 
Nicotine is a transparent, colorless, oily liquid, and one of 
the most active poisons known, even equaling in the rapidity 
of its action hydrocyanic acid. There are however, perhaps, 
only two instances yet recorded of poisoning of the human sub- 
ject by this substance in its pure form; but poisoning by to- 
bacco, which owes its activity entirely to this alkaloid, is not 
of unfrequent occurrence. The following consideration in re- 
gard to the physiological effects of the alkaloid, will, therefore, 
be based chiefly upon its action as observed in cases of poison- 
ing by tobacco. 
Symptoms.—The usual effects produced by a poisonous dose 
of tobacco, when taken into the stomach, are confusion in the 
head, paleness of the countenance, vertigo, nausea, severe retch- 
ing and vomiting, heat in the stomach, great anxiety, a sense 
of sinking at the pit of the stomach, with extreme prostration, 
trembling of the limbs, and sometimes violent purging. The 
pulse is small, feeble, and almost imperceptible ; the respiration 
difficult, and the skin cold and clammy; the pupils are gener- 
ally dilated, but sometimes contracted, and the vision is usually 
more or less impaired. Death is often preceded by convulsions, 
and paralysis. 
In regard to the operation of tobacco, Dr. Pereira remarks, 
that it resembles that of Lobelia inflata. With foxglove, to- 
bacco agrees in several particulars, especially in that of enfee- 
bling the action of the vascular system, though its power in this PHYSIOLOGICAL EFFECTS. 
425 
respect is inferior to that of foxglove. In its capability of 
causing relaxation and depression of the muscular system, and 
trembling, tobacco surpasses foxglove j as it does, also, in its 
power of promoting the secretions. From belladonna, stramo- 
nium, and hyoscyamus, it is distinguished by causing contrac- 
tion of the pupil, both when applied to the eye and when taken 
internally in poisonous doses; and also by the absence of de- 
lirium and of any affection of the parts about the throat. (Mat. 
Med., vol. ii, p. 494.) 
Administered in the form of clyster, tobacco has in several 
instances caused death. In a case of this kind quoted by Dr. 
Christison, in which an enema prepared by boiling about an 
ounce of tobacco for fifteen minutes in water was administered 
by the advice of a quack to an individual laboring under ob- 
stinate constipation, the patient was seized in two minutes 
afterwards with vomiting, violent convulsions, and stertorous 
breathing, and died in three-quarters of an hour. 
So, also, the external application of tobacco to abraded sur- 
faces, and even to the healthy skin, has been attended with 
violent symptoms, and even death. In a case of this kind, in 
which a man applied to himself a decoction of tobacco for the 
cure of an eruptive disease, death took place in three hours, 
with the usual symptoms of tobacco poisoning. (See Amer. 
Jour. Med. Sci., Jan., 1865, p. 268.) 
Even the smoking of tobacco has been known to produce 
dangerous, and even fatal results. Dr. Marshall Hall relates 
the case of a young man, who, having smoked two pipes of 
tobacco, was seized with nausea, vomiting, syncope, stupor, 
stertorous breathing, and general spasms: after a time he re- 
covered. Gmelin mentions two cases of death, caused in one 
instance by the smoking of seventeen, and in the other of 
eighteen pipes of tobacco, at a sitting. 
A most remarkable case of poisoning by nicotine in its pure 
state, occurred in Belgium, in 1850, for which the Count de 
Bocarme was condemned to death, the person murdered being 
his brother-in-law, Gustave Fougnies. An unknown quantity 
of the poison was forcibly administered, and it is believed that 
death took place within five minutes afterwards. Nicotine was 426 
NICOTINE. 
detected in small quantity by M. Stas in the mouth, throat, 
stomach, liver, and spleen of the deceased, and also in the floor 
near which the act was committed. (Orfila’s Toxicology, vol. 
ii, p. 498.) The only other related case of poisoning by this 
substance in its pure state, occurred in London, in 1858, and 
death took place in from three to five minutes after the poison 
had been taken. In this case, a small quantity of the poison 
was detected by Dr. Taylor in the contents of the stomach. 
In this connection, we may briefly relate the following ex- 
periments, in regard to the action of nicotine in its pure state. 
One drop of the poison placed in the mouth of a full-grown 
cat, produced immediate prostration, continued convulsive move- 
ments of the extremities, and death in seventy-eight seconds after 
the poison had been administered. In another case, a small 
drop was placed on the tongue of a cat. In ten seconds, the 
animal fell on the right side perfectly prostrated, then had con- 
vulsive movements of the legs, voided urine, and died in two 
minutes and a half. A third cat, to which a similar quantity 
had been administered, fell in about twelve seconds, had violent 
convulsions of the extremities, and was dead in seventy-five 
seconds after taking the poison. 
Period when Fatal.—ln fatal poisoning by tobacco, death 
does not usually occur until after some hours, but it may take 
place within a very much shorter period. In a case in which 
about an ounce of crude tobacco had been swallowed, death 
took place in about seven hours; while in another, an unknown 
quantity of snuff administered in whisky, proved fatal in about 
one hour. 
Most of the reported cases of death from tobacco have been 
occasioned by its use in the form of clyster. M. Tavignot re- 
lates a case in which an injection prepared by mistake with 
nearly two ounces of tobacco (GO grammes), instead of nine 
grains and a quarter (60 centigrammes), was administered to a 
stout man, aged fifty-five years. In seven or eight minutes 
afterwards, he was seized with stupor, headache, paleness of 
the face, pain in the abdomen, indistinct articulation, and con- 
vulsive tremors, at first of the arms, then of the whole body. 
These symptoms were soon followed by extreme prostration and PATHOLOGICAL EFFECTS. 
427 
slow laborious breathing, and then coma, which terminated 
fatally in about eighteen minutes after the injection had been 
administered. (Gazette Med. de Paris, Nov., 1840, p. 763.) 
In a case quoted by Dr. Beck (Med. Jur., vol. ii, ,p. 878), a 
female affected with worms used an enema of tobacco, and was 
soon seized with violent convulsions, and died from its effects 
fifteen minutes afterwards. 
Fatal Quantity,—ln most of the fatal cases of poisoning 
from the swallowing of tobacco, the quantity taken could not be 
accurately determined. In a case reported by Mr. Skae, a man 
who had swallowed a large mouthful of crude tobacco, became 
suddenly insensible, motionless, and relaxed, with contracted 
pupils, and a scarcely perceptible pulse. These symptoms were 
followed by convulsions, loud cries, dilated pupils, active vom- 
iting and purging, and death by syncope. (Stille’s Mat. Med., 
vol. ii, p. 298.) 
Administered in the form of enema, tobacco has proved 
fatal in comparatively small quantity. Thus, several instances 
are reported in which a decoction of a drachm exhibited in this 
manner caused death. In one of these, quoted by Dr, Christi- 
son, death took place in thirty-five minutes. In a case cited 
by Dr. Pereira'(Mat. Med., ii, 494), an injection containing 
only half a drachm was followed by fatal results. 
Treatment.—This consists in the speedy removal of the 
poison, in case it has been swallowed, from the stomach; and 
the subsequent exhibition of stimulants. Animal charcoal, tan- 
nic acid, and an aqueous solution of iodine in iodide of potas- 
sium have been advised as chemical antidotes. Opium may 
sometimes be found useful, to allay the excessive vomiting. 
Post-mortem Appearances.—These are subject to great 
variation. In a case cited by Dr. Taylor (On Poisons, p. 747), 
in which something less than an ounce of crude tobacco had 
been swallowed and death occurred in about seven hours, the 
following appearances were observed forty hours after death. 
The substance of the brain and the upper part of the spinal 
marrow were somewhat congested; the heart was empty, small, 
and contracted; and the liver and kidneys much congested. 
The mucous membrane of the stomach presented several red 428 
NICOTINE. 
patches. The intestines were contracted throughout and con- 
tained only a mucus fluid tinged with blood; the mucous mem- 
brane Avas of a red color, partially abraded, and full. The 
bladder was contracted and empty. The blood throughout the 
body was dark colored and liquid. 
In a case in which an enema prepared with about an ounce 
of tobacco proved fatal in three-quarters of an hour, the only 
abnormal appearances observed two days after death, were a 
gorged condition and redness of the inner and outer coats of the 
large and small intestines, and patches of extravasation in some 
parts of the mucous membrane, together with an empty state 
of the heart and of the blood vessels of the abdomen. The 
stomach and brain were natural. 
Chemical Properties. 
General Chemical Nature.—Nicotine, when perfectly 
pure, is a transparent, colorless, oily liquid, having a strong 
alkaline reaction, and a density of about PO4B. Its odor is 
usually described as acrid, unpleasant, and resembling some- 
what that of tobacco ; this is true of most samples as met with 
in the shops, but when perfectly pure, it has, as remarked by 
Otto, a rather pleasant, ethereal odor. The odor may be per- 
ceived, but is not characteristic, in a few drops of a pure 
50,000 th aqueous solution of the poison. 
Nicotine has a pungent, acrid taste, even when highly dilu- 
ted, producing a peculiar sensation in the throat and air pas- 
sages. It slowly distills at about 295°, and boils at about 470° 
F., recondensing for the most part unchanged; in an atmos- 
phere of hydrogen gas, it may be distilled without any decom- 
position. It imparts a transient greasy stain to white paper, 
and burns with a white, smoky flame. On exposure to the air, 
nicotine slowly becomes yellow, then brownish and thick, being 
finally converted into a resinous mass. 
Solubility.—Nicotine is freely soluble in all proportions in 
water; it is also soluble in alcohol, ether, chloroform, the fixed 
oils, and in oil of turpentine. By the use of some of these 
latter solvents, the alkaloid may be extracted to a greater or SPECIAL CHEMICAL PROPERTIES. 
429 
less extent, from its solution in water. For this purpose, ether 
has usually been employed, but this liquid is inferior in this 
respect to chloroform, as may be seen from the following' facts. 
1. Extraction hy Ether.—When one volume of a 100 th aque- 
ous solution of nicotine is agitated with five volumes of absolute 
ether, and the latter liquid, after repose, decanted, the aqueous 
solution yields with reagents somewhat better reactions of the 
presence of nicotine than a pure 500 th solution of the alkaloid; 
thus showing that the ether extracted less than four-fifths of the 
vegetable base. When a 100 th solution is agitated with twenty- 
five volumes of ether, the aqueous liquid is reduced to about a 
1,200 th solution. Experiments made with aqueous solutions of 
the chloride of nicotine, by decomposing the salt with caustic 
potash and then extracting with absolute ether, gave results 
similar to those just mentioned; as did also experiments in 
which concentrated commercial ether was employed as the ex- 
tracting liquid. 
2. By Chloroform.—When a 100 th aqueous solution of pure 
nicotine is agitated with five volumes of pmre chloroform, and 
the latter carefully decanted, the former liquid is reduced to 
about a 4,000 th solution of the alkaloid. So, also, under like 
circumstances, a I,oooth aqueous solution is reduced to about 
a 40,000 th solution. These experiments show that under these 
conditions, chloroform separates about 39-40ths of the alkaloid. 
Special Chemical Properties.—lf a drop of nicotine be 
placed in a watch-glass, and this covered by a similar, inverted 
glass containing a small drop of either hydrochloric or nitric 
acid, the glasses become filled with white fumes. These fumes 
are not so dense as those obtained from conine under similar 
circumstances; nor are they, as in the case of conine, attended 
with the formation of crystals. When the pure alkaloid is 
treated directly with concentrated hydrochloric acid, it yields a 
syrupy liquid, without the formation of crystals; with nitric 
acid, it yields a reddish syrupy fluid. When the alkaloid is 
touched with concentrated sulphuric acid, it undergoes little or 
no change, until the mixture is heated, when it acquires a 
brownish color. It need hardly be added, that these reactions 
in themselves are not characteristic of this alkaloid. 430 
NICOTINE. 
A pure aqueous solution of nicotine is colorless, lias the pe- 
culiar odor and taste of the alkaloid, and an alkaline reaction. 
When such a solution is distilled, the alkaloid passes over with 
the vapor of water. Nicotine readily unites with acids, forming 
salts, some of which are readily crystallisable. 
The salts of nicotine have the peculiar taste of the alkaloid, 
but are destitute of odor. They are mostly soluble in water, 
and alcohol, but insoluble in ether. Their aqueous solutions 
lose part of the alkaloid upon evaporation, and are decomposed 
by the mineral alkalies, evolving the odor of nicotine. When 
such an alkaline mixture is agitated with chloroform, this liquid, 
after decantation and evaporation, leaves the extracted alkaloid 
in the form of oily drops or streaks. On distilling a solution of 
a salt of nicotine which has been treated with excess of caustic 
potash or soda, the free alkaloid will be found in the distillate, 
together with any ammonia that may have been present in the 
mixture. If the distillate thus obtained, be neutralised with 
oxalic acid, then gently evaporated to dryness, and the residue 
treated with alcohol, this liquid will dissolve the oxalate of 
nicotia, produced by the neutralisation, while any oxalate of 
ammonia present will remain, it being insoluble in this men- 
struum. On now evaporating the alcoholic solution to dryness, 
the oxalate of nicotine may be obtained in its pure state. 
In the following examinations of the limit of different tests 
for nicotine when in solution, the pure, colorless alkaloid was 
dissolved in distilled water. The fractions indicate the frac- 
tional part of a grain of the alkaloid in solution in one grain 
of water. The results, except when otherwise stated, refer to 
the behavior of one grain of the solution. 
1. Bichloride of Platinum. 
This reagent throws down from somewhat strong aqueous 
solutions of nicotine and of its salts, a yellow precipitate of the 
double chloride of platinum and nicotine, having, according to 
Ortigosa, the composition 
itate produced from free aqueous solutions of the alkaloid by 
the pure reagent, is at first amorphous, but after a little time it BICHLORIDE OF PLATINUM TEST. 
431 
becomes, in part at least, crystalline. But when from solutions 
of the chloride of nicotine, or if the reagent contains free hy- 
drochloric acid, the precipitate immediately assumes the crys- 
talline form. From more dilute solutions of the alkaloid or of 
its salts, the precipitate separates only after a time, and then 
in the crystalline state ; its separation is much facilitated by 
stirring the mixture. The precipitate, in its crystalline form, 
dissolves but slowly in large excess of hydrochloric acid; in its 
amorphous condition, however, it is much more readily sol- 
uble. It is insoluble in acetic acid, alcohol, and in ether, but 
soluble in excess of free nicotine. The crystals are permanent 
in the air. 
1. yJi grain of nicotine, in one grain of water, yields with the 
reagent a quite good deposit of orange-yellow crystals, 
2. 5-5-0- grain: after a little time, the mixture becomes turbid, 
Plate VI, fig. 1. 
and ultimately yields small crystals of the double salt. If 
the mixture be stirred with a glass rod, it very soon yields 
granular streaks on the dish or glass-slide over the path 
of the rod ; and in a little time, a quite satisfactory crys- 
talline deposit. 
Bichloi’ide of platinum also produces yellow crystalline pre- 
cipitates in solutions of potash and ammonia; but the forms of 
the crystals thus produced are wholly different from those of 
the double nicotine salt. (Compare Plate I, fig. 1.) The ap- 
plication of some of the tests, such as the iodine reagent, which 
produce precipitates with nicotine but none with the inorganic 
alkalies, would also readily distinguish the former from the 
latter. If the solution under examination has been prepared by 
extraction from a suspected mixture by chloroform or ether, 
then a mineral alkali could not be present, since they are insol- 
uble in each of these liquids. 
This reagent also throws down yellow precipitates from solu- 
tions of most of the other alkaloids, some of which, like the 
nicotine deposit, are crystalline; but in no instance have the 
crystals the same microscopic forms as those obtained from 
somewhat strong solutions of nicotine. The production of this 
crystalline precipitate, together with the odor and physical state 432 
NICOTINE. 
of nicotine, readily serve to distinguish this alkaloid from all other 
substances. 
2. Corrosive Sublimate. 
This reagent produces in strong solutions of nicotine a copi- 
ous, white, curdy precipitate, which soon acquires a yellow color 
and deposits beautiful groups of colorless crystals, which are 
permanent in the air. The precipitate produced from some- 
what dilute solutions of the alkaloid, remains white, and after a 
time yields the same crystals as from strong solutions. These 
precipitates are readily soluble in hydrochloric and acetic acids. 
The white precipitate is soluble in chloride of ammonium, from 
which after a time it is redeposited; the yellow precipitate is 
immediately decolorised by chloride of ammonium, and, in part 
at least, dissolved, but after a time it separates in the form of 
a white powder. The precipitates are to a greater or less ex- 
tent dissolved upon the application of heat, but again repro- 
duced as the solution cools. 
1. x4o grain of nicotine, in one grain of water, yields a copi- 
ous, white precipitate, which in a little time becomes yel- 
low and yields a mass of large groups of crystals, Plate 
VT, fig. 2. These crystals are especially beautiful under 
polarized light. 
2. mTo grain, yields a rather copious, dirty-white precipitate, 
which soon deposits colorless crystals. 
3. r,(Too grain: in a few seconds, the mixture becomes turbid, 
and soon there is a quite good, white, flocculent precipi- 
tate, which after a time yields crystals having the same 
forms as illustrated above. If upon the addition of the 
reagent, the mixture be stirred with a glass rod, it imme- 
diately yields streaks on the bottom of the watch-glass 
over the path of the rod, and soon innumerable opake 
granules and granular masses appear, which after a little 
time present the appearances illustrated in the lower por- 
tion of the above figure. 
4. 27x0-0 grain: if the mixture be stirred and allowed to stand, 
it yields after some time, quite a number of large crystal- 
line groups. CARBAZOTIC ACID TEST. 
433 
Although corrosive sublimate also produces white precipi- 
tates with ammonia and various inorganic substances, as well 
as with most of the alkaloids and many other kinds of organic 
matter, yet all these deposits, unlike that from nicotine, remain 
amorphous, except the precipitate from strychnine, and in this 
case, the crystals, which are usually obtained with difficulty, 
are always of a wholly different form from those produced by 
the nicotine deposit. (Compare Plate XI, fig. 2.) It may be 
added, that the nicotine precipitate is very readily soluble in 
excess of acetic acid, whereas the strychnine compound is sol- 
uble with difficulty in this acid. 
We have found, in repeated experiments, that the precipi- 
tate produced by this reagent from quite impure solutions of 
nicotine, will after a time yield characteristic crystals, even in 
the midst of a dense deposit of foreign matter. Nevertheless, 
it must be borne in mind, that under these circumstances, the 
precipitate may fail to crystallise. In applying this test to 
somewhat complex organic liquids, the precipitate should be 
stirred and allowed to stand for at least an hour, with the occa- 
sional addition of very small quantities of pure water to prevent 
the deposit becoming dry, before it is fully concluded that crys- 
tals will not form. 
This is the most valuable test yet known for the detection 
of nicotine, when in solution. 
3. Carbazotic Acid. 
An alcoholic solution of carbazotic, or picric, acid throws 
down from aqueous solutions of nicotine, a yellow, amorphous 
precipitate, which soon becomes a mass of crystalline tufts. It 
is necessary to use large excess of the reagent, otherwise either 
uo deposit will form, or if produced it will soon disappear. 
1- teo grain of nicotine, yields an immediate, yellow or green- 
ish-yellow precipitate, which soon becomes a mass of 
groups of yellow, crystalline tufts, Plate VI, fig. 3. 
2. rroVo grain : a rather copious precipitate, which soon crys- 
tallises. 
3- roarro grain, yields a very good, crystalline precipitate. 
28 434 
NICOTINE. 
4. grain, yields a just perceptible precipitate. 
This reagent also throws down from solutions of the inor- 
ganic alkalies, and of several of the other alkaloids, besides 
nicotine, yellow precipitates which become crystalline. But, by 
the aid of the microscope, the crystallised nicotine compound 
may generally be readily distinguished from all of these deposits 
except that produced from very strong solutions of soda (Plate 
I, fig. 6), which has frequently much the same crystalline form 
as that assumed by the nicotine salt. Any doubt as to the true 
nature of the deposit, may, of course, be readily removed by 
the application of other reagents. 
This reagent will often produce crystals with only the 10,- 
000 th part of a grain of nicotine, in one grain of water, in the 
presence of foreign organic matter. But in mixtures of this 
kind, the formation of crystals is more readily interfered with 
than in the application of the preceding reagent. 
4. lodine in lodide of Potassium. 
This reagent may be prepared by dissolving three grains of 
iodide of potassium in one fluid drachm of distilled water, and 
then adding one grain of pure iodine. A drop or two of this 
mixture throws, down from solutions of nicotine and of its salts, 
a reddish-brown, brownish-yellow or yellowish, amorphous pre- 
cipitate, its exact color depending somewhat upon the strength 
of the alkaloidal solution, and also upon the quantity of reagent 
added. After a little time, the precipitate may entirely disap- 
pear ; but it is immediately reproduced upon further addition 
of the reagent. The precipitate is readily soluble in caustic 
potash and in alcohol. 
1. y-jnr grain of nicotine, in one grain of water, yields a very 
copious deposit. 
2. rroWo grain: a copious, reddish-brown precipitate. 
3. rojoo grain, yields a good, reddish-yellow deposit. 
4. 2 5,0d0 grain: a quite distinct, greenish-yellow precipitate. 
5. s-oTFoT grain: a quite good turbidity. 
6. vtoVoo grain: a very obvious turbidity. 
7. yroVcTo grain, yields a perceptible cloudiness. CHLORIDE OF GOLD TEST. 
435 
As a solution of iodine in iodide of potassium causes no 
precipitate in solutions of tlie inorganic alkalies and has its 
color immediately discharged by them, it readily serves to dis- 
tinguish nicotine from these substances. But, as the reagent 
produces with most of the alkaloids and many other substances, 
precipitates similar to that from nicotine, it has no positive 
value, for the detection of this alkaloid, further than to confirm 
the reactions of other tests. 
From the fact that the limit of the reaction of this reagent 
exceeds that of either of the other tests for nicotine, it is obvi- 
ous that should this test fail to produce a precipitate, in a solu- 
tion suspected to contain nicotine, it would be fruitless to apply 
any of the other tests to the same solution, unless possibly there 
should be some substance present that interfered with the reac- 
tion of this reagent. 
5. Ter chloride of Gold. 
• This reagent produces in aqueous solutions of nicotine a yel- 
low, amorphous precipitate, which is nearly insoluble in acetic 
and hydrochloric acids, but soluble, to a clear solution, in ex- 
cess of the caustic alkalies. 
1. y'o o grain of nicotine, yields an immediate, copious, yellow 
precipitate, which remains amorphous; the deposit is not 
entirely soluble in several drops of strong acetic acid. If 
several grains or more of the nicotine solution be precipi- 
tated by the reagent and the mixture then heated, the 
precipitate dissolves to a beautiful purple solution. 
2. rrFoF grain, yields a good, yellow deposit, which is slowly 
soluble in a few drops of a strong solution of potash. If 
the precipitate produced from several grains of the solu- 
tion be heated in the mixture, it dissolves, and is repro- 
duced unchanged as the mixture cools. 
3. sToVo grain: an immediate, greenish-yellow precipitate, which 
soon increases to a quite good, dirty-yellow deposit; the 
precipitate is readily soluble in a drop of potash solution. 
4* ToTtToo grain, yields a good, yellowish precipitate, which im- 
mediately disappears upon the addition of an alkali. 436 
NICOTINE. 
sTTTo'o grain : in a few moments, a distinct turbidity, and in 
a little time, a quite satisfactory precipitate. 
G. yoTSiro grain : in a little time, the mixture becomes turbid, 
and soon there is a quite distinct deposit. 
itates with most of the alkaloids and various other substances. 
Tercliloride of gold also produces yelloAV, amorphous precip- 
6. Bromine in Bromohydric Acid. 
Aqueous solutions of nicotine yield with a strong aqueous 
solution of bromohydric acid saturated with bromine, a yellow 
amorphous precipitate, which in a little time disappears. 
1. ywo grain of nicotine, yields a copious, bright yellow precip- 
itate, which soon disappears, but is reproduced upon fur- 
ther addition of the reagent. 
2. rroVo grain: a rather copious precipitate. 
3. yWo grain, yields a very good, greenish-yellow deposit, 
which soon dissolves, and is not reproduced upon further 
addition of the reagent. 
4. rovWo grain, yields a slight turbidity. 
The reaction of this reagent is common to most of the alka- 
loids and many other organic compounds. The reagent pro- 
duces no precipitate and has its color discharged, when added 
to solutions of the caustic alkalies. 
7. Tannic Acid. 
Tannic acid produces in aqueous solutions of nicotine a 
white, amorphous precipitate, which readily dissolves to a clear 
solution on the addition of a small quantity of hydrochloric 
acid, but is reproduced upon further addition of the acid, and 
is then insoluble in large excess. The precipitate is readily 
soluble in acetic and nitric acids, without being reproduced upon 
further addition of the acid. 
1. Yifo grain of nicotine, in one grain of water, yields a copious 
precipitate. 
2. rrooo grain : a good, bluish-white deposit. 
3. ro,ij“oo grain: the mixture becomes slightly turbid. SEPARATION FROM ORGANIC MIXTURES. 
437 
This reagent also throws down white precipitates from solu- 
tions of very many other substances. The behavior of the 
nicotine precipitate with hydrochloric acid, however, is some- 
what peculiar. 
Other Reactions of Nicotine.—As nicotine has strong basic 
properties, it, like the caustic alkalies, precipitates the oxides 
of many of the metals from solutions of their salts. Nitrate 
of suboxide of mercury throws down from somewhat strong- 
solutions of the free alkaloid, a copious, dirty-yellow precip- 
itate, which almost immediately becomes brown, then nearly 
black: this transition of color is due to the successive reduction 
of the precipitated oxide of mercury. With one grain of a 
5,000 th solution of the alkaloid, this reagent produces a rather 
good, dirty-white precipitate. 
Sulphate of copper produces with aqueous solutions of the 
alkaloid, when not too dilute, a bluish, flocculent precipitate of 
the oxide of copper, which is insoluble in excess of nicotine. 
The statement of some writers that this precipitate dissolves in 
excess of the pure alkaloid to a blue solution, similar to that 
formed by ammonia, is certainly erroneous. Solutions of salts 
of lead, silver, nickel, cobalt, and several other metals, also 
produce precijiitates from somewhat strong solutions of the 
alkaloid. A 100 th solution of the poison yields with nitrate of 
silver a quite good, white precipitate, which but very slowly 
darkens upon exposure to sunlight. 
Solutions of nicotine, even when concentrated, fail to yield a 
precipitate with either sulphocyanide of potassium, the chromates 
of potash, ferro- or ferri-cyanide of potassium, or gallic acid. 
Separation from Organic Mixtures. 
In suspected poisoning by tobacco, before proceeding to the 
chemical examination for nicotine, the analyst should carefully 
examine the suspected mixture or contents of the stomach, for 
the presence of tobacco in its solid state. Any portions of the 
plant thus found, separated from all adhering matter, should be 
carefully examined, by means of the microscope if necessary, 438 
NICOTINE. 
in regard to their botanical characters, then digested at a gentle 
heat in acidulated water, and the solution examined in the man- 
ner just to be described. 
Suspected Solutions and Contents of the Stomach.—The mix- 
ture submitted for examination, diluted with distilled water if 
necessary, is slightly acidulated with acetic acid and digested 
for some little time at a moderate heat; it is then allowed to 
cool, the liquid strained through muslin, the solids on the mus- 
lin washed with water and well pressed, and the united strained 
liquids filtered. The clear liquid is now evaporated to a small 
volume on a water-bath, then mixed with about an equal vol- 
ume of strong alcohol, and the mixture gently warmed for some 
minutes, with constant stirring; the cooled liquid is again fil- 
tered, and the filtrate evaporated on a water-bath to very near 
dryness. Any nicotine originally present will now be in the 
residue, in the form of acetate of the alkaloid. 
This residue is gently warmed with about a fluid drachm or 
even less of pure water, the mixture thoroughly stirred, trans- 
ferred to a wet paper filter, and the filtrate collected in a stout 
test-tube. The contents of the tube are now rendered alkaline 
by a few drops of caustic soda or potash, when the nicotine will 
be liberated from its saline combination, and perhaps emit its 
peculiar odor. 
The mixture is now violently shaken for some minutes with 
about two volumes of chloroform or about five volumes of ether, 
and this mixture allowed to repose, until the fluids have com- 
pletely separated. In case chloroform has been used as the 
solvent of the liberated alkaloid, the supernatant aqueous fluid 
is removed by means of a pipette, the chloroform carefully de- 
canted into another, perfectly dry test-tube, and from this into 
a large watch-glass. By these decantations, any globules of 
water which may have escaped removal by the pipette, may, 
by care, be made to adhere to the sides of one or other of the 
test-tubes. Should, however, globules of the alkaline aqueous 
fluid have passed along with the chloroform into the watch- 
glass, these must be removed before the latter liquid is evap- 
orated to dryness, otherwise the residue will contain a trace of 
soda or potash, which might subsequently interfere with some SEPARATION FROM ORGANIC MIXTURES. 
439 
of the tests for nicotine. The alkaline aqueous liquid removed 
by the pipette, is now washed with something less than its own 
volume of fresh chloroform, and this, after repose, decanted and 
added to the first chloroform extract. If ether has been em- 
ployed as the solvent of the alkaloid, the aqueous fluid is 
agitated a second time with two or three volumes of ether, 
and the united ethereal liquids carefully collected in a large 
watch-glass. 
The contents of the watch-glass are now allowed to evapo- 
rate spontaneously, in a cool place, when any nicotine present 
will be left in the form of oily drops or streaks, having the 
peculiar odor of the alkaloid, especially upon the application of 
a very gentle heat. As the residue from extracts of this kind 
has frequently a strong animal odor, this may more or less con- 
ceal that of the poison. 
If the residue thus obtained, indicates the presence of a 
comparatively large quantity of the alkaloid, the contents of 
the watch-glass are stirred with about half a drachm or more 
of pure water, and the mixture, if it contains white, flocculent 
masses or if turbid, transferred in small portions to a very small 
moistened filter; when the whole of the fluid has passed through, 
the filter is washed with a few drops of water and this collected 
with the first filtrate. If, on the other hand, the chloroform 
residue fails to reveal any distinct evidence of the presence of 
the alkaloid, only a few drops of water are used for its solution. 
A drop of the clear liquid, transferred by means of a pipette 
to a watch-glass, may now be treated with a small drop of cor- 
rosive sublimate solution, the mixture allowed to stand quietly 
for some little time, and then examined by the microscope. If 
this examination indicates the presence of nicotine, other por- 
tions of the clear liquid may be examined by bichloride of 
platinum, carbazotic acid, and any of the other tests for this 
alkaloid. If, however, the corrosive sublimate mixture fails to 
yield crystals, it should be stirred with a glass rod, and allowed 
to stand half an hour or longer. Should it still fail to yield any 
evidence of the presence of the poison, the original liquid may 
be concentrated, and then a drop examined by this reagent. 
On the other hand, should this test as first applied, indicate the 440 
NICOTINE. 
presence of much foreign matter, the original solution is again 
extracted by chloroform, this liquid evaporated to dryness, and 
the residue treated as before. 
By the method now considered, nicotine was detected in 
very notable quantities in the stomachs of the first two cats 
before referred to [ante, p. 426), each of which was killed by 
a single drop of the alkaloid placed in the mouth of the animal. 
And by it we have also obtained perfectly satisfactory evidence 
of the presence of the poison in an ounce of a very complex 
organic mixture, to which only the 100 th part of a grain of the 
alkaloid had been added. 
From the Tissues.—For the separation of absorbed nicotine 
from the tissues, the solid organ, such as the liver, spleen or 
lungs, is cut into very small shreds, then made into a thin 
paste with water, the mixture acidulated with acetic acid, and 
digested, with frequent stirring, for some time at a very gentle 
heat. The cooled mixture is then treated after the same 
manner as before described, for the examination of suspected 
solutions. 
As the quantity of the alkaloid present in the tissues, in 
poisoning by this substance, is at most extremely small, the resi- 
due obtained from the chloroform extract, should be treated with 
only a few drops of water and great care exercised in the prep- 
aration of this solution for the application of the different tests. 
M. Stas was, perhaps, the first to show that nicotine was 
absorbed and might be separated from the tissues in its un- 
changed state. The same fact was also pointed out about the 
same time by Orfila. This observer cites several instances 
(Toxicologie, 1852, ii, 493), in which he obtained the poison 
from the liver and spleen of dogs killed by from fifteen to 
twenty drops of the alkaloid. 
From the Flood.—Nicotine, when present in the blood, may 
be recovered by acidulating the liquid with about five drops of 
strong acetic acid for each ounce of fluid, and agitating it in a 
closed bottle with about its own volume or more of a mixture 
of equal parts of water and alcohol, until the whole becomes 
perfectly homogeneous. The mixture is then digested at a mod- 
erate heat, with frequent stirring, until the albuminous matter SEPARATION FROM ORGANIC MIXTURES. 
441 
present collects into small, brownish flakes. The cooled liquid 
is strained through wet muslin, and the solid residue washed 
and strongly pressed. If the liquid is still turbid, it is passed 
through the strainer a second or even a third time. The fluid 
is now evaporated at a moderate heat on a water-bath to about 
half its volume, and while still warm, mixed with a little strong 
alcohol, and the reddish-brown, coagulated matter removed by 
a muslin Alter. When the quantity of blood operated upon is 
comparatively small, the strained liquid thus obtained is usually 
clear and has only a slight yellow color • but when a large 
amount of the fluid is examined, the strained liquid is generally 
turbid and highly colored. Under these circumstances, it may 
be passed through a wet paper Alter. 
The liquid is now slowly evaporated on a water-bath to near 
dr yness. If during the concentration, much solid matter sepa- 
rates, it should be removed by a small Alter. The nearly dry 
residue is stirred with about half a drachm of water, the solu- 
tion Altered, the Altrate rendered alkaline by caustic soda, and 
extracted by chloroform in the usual manner. The chloroform 
residue is well stirred with a few drops of water, and the liquid 
carefully separated from any flakes of animal matter present, 
either by means of a pipette or by a very small Alter. The 
liquid is then examined by the ordinary reagents. 
By the above method, perfectly satisfactory evidence of the 
presence of nicotine was obtained from one ounce of healthy 
blood to which the 100 th part of a grain of the alkaloid had 
been purposely added—the dilution being one part of the poison 
in about 50,000 parts of the fluid. 
In the case of the second of the three cats before referred 
to—in which a small drop of nicotine proved fatal in two min- 
utes and a half—seven fluid drachms of blood were recovered 
from the body immediately after death ; Ave drachms of the 
liquid were then treated after the above method, and the Anal 
aqueous solution reduced to three drops. One drop of this mix- 
ture when treated with corrosive sublimate, gave, after a little 
time, perfectly satisfactory evidence of the presence of nico- 
tine, it yielding about twenty large groups of crystals similar to 
those shown in Plate VI, Ag. 2. A second drop, treated with 442 
NICOTINE. 
carbazotic acid, also furnished a fine deposit of characteristic 
crystals. The third drop, when treated with bichloride of pla- 
tinum, gave a slight precipitate, but no crystals were obtained. 
From the third cat—which was killed in seventy-five seconds 
by a drop of the alkaloid—ten fluid drachms of blood were 
obtained with the greatest possible speed and care, and then 
treated as before shown, excepting that a drop of sulphuric acid 
was used as the acidifying agent and ether for the extraction of 
the poison. The final solution, when reduced to two drops, gave 
with corrosive sublimate, and carbazotic acid, perfectly satisfac- 
tory evidence of the presence of the alkaloid; but at the same 
time, indicated that it was present in smaller quantity than in 
the preceding case. This case shows the extreme rapidity with 
which this poison may enter the circulation. 
It is a singular fact, that the chloroform and ether residues in 
both the foregoing cases possessed in a very marked degree, the 
peculiar ethereal odor of the pure alkaloid administered; whilst 
in another case, in which the poisoning was occasioned by an 
extract of tobacco, the chloroform residue obtained in precisely 
the same manner, had the acrid tobacco odor usually observed 
in commercial samples of nicotine. 
In the examination of organic mixtures for the separation of 
nicotine, it has heretofore been usual for analysts to advise either 
oxalic, tartaric, or sulphuric acid as the acidifying agent. But, 
we have not found that either of these acids possess, for this 
purpose, any advantage over acetic acid, and on the whole pre- 
fer the latter. If sulphuric acid be employed, no more should 
be added than just sufficient to give the mixture a very slight 
acid reaction. It may here be remarked that anhydrous acetate 
of nicotine is more or less volatilised by continued heating on a 
water-bath 5 and, also, that this salt is soluble to a notable ex- 
tent in ether. 
For the separation of the liquid alkaloids, nicotine and co- 
nine, from organic mixtures, the following method, based upon 
the volatility of these alkaloids, has been proposed. The mix- 
ture, acidified with from ten to twenty grains of oxalic or 
tartaric acid, is treated with about twice its weight of strong CONINE. 
443 
alcohol and heated to about 150° F., the cooled liquid strained, 
the residue washed with alcohol and pressed. The extract thus 
obtained, is concentrated at a gentle heat, the resulting aqueous 
solution separated by filtration from any insoluble matter pres- 
ent, then rendered alkaline by caustic potash or soda, and dis- 
tilled to very near dryness, in a retort provided with a proper 
receiver: the residue in the retort may be treated with a little 
water and again distilled, the product being received with the 
first distillate. The alkaloid will now be present in the distillate. 
This liquid may either be agitated with several volumes of 
ether, the ethereal solution decanted, and the operation repeated 
with fresh portions of ether, until a drop of this fluid upon 
spontaneous evaporation no longer leaves a residue of the alka- 
loid ; the mixed ethereal solutions are then evaporated sponta- 
neously at a low temperature, and the residue placed for a few 
moments over sulphuric acid under a glass receiver. Or, the 
distillate may be neutralised with oxalic acid, concentrated at 
a low temperature to a small volume, the residual liquid ren- 
dered alkaline by potash or soda, and the alkaloid then ex- 
tracted by ether. Chloroform might, of course, be substituted 
for ether in either of these processes. 
Since this method, by distillation, is always attended with a 
quite notable loss of the alkaloid, it is not as well adapted for 
the detection of very minute quantities of the poison, as the 
method before considered. 
Section II.—Conine. (Conium Maculatum.) 
History.—Conine, known also as conicine, conia, and coni- 
cina, is the active principle of Conium maculatum, or common 
hemlock. It exists, in the form of an organic salt, perhaps in 
all parts of the plant, but is most abundant in the fruit. The 
relative quantity of the alkaloid present in the plant varies 
with the growth of the latter: according to Geiger, six pounds 
of the fresh, green, unripe seeds, or nine pounds of dry, ripe 
seeds, yield one ounce of conine. This alkaloid was first ob- 
tained as an impure sulphate by Giseke, in 1827 ; Geiger, in 444 
CONINE. 
1831, obtained it in its pure state, and described some of its 
properties and effects upon animals. Its effects upon animals 
were more fully examined, in 1835, by Dr. Cbristison. In re- 
gard to its composition, four different formulae have been ad- 
vanced, namely: Cl 2H14NO, by Liebig; Cl 7H17N, by Blyth; 
Cl 6H16N, by Ortigosa; and Cl 6H15N, by Gerhardt. The formula 
of Gerhardt is the one usually adopted. 
Preparation.—Conine may be obtained, according to Dr. 
Christison, by exhausting the ripe seeds of hemlock with alco- 
hol, distilling off the alcohol, mixing the residual syrup with an 
equal volume of water and a little hydrate of potash, distilling 
the mixture in a chloride of calcium-bath and collecting the dis- 
tillate in a proper receiver. The conine passes over with the 
water and yields an aqueous solution of the alkaloid, containing 
oily drops floating upon its surface. If the conine contains am- 
monia, this may be removed by placing the mixture in vacuo 
over sulphuric acid, when the gas will escape in the form of 
bubbles. 
Conine is a most virulent poison, almost equaling in the 
activity of its action hydrocyanic acid. As yet there seems to 
be only a single recorded case of poisoning in the human sub- 
ject, by this substance in its pure state (Arch, der Pharma., 
Sept., 1861, p. 257); but, poisoning by hemlock is of not un- 
frequent occurrence. Most of these cases have resulted from 
the mistaking of hemlock for other plants. 
Symptoms.—The symptoms occasioned by hemlock are sub- 
ject to considerable variation, as may be seen from the following 
cases. In an instance related by Dr. Haaf, a soldier having 
eaten some soup containing hemlock leaves, soon fell asleep : in 
an hour and a half afterwards, he was insensible and breathed 
with difficulty; his pulse was slow and hard; the extremities 
cold; and the face bluish, and distended with blood, like that 
of a person strangulated. An emetic of tartarised antimony 
was then administered, but it only produced vain efforts to 
vomit. He complained of being cold, and soon again lost the 
power of speech and consciousness, and died in about three 
hours after taking the poison. (Orfila’s Toxicology, vol. ii, p. 
537.) In a case quoted by Dr. A. Stilffi (Mat. Med,, vol. ii, PHYSIOLOGICAL EFFECTS. 
445 
p. 268), a man, who took ten drachms of an extract of hem- 
lock, experienced great restlessness and anxiety, dropped insen- 
sible from his chair, had convulsions, and expired in two hours 
after taking the dose. Dr. Christison relates a case (Op. cit., 
657), in which an old woman swallowed two ounces of a strong 
infusion of hemlock leaves with the same quantity of whisky, 
and died an hour afterwards, comatose and convulsed. 
The following case is reported by Dr. J. H. Bennett (Edin. 
Med. and Surg. Jour., July, 1845, p. 169). A man ate a large 
quantity of hemlock, believing it to be parsley. He soon after- 
wards lost the power of walking, staggered, and finally fell, but 
still retained his consciousness and intelligence. In about two 
hours after taking the poison, there was complete paralysis of 
the upper and lower extremities, with occasional spasmodic 
movements of the left leg; and the patient had lost the power 
of sight, deglutition and speech, but was still sensible : his pulse 
and breathing were natural. The pupils became fixed, the ac- 
tion of the heart very feeble, and death ensued in about three 
hours and a quarter after the poison had been taken. In a case 
quoted by Dr. Pereira (Mat. Med., ii, 732), an overdose of this 
plant also produced general paralysis: the under jaw fell, the 
saliva ran from the mouth, the urine dropped from the bladder, 
and the contents of the rectum were discharged. The patient 
continued for nearly an hour in this condition, unable to move 
or to command the slightest muscular exertion, though all the 
time perfectly sensible; but under the use of stimulants, he 
finally recovered. 
Conine, when administered in its pure state, according to 
the experiments of Dr. Christison, acts at first as a local irri- 
tant ; but its local effects are quickly followed by general palsy 
°f the muscles, affecting first those of voluntary motion, then 
the respiratory muscles of the chest and abdomen, and lastly 
the diaphragm, ending in death by asphyxia. In some cases, 
convulsive tremors were observed. The heart continued to pul- 
sate after other signs of life had ceased. In no case, did the 
external senses seem to be affected until respiration was im- 
paired. This observer states, that a single drop of the alkaloid, 
applied to the eye of a rabbit, killed it in nine minutes; and 446 
CONINE. 
three drops, applied in the same manner, killed a strong cat in 
a minute and a half. Five drops, introduced into the throat of 
a small dog, began to act in thirty seconds, and proved fatal in 
one minute ; and two grains of the chloride, injected into the 
femoral vein of a young dog, killed it before there was time to 
note the interval. (On Poisons, p. 655.) 
The following results were observed in some of our own ex- 
periments, with the pure alkaloid. A single drop of the alkaloid 
was placed upon the tongue of a large and healthy cat. In a 
few seconds, the animal was inclined to stand still, and mani- 
fested an unsteady gait when disturbedin two minutes and a 
half, it fell on its right side, then voided urine, had violent con- 
vulsive movements of the limbs and a tremulous motion of all 
parts of the body, and was dead in three minutes after the poi- 
son had been administered. In another experiment, the animal 
being immediately placed upon its feet, stood perfectly still, and 
the pupils of the eyes became dilated and insensible; in forty- 
five seconds, the legs of the animal became powerless and it 
sank upon its abdomen, then passed urine, had violent spasms 
of the extremities, and died in four minutes after the exhibition 
of the poison. 
Treatment.—The treatment in poisoning by hemlock, is 
much the same as that already pointed out for an overdose of 
tobacco {ante, p. 427). As an emetic, mustard has been strongly 
advised. Dr. Pereira was of the opinion that strychnine might 
be found beneficial, on account of its opposite physiological 
effects to those of conine. 
Post-mortem Appearances.—There is generally more or 
less venous congestion, especially in the brain, and a fluid con- 
dition of the blood. In the case reported by Dr. Haaf, the 
stomach was found half filled with undigested matters, and 
there were some red spots around the pylorus. The intes- 
tines were natural", and the vena cava and heart empty, but 
all the vessels of the brain were highly gorged with liquid 
blood. In the case examined by Dr. Christison, in which 
death took jflace in an hour, the vessels of the brain were 
not particularly turgid, but the blood throughout the body was 
remarkably fluid. CHEMICAL PROPERTIES. 
447 
In Dr. Bennett’s case, sixty-three hours after death, an un- 
usual quantity of fluid blood was found in the vessels of the 
scalp, and in the sinuses of the brain; with slight serous effu- 
sion beneath the arachnoid membrane, and into the ventricles, 
and numerous bloody points in the substance of the brain. The 
lungs were gorged with dark-red, fluid blood. The blood, 
throughout the body, was of a dark color and fluid. The 
stomach contained a pultaceous, vegetable mass; and the mu- 
cous membrane was much congested, especially at its cardiac 
extremity. The intestines and other viscera were healthy, but 
partially congested. On examining the contents of the stomach, 
they were found to contain fragments of leaves of the Conium 
maculatum, which on being bruised in a mortar, with a solution 
of caustic potash, evolved the peculiar mousy odor of conine. 
Chemical Properties. 
General Chemical Nature.—Conine, in its perfectly pure 
state, is a colorless, transparent, oily liquid, having a strong 
alkaline reaction, and, according to Blyth, a specific gravity of 
o’B7 5 it has a peculiar, repulsive and suffocating odor, resem- 
bling somewhat that of a long-used tobacco-pipe. When the 
alkaloid is diluted with water, it emits an odor similar to that 
of mice. This peculiar odor is perceptible even in highly 
diluted solutions: a few drops of a pure aqueous solution con- 
taining only the 50,000 th part of its weight of the free alkaloid, 
when inclosed for a little time in a small test-tube, imparts its 
odor, in a very marked degree, to the contained air. 
Conine imparts a transient, greasy stain to white paper, and 
burns with a bright, smoky flame 5 its taste is repulsive and 
persistent. Its boiling point is about 350° F., but it distills 
with the vapor of water at 212°, with, however, partial decom- 
position. The more rapidly it is distilled, the less decomposi- 
tion it suffers. When heated in an atmosphere of hydrogen 
gas, it may be distilled without change. When preserved from 
the action of the air, it remains colorless, but upon exposure, 
becomes yellow, then brownish, and it is finally resolved into 
a brownish resin and ammonia. 448 
CONINE. 
Solubility.—According to Geiger, with whose observation 
our own closely agrees, conine dissolves at ordinary tempera- 
tures in about one hundred parts of pure water ; its aqueous 
solutions, when not too dilute, have a strongly alkaline reaction. 
When excess of conine is agitated with water, it divides into 
minute drops and gives the mixture a milky appearance ; on 
repose, the excess of the alkaloid collects on the surface of the 
water, as an oily layer. It is very soluble in alcohol, ether, 
and in chloroform. Both ether and chloroform readily separate 
the alkaloid from its aqueous solutions, and upon spontaneous 
evaporation leave it in the form of oily drops ; the former of 
these liquids separates the poison from water much more readily 
than it does in the case of nicotine. 
1. Extraction by Ether.—When a 100 th aqueous solution of 
free conine is agitated with five volumes of ether, and this fluid 
decanted, the aqueous liquid is reduced to about a 4,000 th solu- 
tion of the poison. Under these circumstances, therefore, ether 
extracts about 39-40ths of the alkaloid. 
2. Ey Chloroform.—When a 100 th solution of the free poi- 
son is agitated with five volumes of chloroform, the aqueous 
solution is reduced to about the same extent as when treated 
under similar circumstances with ether. 
Special Chemical Properties.—Exposed to the vapors of 
volatile acids, conine gives rise to dense white fumes. It neu- 
tralises acids completely, forming odorless salts, but few of which 
have been obtained in the crystalline state. The conine used 
in the present investigations was freshly prepared, had a just 
perceptible yellowish tint, and was perfectly free from ammonia: 
at least Nessler’s test, which will indicate the presence of am- 
monia in a few drops of a 500,000 th solution of the alkali, failed 
to indicate its presence in a saturated aqueous solution of the 
alkaloid. 
If a drop of the alkaloid be placed in a watch-glass and 
covered by an inverted watch-glass containing a drop of hydro- 
chloric acid, the glasses immediately become filled with dense, 
white fumes, and the drop of conine very soon solidifies to a 
mass of beautiful, crystalline needles, Plate VI, fig. 4; after a 
time, similar crystals form in the hydrochloric acid drop. When SPECIAL CHEMICAL PROPERTIES. 
449 
diluted solutions of the alkaloid are exposed to the vapor of 
hydrochloric acid, they also give rise to white fumes, and the 
conine solution when concentrated spontaneously deposits crys- 
talline needles of chloride of conine. The same crystals are 
obtained by neutralising an aqueous solution of the alkaloid with 
the diluted acid, and allowing the mixture to evaporate sponta- 
neously. The crystals of chloride of conine are permanent in 
the air: the statement of some writers that they are deliques- 
cent, is erroneous. 
When strong hydrochloric acid is brought in contact with 
pure conine, the mixture assumes a pale red color, which in- 
creases in intensity, and after a time becomes nearly blood-red ; 
if the mixture be evaporated spontaneously to near dryness, it 
deposits a mass of long, crystalline needles, which are readily 
soluble in water and in alcohol, and redeposited as the liquid 
evaporates. 
An aqueous solution of conine, when treated with a saturated 
solution of chlorine gas, becomes turbid. A drop of a 100 th 
solution, yields in this manner, a dense, white turbidity; the 
same quantity of a I,oooth solution, yields after a time, a 
slight cloudiness. 
Nitric acid exposed to the vapor of conine gives rise to 
dense, white fumes. When the alkaloid is treated directly with 
excess of the acid, it yields after a little time, a pale red mix- 
ture, which after a few days becomes converted into a deep red 
liquid containing a mass of colorless, crystalline needles. 
Sulphuric acid forms with the pure alkaloid a pale red liquid, 
which after a few days, deposits crystalline needles along the 
margin of the mixture. If a sulphuric acid solution of the 
alkaloid or of any of its salts, be treated with a small crystal of 
bichromate of potash, the mixture upon being stirred, slowly 
assumes a green color, due to the formation of sesquioxide of 
chromium. 
Upon neutralising pure conine or its aqueous solution with 
oxalic acid, the mixture upon spontaneous evaporation, yields 
prismatic crystals of the oxalate of conia. If the mixture be 
evaporated in a water-bath, the salt is left in the form of a 
gummy mass. 450 
CONINE. 
Most of the salts of conine are soluble in water and in alco- 
hol, but nearly or altogether insoluble in ether. When their 
aqueous solutions are treated with a mineral alkali, the alkaloid 
is liberated and emits its peculiar odor; from somewhat strong 
solutions of its salts, the alkaloid separates in the form of minute 
drops, which finally collect upon the surface of the mixture as 
an oily layer. On distilling an aqueous mixture of a salt of 
conine and caustic potash or soda, the liberated alkaloid passes 
over with the distillate. If the distillate be neutralised with 
oxalic acid, evaporated to dryness, and the residue digested 
with alcohol, the oxalate of conia will dissolve, while any oxa- 
late of ammonia present will remain, it being insoluble in this 
menstruum. 
In the examination of the following tests for conine when 
in solution, the pure alkaloid was dissolved in distilled water. 
When a solution of this kind is agitated it forms a very frothy 
liquid, even when the mixture contains only the 10,000 th part 
of its weight of the poison. The fractions indicate the frac- 
tional part of a grain of the alkaloid in solution in one grain of 
water. Unless otherwise stated, the x'esults refer to the reac- 
tions of one grain of the solution. 
1. Terchloride of Gold. 
A saturated aqueous solution of conine yields with excess of 
terchloride of gold a copious, bright yellow, amorphous precip- 
itate, which is insoluble in acetic acid and in diluted hydrochlo- 
ric acid; with a less quantity of reagent, the precipitate has a 
brownish or reddish-brown color. When treated with potash, 
the precipitate assumes a dark color and finally becomes nearly 
black. 
1. yftt grain of conine, in one grain of water, yields a quite 
copious precipitate. 
2. ---wo grain: a quite good, yellow deposit. 
0. r_wu grain: an immediate cloudiness, and soon a very satis- 
factory, yellow precipitate. 
4. grain, gives but little indication of the presence of the 
alkaloid, even after the mixture has stood for some time. lODINE TEST. 
451 
There was a failure to obtain crystals from any of the fore- 
going mixtures. 
2. Carbazotic Acid. 
Strong aqueous solutions of conine, yield with an alcoholic 
solution of carbazotic acid a yellow, amorphous precipitate, 
which in a little time, changes into microscopic globules, and 
these after a time, deposit large, yellow crystals. The precip- 
itate is insoluble in excess of the reagent, but readily soluble 
in excess of the alkaloid, and also in acetic acid. 
1. xo”o grain of conine, yields a copious precipitate, which soon 
becomes crystalline, Plate VI, fig. 5. If the mixture be 
stirred with a glass rod, it immediately yields streaks of 
granules and small crystals. 
2. grain: an immediate cloudiness, and in a little time, a 
quite good, yellow amorphous deposit. 
3. x.ifoo grain, yields but little indication of the presence of the 
alkaloid. 
3. Corrosive Sublimate. 
white, curdy precipitate, which is but sparingly soluble in 
This reagent produces in aqueous solutions of conine a 
water, but readily soluble in acetic and the mineral acids. 
1. two grain of conine, yields a copious, white precipitate, which 
does not change in color, and remains amorphous. 
2. xxe grain, yields an immediate turbidity, and soon, a good 
deposit. 
3. itoVo grain, yields in a few moments, a distinct cloudiness, 
and in a little time, the mixture becomes quite turbid. 
4. lodine in lodide of Potassium. 
A solution of iodine in an aqueous solution of iodide of po- 
tassium produces in solutions of conine, an immediate, reddish- 
krown, amorphous precipitate, which soon turns yellow, then 
dissolves to a clear solution j upon further addition of the re- 
agent, the precipitate may be reproduced, even several times, 
from somewhat strong solutions of the alkaloid. If a very large 452 
CONINE. 
excess of the reagent be at first added, the precipitate is per- 
manent. It is readily soluble in acetic acid. 
1. xo'cr grain of conine, yields a very copious precipitate. 
2. rroVo grain: a copious deposit. 
3. roToi)^o grain: a very good, brownish-yellow precipitate. 
4. grain: a very satisfactory, yellowish deposit. 
5. 5-075-5-5 grain, yields a quite good, yellowish turbidity. 
6. y0'075-5-5 grain; a distinct turbidity. 
5. Bromine in Bromohydric Acid. 
If a small drop of anhydrous conine be placed in a watch- 
glass, and this covered by an inverted glass containing a drop 
of an aqueous solution of bromohydric acid saturated with bro- 
mine, the glasses become filled with dense, white fumes, and 
soon crystalline needles form in the conine drop, and this on 
spontaneous evaporation of the liquid leaves a mass of long, 
colorless needles 5 the drop of reagent also leaves on spontane- 
ous evaporation, a very good deposit of similar crystals. When 
an aqueous solution of the alkaloid is exposed to the vapor of 
the reagent, it also evolves white fumes, even when the solution 
contains only the I,oooth of its weight of conine. 
On treating anhydrous conine directly with the above re- 
agent, it yields a yellow, amorphous mass, which soon becomes 
converted into large, orange-colored globules; these soon be- 
come yellow, and after a time, deposit colorless, prismatic crys- 
tals. If the mixture be evaporated spontaneously, it leaves a 
mass of large, crystalline needles, which are readily soluble in 
alcohol, and reproduced as this liquid evaporates. These reac- 
tions, however, are modified somewhat by the relative quantities 
of conine and the reagent present. 
When the reagent is added to an aqueous solution of the 
alkaloid, it produces a yellow, amorphous precipitate, which 
after a time changes into oil-like globules | upon further addi- 
tion of the reagent, the yellow, amorphous precipitate is repro- 
duced. On allowing the mixture to evaporate spontaneously, 
it sometimes leaves a crystalline residue, whilst at others a 
gummy mass, the result depending upon the relative quantity NITRATE OF SILVER TEST. 
453 
of reagent present. The precipitate is readily soluble in acids, 
even in acetic acid. 
1. YoTo grain of conine, in one grain of water, when exposed to 
the vapor of the reagent, yields after a time, a deposit of 
crystalline needles; if this mixture be allowed to evapo- 
rate, it leaves a mass of similar crystals. When the conine 
solution is treated directly with the reagent, it yields a 
copious, yellow precipitate, which soon becomes converted 
into oily globules. If large excess of the reagent has been 
avoided, the mixture on spontaneous evaporation leaves a 
mass of crystals. 
2. rrcToi) grain, yields with the reagent, a copious, yellow de- 
posit, which soon dissolves, but is reproduced upon further 
addition of the reagent. 
3. yiroi) grain: a good, yellowish deposit. 
4. yo,oo o grain, yields a very distinct precipitate, which soon 
dissolves, and is not reproduced upon further addition of 
the reagent. 
6. Nitrate of Silver. 
When an aqueous solution of conine is treated with a solu- 
tion of nitrate of silver, it yields a brownish precipitate of pro- 
toxide of silver, which soon becomes converted into the suboxide 
of the metal, having a nearly black color. 
1. yfo grain of conine, yields a quite good deposit. 
2. yt&o'o grain: an immediate precipitate, and in a little time, a 
good, flocculent deposit. 
3* stsVo grain: a slight cloudiness, and in a little time, a quite 
fair deposit. 
4* rorewo grain: after some minutes, the mixture presents a 
slight cloudiness. 
7. Tannic Acid. 
This reagent produces in aqueous solutions of conine a 
white, amorphous precipitate, which is readily soluble in a small 
quantity of hydrochloric acid, but again reproduced upon fur- 
ther addition of the acid and then is insoluble in large excess. 454 
CONINE. 
The precipitate is permanently soluble in acetic and nitric acids, 
as also in excess of the conine solution. 
1. yoo grain of conine, yields a copious precipitate. 
2. ttoVo grain: a quite good precipitate. 
8. ro7oo~o grain: the mixture becomes slightly turbid. 
Other Reagents.—As conine has strong basic properties, it 
precipitates the oxides of several of the metals from solutions of 
their salts. Nitrate of suboxide of mercury produces in strong 
aqueous solutions of the alkaloid a dirty-brown precipitate, 
which soon becomes nearly black. One grain of a 100 th solu- 
tion of the alkaloid, yields a very copious deposit; the same 
quantity of a I,oooth solution, yields a good, yellowish-white, 
and a 5,000 th solution, a dirty-white precipitate. Acetate of 
lead produces in a 100 th solution of the alkaloid, a quite good, 
white deposit. Sulphate of copper gives a bluish precipitate, 
which is insoluble in excess of the conine solution. 
A saturated aqueous solution of conine yields no precipitate 
with either bichloride of platinum, iodide of potassium, chromate 
or bichromate of potash, ferro- or ferricyanide of potassium, or 
with ammonio-sulphate of copper. Should the alkaloid con- 
tain ammonia, as is often the case, it may of course, when 
treated with bichloride of platinum, yield a yellow precipi- 
tate of the double chloride of platinum and ammonium 5 but 
the corresponding salt of conine is freely soluble in water, in 
which respect this alkaloid differs from nicotine. The state- 
ment of Orfila, that acetate of lead produces no precipitate 
with conine, is only true of somewhat dilute solutions of the 
alkaloid. 
Fallacies.—An affirmative reaction of none of the above 
tests for conine in solution, when taken alone, is characteristic 
of this alkaloid, since each of them produces similar results with 
solutions of various other substances. But, by the concurrent 
action of two or more of these tests, especially when taken in 
connection with the odor and physical state of conine, the pres- 
ence of the alkaloid, even in minute quantity, may be determ- 
ined with certainty. SEPARATION FROM ORGANIC MIXTURES. 
455 
Conine and nicotine are distinguished from other alkaloids, 
in being liquid at ordinary temperatures, by their peculiar odor, 
and in that when their aqueous solutions or solutions of their 
salts previously mixed with a fixed alkali, are distilled, they 
appear in the distillate and impart to it, at least after concen- 
tration, an alkaline reaction. In this connection, however, it 
must be borne in mind that on distilling a mixture containing 
ammonia, this alkali will also appear in the distillate and impart 
to it an alkaline reaction; but this substance is readily distin- 
guished, even by its odor, from the volatile alkaloids. 
Conine is distinguished from nicotine: 1. By its peculiar 
odor, which is characteristic even in highly diluted solutions ; 
2. Its sparing solubility in water; 8. In yielding crystalline 
needles when exposed to the vapor or treated directly with 
hydrochloric acid; 4. By yielding a white precipitate with cor- 
rosive sublimate, which remains amorphous and unchanged in 
color; 5. By its behavior with carbazotic acid; 6. Its behavior 
with bromine in bromohydric acid; 7. In giving a dark-brown 
precipitate with nitrate of silver; and, 8. By failing to yield 
a precipitate with bichloride of platinum. On comparing the 
special reactions of these alkaloids, as already detailed, other 
differences will be observed. 
A solution of conine may be distinguished from ammonia in 
the same manner as already pointed out for distinguishing this 
alkali from nicotine in the special reactions of the latter. 
Separation from Organic Mixtures. 
If, in poisoning by hemlock, any solid parts of the plant are 
found, they may, sometimes, be identified by their botanical 
characters (See Pereira’s Mat. Med., vol, ii, p. 727), and by 
evolving the peculiar odor of conine, when moistened with a 
solution of potash and bruised in a mortar. 
Conine may be recovered from organic solutions, the con- 
tents of the stomach, the tissues, and from the blood, in pre- 
cisely the same manner as already pointed out for the recovery 
of nicotine. Since most of the salts of conine are not altogether 
insoluble in ether, if this liquid be employed for the separation 456 
CONINE 
of foreign organic matter from an aqueous solution of a salt of 
this kind, the decanted ether should be reserved for future ex- 
amination, if necessary. 
A fluid ounce of blood taken from each of the two cats 
before referred to—each of which was killed by a single drop 
of conine was examined after the method pursued in the 
investigation of the blood from the cats poisoned by nicotine, 
as already described. The final solution from the blood of both 
animals, when reduced to three drops and tested by its odor 
and three different reagents, gave results, which, knowing all 
the circumstances, there is no doubt were due to the presence 
of conine ; yet, in an unknown case, the results would by no 
means have justified the assertion that the poison was certainly 
present. On mixing the 100 th part of a grain of conine with 
an ounce of normal blood, and pursuing the above method of 
analysis, the results were equivocal; but when the 25th of a 
grain of the poison was added, the results were quite satisfac- 
tory. From a comparison of the special tests for conine and 
nicotine, it is quite obvious that they will indicate with cer- 
tainty the presence of a much smaller quantity of the latter 
than of the former alkaloid. OPIUM 
457 
CHAPTER 11. 
OPIUM AND SOME OF ITS CONSTITUENTS. 
I. Opium. 
History and Chemical Nature.—This substance is the con- 
crete juice of the Papaver somniferum, or white poppy, and is 
obtained by making incisions into the capsules when in their 
unripe state. In regard to its chemical nature, opium is ex- 
tremely complex; and its composition varies somewhat in the 
several commercial varieties. Thus, besides gum, resin, color- 
ing matter, and inorganic substances, it contains, according to 
some observers, not less than twelve crystallisable organic prin- 
ciples. Of these, the only ones that will be separately noticed 
at present are, the alkaloids morphine, narcotine, codeine, and 
narceine, the neutral substance opianyl, or meconin, and the 
organic acid, meconic. 
The poisonous properties of opium are due chiefly to the 
morphine which it contains, which is present principally in com- 
bination with meconic acid, as meconate of the alkaloid. Of 
the several varieties of opium, the Smyrna is usually regarded 
as containing the greatest proportion of morphine. From the 
best samples of this variety, Merck obtained thirteen per cent, 
or more, of the alkaloid, while from the poorest, he obtained 
only from three to four per cent. On an average, perhaps, 
opium as found in the shops contains from six to eight per 
cent, of the poison. 
This drug is sometimes taken as a poison in its solid state, 
but more frequently in the form of Laudanum, or. Tincture of 
opium, which is an alcoholic solution of the drug. The me- 
dicinal dose of opium in its solid form for an adult, varies, 
according to circumstances, from half a grain to five grains; 
the dose of the tincture, under like circumstances, varies from 458 
OPIUM 
ten minims to one fluid drachm. According to the formulae of 
most of the Pharmacopoeias, about thirteen minims or twenty- 
five drops of laudanum contain the soluble portion of one grain 
of opium. One fluid drachm will, therefore, represent nearly 
five grains of the solid drug. Laudanum yields about one 
hundred and twenty drops to the fluid drachm. Since opium 
is liable to considerable variation in regard to the proportion of 
morphine present, and as the strength of the tincture is much 
influenced by the strength of the spirit used and the period of 
maceration, and, also, as the tincture itself is sometimes fraudu- 
lently diluted, it is obvious that laudanum, as found in the shops, 
is subject to great variation in quality. Poisoning by opium 
has been of more frequent occurrence than that by any other 
known substance. 
Symptoms.—When a poisonous dose of opium or of its tinc- 
ture has been swallowed, the patient is sooner or later seized 
with confusion in the head, giddiness, and stupor *, the stupor 
soon increases in intensity, and eventuates in complete insensi- 
bility. In this state, the respiration becomes slow; the pulse 
full, slow, and laboring; the eyes closed; the pupils usually 
contracted and insensible to light, and the person appears as if 
in a profound sleep. As the case advances, the countenance 
becomes pale and ghastly; the lips livid; the skin cold and 
moistened with perspiration; the breathing slow and stertorous; 
the pulse feeble and almost imperceptible; the limbs relaxed, 
and death in some instances is preceded by convulsions. Con- 
vulsions, however, are rarely met with in adults, yet they are 
not uncommon in children: when they do occur they are often 
very severe. The pupils, as already stated, are usually con- 
tracted, being in some cases nearly closed, yet they are not 
unfrequently dilated, especially in the advanced stage of the 
case. The state of the pulse is also liable to considerable vari- 
ation. In some few cases vomiting, and in others purging, has 
occurred. In fact, a few instances are related in which vomit- 
ing was about the only symptom produced by large doses of 
the drug. In cases of recovery from large doses of the poison, 
the stupor is often followed by giddiness, headache, nausea, 
and vomiting. PHYSIOLOGICAL EFFECTS. 
459 
The time within which the symptoms first manifest them- 
selves is somewhat various, depending upon a variety of cir- 
cumstances, but they are not often delayed beyond an hour. 
In some instances, especially when the poison is taken in a 
state of solution and on an empty stomach, its effects appear 
within a few minutes. Dr. Christison (Op. cit., 543) refers to 
several instances in which the symptoms occurred, in adults, 
within about ten minutes; in one of these, the sopor was fairly 
formed in fifteen minutes after two drachms of solid opium had 
been taken. In a case quoted by Dr. Taylor (On Poisons, p. 
588), the patient was totally insensible in fifteen minutes, after 
the poison had been swallowed. 
On the other hand, a case is reported in which a woman 
swallowed about eight ounces of solid opium, and in an hour 
afterwards was able to tell connectedly all she had done (see 
post). Another instance is related, in which an habitual drunk- 
ard took, while intoxicated, two ounces of laudanum, and had 
no material stupor for five hours, during which period vomiting 
could not be induced. Five hours afterwards, he was found 
insensible, and he eventually died under symptoms of opium 
poisoning. In a case reported by Dr. G. C. Gibb, a healthy 
man swallowed, with suicidal intent, twelve drachms of lauda- 
num, and no symptoms of poisoning manifested themselves until 
nine hours after the dose had been taken; spontaneous vomiting 
then occurred, and under careful treatment the patient entirely 
recovered, (Amer. Jour. Med. Sci., Jan., 1858, p. 288.) In 
a remarkable instance related by Dr. Christison, a man swal- 
lowed an ounce and a half of laudanum, and in an hour after- 
wards, half as much more, and no well-marked symptoms 
appeared until the eighteenth hour. The patient then became 
msensible and continued in this condition for several hours; but 
he eventually recovered. 
The external application of opium to an ulcerated or abraded 
surface, and even to the sound skin, has in several instances 
been followed by serious results. Thus, a child, two months 
°ld, nearly perished in consequence of a cerate containing fifteen 
(lrops of laudanum having been kept for twenty-four hours on 
a slight excoriation produced by a fold of the skin. And Sir 460 
OPIUM 
A. Cooper, says he has known a solution of opium applied to 
an extensive scald on a child, prove fatal. In another case, a 
young man, suffering under some slight ailment, applied a 
poultice containing a large quantity of laudanum to the sound 
skin over the pit of the stomach, after which he went to sleep. 
Symptoms of narcotism soon appeared, and although the usual 
treatment was employed, the patient died from the effects of the 
application. (Stifle’s Mat. Med., vol. i, p. 671.) 
The administration of opium in the form of enema, has also 
been followed by fatal results. In a case quoted by Dr. Beck, 
twelve drops of laudanum, used as an injection to allay the pain 
consequent on cauterization for a strictured rectum, produced 
all the symptoms of narcotic poisoning, and death in seventeen 
hours. (Med. Jur., vol. ii, p. 796.) In a case related by Dr. 
J. B. Jackson, five drops of laudanum, injected into the rectum 
of a child eighteen months old, caused death in six hours. 
(Amer. Jour. Mod. Sci., Oct., 1854, p. 884.) In this connection 
it may be mentioned that, Dr. Christison states that he has 
given by injection, one fluid drachm and even two drachms of 
laudanum, without producing any serious symptoms. 
Period when Fatal.—The ordinary duration of fatal poison- 
ing by opium, according to the observations of Dr. Christison, 
is from seven to twelve hours. Several instances, however, are 
recorded in which death took place with much more than the 
usual rapidity. In a case quoted by Dr. Beck, a soldier, who 
having taken two ounces and a half of liquor opii sedativus, was 
rendered totally insensible in fifteen minutes, and died from its 
effects in one hour and twenty minutes. (Med. Jur., vol. ii, p. 
792.) Dr. Gr. Lyman reports a case in which an ounce of lauda- 
num, taken by a woman, aged fifty-two years, produced violent 
symptoms in thirty-five minutes, and death in three-quarters of 
an hour. (Amer. Jour. Med. Sci., Oct., 1854, p. 383.) And, in 
the Journal just cited, a case is reported by Dr. Coale, in which 
death took place within the same brief period. These are among 
the most rapidly fatal cases yet recorded. 
On the other hand, cases are related in which death was 
delayed much beyond the usual period. Thus, several instances 
are reported in which death did not take place until from fifteen FATAL QUANTITY. 
461 
to twenty hours after the poison had been taken. In an instance 
related by Dr. H. F. Campbell, in which nearly three ounces 
of laudanum had been swallowed, by a young man aged twenty- 
eight years, death did not ensue until after twenty hours. 
(Amer. Jour. Med. Sci., Oct., 1860, p. 570.) In a case reported 
by M. Alibert, death did not occur until the twenty-fourth hour; 
and in another, mentioned by Dr. Beck, life was prolonged 
until the forty-eighth hour. The time within which death 
takes place seems to have but little relation to the quantity of 
poison taken. 
Fatal Quantity.—The smallest quantity of opium that may 
destroy life, can not be stated with certainty. Dr. Taylor 
refers to an instance in which ten grains of the solid drug 
proved fatal to a man; and another, in which eight grains 
destroyed the life of a woman. (On Poisons, p, 598.) And 
Dr. Christison mentions a case in which four grains and a half \ 
mixed with nine grains of camphor, taken by an adult, was 
followed by the usual symptoms of narcotism, and death in nine 
hours. In a case reported by Dr. Morland (Amer. Jour. Med. 
Sci,, Oct., 1854), five grains of solid opium, taken in mistake 
by a gentleman, produced all the usual symptoms of the drug, 
mad the patient barely escaped with his life. 
A case has already been cited in which an ounce of lauda- 
num proved fatal to an adult in three-quarters of an hour. And 
m another instance, reported by Dr. W. F. Norris (Amer. Jour. 
Med. Sci., Oct., 1862, p, 397), a similar quantity caused the 
death of a healthy man, in about eighteen hours, although the 
most active remedies were employed. In a case which recently 
occurred in this city, and for the details of which I am indebted 
fo Dr. R. M. Denig, a robust, healthy girl, aged seventeen years, 
m a fit of despondency, swallowed two drachms by measure of 
laudanum. In about three hours afterwards, she was seized 
with stupor, and died under the usual symptoms of narcotic 
poisoning in about seven hours after the dose had been taken. 
The respectable druggist who prepared and sold her the lauda- 
num, testified that at most it contained the soluble portion of 
°nly seven grains of opium. Dr. Toogood relates an instance 
m which twelve drops of u Battley’s sedative”—which is usually 462 
OPIUM 
regarded to have about three times the strength of ordinary 
laudanum—taken by a feeble woman, aged fifty-five years, pro- 
duced the usual symptoms of opium poisoning, and death on the 
following day. (Provincial Med. and Surg. Jour., Nov., 1841, 
p. 129.) 
Numerous instances are recorded in which extremely small 
quantities of opium proved fatal to very young children. In a 
case that fell under our own observation, three drops of lauda- 
num caused the death of a child two weeks old, in about six 
hours. In a case mentioned by Dr. Beck, two drops of lauda- 
num, given four times during a period of eighteen hours, proved 
fatal to a child six weeks old. Even a single dose of two drops 
of laudanum caused the death of an infant four days old; and 
in another instance, an infant six days old was killed by a single 
drop of the opiate preparation. 
Notwithstanding these facts, recovery has not unfrequently 
taken place after very large quantities of the drug had been 
taken. In a case reported by Dr. J. B. Jackson, a woman 
swallowed ninety grains of solid opium, and was not seen by a 
physician until three hours after the occurrence. She was then 
laboring under all the symptoms of opium poisoning; yet under 
active treatment she eventually recovered. (Amer. Jour. Med. 
Sci., Oct., 1854, p. 385.) In another case, a stout, muscular 
woman, who, under disguise, had served several months as a 
common soldier in the late war, took for the purpose of self- 
destruction, sixty grains of solid opium; in about two hours 
afterwards, being disappointed in the effects of the drug, she 
swallowed half an ounce of laudanum, and about half an hour 
later, took as much more. When seen, about three hours and 
a half after taking the first dose, by Dr. J. B. Thompson, to 
whom I am indebted for the particulars of the case, she was 
perfectly rational, and told all she had done. Emetics of sul- 
phate of zinc and ipecacuanha were then administered, but 
they did not operate until after about half an hour, when they 
brought awray a large mass of matter having a strong opiate 
odor; the vomiting was kept up for about three-quarters of an 
hour. She at no time suffered severe narcotism, was soon out 
of danger, and rapidly recovered. From several circumstances ANTIDOTES. 
463 
connected with this case, there is no doubt that the patient took 
the quantities of opium and laudanum stated, which are equal 
to nearly one hundred grains of the crude drug. 
One of the most remarkable cases of this kind yet recorded, 
is the following. A pregnant woman, aged thirty-two years, 
took, with suicidal intent, between seven and eight ounces of 
solid opium. When seen by a physician in about an hour 
afterwards, she was able to relate in a connected manner the 
history of her case. The administration of an emetic caused 
copious vomiting, by which lumps of opium of the size of 
hazelnuts were ejected. The emetic wras repeated, and its 
operation encouraged by large draughts of warm water: it was 
presumed that this vomiting brought away at least three ounces 
more of opium. The patient then fell into a deep sleep, from 
which she could with difficulty be roused; but at length she 
became more sensible, and complained of violent burning pain 
in the stomach. After a little time, a reaction took place and 
symptoms of phrenitis manifested themselves, but she finally 
recovered. (American Medical Recorder, vol. xiii, p. 418.) 
Treatment.—ln poisoning by opium or any of its prepara- 
tions, any portions of the unabsorbod poison should be quickly 
removed from the stomach. For this purpose, the stomach- 
pump will usually be found the most efficient; but in the absence 
°f this instrument, an emetic of from twenty to thirty grains of 
sulphate of zinc or about ten grains of sulphate of copper, 
should be exhibited. If neither of these emetics be at hand, 
powdered mustard or a solution of common salt, should be freely 
administered. If symptoms of narcotism have already mani- 
fested themselves, an emetic may fail to act. Under these 
circumstances, therefore, great caution should be exercised in 
fhe administration of any of the more poisonous emetics, such 
as the sulphate of copper and tartar emetic. 
During the progress of the case, it is of the utmost import- 
ance that the patient be kejDt constantly roused. For this pur- 
pose, various methods have been advised, such as keeping/the 
patient in continual motion, flagellations with wet cloths, and 
flic dashing of cold water over the head and chest. Sometimes 
flic dashing of cold water over the patient insures the operation 464 
OPIUM 
of an emetic. One of the most efficient methods yet proposed 
for preventing a state of insensibility or for rousing the indi- 
vidual from this condition, is a current of magneto-electricity 
applied to the spine and chest. Many cases are reported in 
which this method was employed with complete success; and 
we have in two instances used it with similar results. (Ohio 
Med. and Surg. Jour., May, 1858, p. 388.) As a stimulant, a 
strong decoction of coffee has been highly recommended; in 
fact, several instances are reported in which it is claimed that 
a decoction of this kind was the means of saving life. In ex- 
treme cases, artificial respiration has been employed with great 
advantage. 
As a chemical antidote, Orfila advised the free administra- 
tion of vegetable solutions containing tannic acid, on the ground 
that this acid forms with the active principle of opium a com- 
pound only sparingly soluble in water. So also, solutions of 
iodine and of bromine, have been strongly recommended. In 
practice, however, these substances have been found of little 
service. Various other chemical antidotes have been proposed; 
but the utility of these seems to be even more doubtful than 
that of the substances already mentioned. 
From the apparent antagonistic action existing between the 
physiological effects of opium and those of belladonna, it has been 
asserted that these substances are mutually antidotal to each 
other; and within the last several years, numerous cases have 
been reported in which it is claimed that treatment based upon 
this view of their action, was the means of averting death. A 
recent case of this kind, in which it is believed that three ounces 
of laudanum had been taken, is related by Dr. H. J. Horton. 
(Med. and Surg. Reporter, Philadelphia, Sept., 1866, p. 225.) 
Out of nine cases of opium poisoning treated by belladonna, 
and eighteen of belladonna poisoning treated by opium, collected 
by Dr. W. Forris, of Philadelphia, only two of the former and 
one of the latter, proved fatal. (Amer. Jour. Med. Sci., Oct., 
1862, p. 395.) Since, however, recovery has so frequently 
taken place, even under apparently the most unfavorable cir- 
cumstances, after enormous doses of opium and of belladonna 
had been taken, it is impossible to say how far the recovery in PHYSICAL AND CHEMICAL PROPERTIES. 
465 
cases treated after this method, was really due to the alleged 
antidote. 
Post-mortem Appearances.—The most common morbid ap- 
pearances after death from poisoning by this substance are, 
turgescence of the blood-vessels of the brain, effusion between 
the membranes and into the ventricles of this organ, a con- 
gested state of the lungs, and general fluidity of the blood. 
But these appearances are by no means constant, nor are they 
peculiar to death from opium. In some few instances, the mu- 
cous membrane of the stomach has presented a reddened ap- 
pearance ; but not, perhaps, as the direct result of the action 
of the poison. When the poison has been taken in its crude 
state or in the form of laudanum, the contents of the stomach 
not unfrequently evolve the peculiar odor of opium; but even 
this character is often wanting, the poison having disappeared 
from the stomach prior to death. 
In a case related by Dr. C. A. Lee, in which a large quan- 
tity of laudanum had been taken and death did not occur until 
the sixteenth hour, the superficial veins of the scalp were found 
very full of dark uncoagulated blood. The longitudinal and 
lateral sinuses of the brain were distended with blood; and be- 
tween the pia mater and arachnoid membrane, there was a large 
collection of serum, of a yellowish hue. The choroid plexus 
was very vascular, and in the bottom of the ventricles there 
were small flakes of purulent matter. The lungs wrere con- 
gested ’ and the right side of the heart was full of coagulated 
hlood. The mucous villi of the cardiac orifice of the stomach 
were redder than natural, and much softened. The termination 
°f the oesophagus seemed inflamed, and the mucous lining of 
the intestines erythematous. (New York Med. and Phys. Jour., 
■No. xxx, p. 297.) 
Physical and Chemical Properties.—Opium, in its solid 
state, has a reddish-brown color, a well-marked and peculiar 
°dor, and a bitter, acrid taste. The odor of this drug readily 
serves to distinguish it from Ml other substances excepting lac- 
tucarium, which has a somewhat similar odor. When fresh, 
opium is quite soft and plastic, but on exposure to the air, it 
30 466 
MORPHINE. 
slowly becomes hard and brittle, and is then readily reduced to 
a yellowish-brown powder. When moderately heated, it melts 
to a semi-fluid mass, which readily takes fire, burning with a 
bright flame. It is somewhat heavier than water, its density 
being about LB2. Laudanum, or the alcoholic solution of opium, 
as found in the shops, has a deep brownish-red color, and the 
odor and taste of the solid drug. The active properties of 
opium are also taken up by water, when the drug is digested 
in this liquid; this extraction is much facilitated by a moderate 
heat, and also by the presence of a free acid. Chloroform and 
ether, in their pure state, fail to withdraw the active principles 
of the drug. 
Since, as already pointed out, opium consists of quite a 
number of different substances, it is obvious that there can be 
no single chemical reagent that will show its presence as a 
whole; but this may be inferred by proving the presence of one 
or more of the substances peculiar to it. Although opium con- 
tains several such substances, the ones usually sought for, in 
medico-legal investigations, are morphine and meconic acid. 
Since morphine, as well as several of its salts, is frequently ad- 
ministered or taken alone, it is obvious that proof of the pres- 
ence of this alkaloid alone, would not in all cases justify the 
inference that opium was present. This deficiency, however, 
is always supplied when the presence of meconic acid has been 
established. 
Before considering the methods by which morphine and me- 
conic acid may be separated from complex organic mixtures of 
the crude drug, the special properties of these substances will 
be described. The chemical properties of some of the other 
principles peculiar to opium, will then be considered. 
11. Morphine. 
History and Preparation.—Morphine, as found in nature, 
occurs only in opium, in which it exists chiefly in combination 
with meconic acid, but partly with sulphuric acid. This alka- 
loid was discovered, in 1804, by Serturner; its composition, 
according to Laurent, is PHYSIOLOGICAL EFFECTS. 
467 
Morphine may he obtained, according to the method of 
Gregory, by treating a concentrated aqueous solution of opium 
with slight excess of a solution of chloride of calcium. After 
a little time, especially if warmed, the mixture deposits a copi- 
ous precipitate, consisting of a mixture of meconate and sul- 
phate of lime, Avhile chloride of morphine remains in solution. 
The liquid is then filtered, and the highly colored filtrate con- 
centrated to the consistency of a thin syrup, when, on cooling, 
the chloride of morphine separates in its crystalline state, form- 
ing a neai’ly solid mass. This is strongly pressed in muslin, 
redissolved in a small quantity of hot water, the solution filtered, 
and the salt allowed to recrystallise; this operation is repeated 
a second and, if necessary, a third time, using a little prepared 
animal charcoal to absorb the coloring matter. The salt is now 
dissolved in hot water, and the solution slightly supersaturated 
with ammonia, when, on standing, the liberated alkaloid is de- 
posited in snow-white crystals. 
For the estimation of the quantity of morphine in' opium, 
M. Roussille has recently advised the following method. Fifteen 
parts (15 grammes, or about 225 grains) of opium are treated 
with twenty-five parts of boiling water till complete disaggrega- 
tion has taken place ; sixty parts of boiling alcohol are then 
added, and the mixture digested for an hour. The liquid is 
then filtered through a linen cloth, and the residue treated with 
ten parts of water and sixty parts of alcohol, after which it is 
extracted with fifty parts of boiling absolute alcohol. The 
united liquids are then allowed to cool, filtered, concentrated to 
one-third, and again filtered. The morphine is now precipitated 
by ten parts of ammonia, and the mixture evaporated over sul- 
phuric acid. At the end of three days, the deposited crystals 
are collected, washed with ether, then with water, dried, and 
weighed. (Chemical News, London, Oct., 186G, p. 162.) 
Symptoms.—Considerable difference of opinion has existed 
as to whether or not the effects of morphine and its salts were 
identical with those occasioned by opium; but on the whole, 
the symptoms are much the same, only that the effects of the 
saline combinations of the alkaloid usually manifest themselves 
more promptly, than in the case of the crude drug. In addition 468 
MORPHINE. 
to the usual narcotic symptoms, itching of the skin, impaired 
or total loss of vision, and inability to void urine, have fre- 
quently been observed. Great lividity of the skin has also fre- 
quently been present. The relative strength of morphine and 
its salts, is generally estimated to be about five or six times 
that of the crude drug. 
In a case reported by Dr. Houston, ten grains of the sul- 
phate of morphia, given by mistake to a gentleman, aged fifty- 
nine years, who was laboring under intermittent fever, caused 
death in less than two hours, although various remedies were 
employed. Deep stertorous breathing was the only symptom 
observed. (Beck’s Med. Jur., vol. ii, p. 799.) Dr. Christison 
mentions an instance in which a girl, who had taken ten grains 
of the chloride, was seized with narcotic symptoms within fif- 
teen minutes afterwards, and died from its effects in twelve 
hours. (Op. cit., 558.) And Dr. Taylor cites an instance (On 
Poisons, p. 617), in which six grains of the same salt, proved 
fatal to a woman, aged sixty-six years, in nine hours after the 
poison had been taken. 
In a case quoted by Wharton and Stille (Med. Jur., p. 581), 
a gentleman affected with acute rheumatism died from the effects 
of one grain and a third of morphine, taken in four pills at 
intervals of an hour between each. In another instance, one 
grain of the chloride, taken in divided doses over a period of 
six hours, proved fatal to a girl nineteen years old. In a case 
reported by Dr. Toogood, seven drops of a solution of the ace- 
tate of morphia (strength not stated), destroyed the life of an 
aged woman, under the usual narcotic symptoms, in about twelve 
hours. (Provincial Med. and Surg. Jour., Nov., 1841, p. 129.) 
In a recent case, a solution containing only the twelfth part of 
a grain of morphine, administered by mistake, caused the death 
of an infant. (Chemical News, London, Aug., 1863, p. 98.) 
On the other hand, Mr. Winterbotham reports a case in 
which a child, two years and three months old, swallowed one 
grain of the acetate of morphia in solution, and the poison 
remained undisturbed in the system for two hours and a half. 
At the end of this period, free vomiting was induced by an 
emetic of sulphate of zinc; and under the use of the ordinary PHYSIOLOGICAL EFFECTS. 
469 
remedies, the child entirely recovered. (Amer. Jour. Med. Sci., 
April, 1863, p. 520.) In a case related by Orfila, a young man 
entirely recovered within three days, after having taken, with 
suicidal intent, twenty grains of the chloride of morphine. 
Within ten minutes after taking the poison, the patient experi- 
enced a sense of heat in the stomach, with intense itching of 
the skin; but over four hours elapsed before symptoms of stu- 
por manifested themselves. Profound insensibility then super- 
vened, and he was affected with trismus; the pupils became 
slightly dilated; the surface of the body cold; the pulse rapid; 
the breathing hurried and stertorous; the abdomen tense and 
tympanitic, and there were occasional convulsions; and after- 
wards he had difficult and scanty micturition, with pain in the 
kidneys and bladder, and difficulty of swallowing. 
A somewhat similar case, to that just mentioned, is cited by 
Dr. Christison, in which a young man swallowed fifty grains of 
the acetate of morphia, and although he was seized within fif- 
teen minutes with the usual narcotic symptoms of the poison in 
an aggravated degree, and vomiting could not be induced until 
four hours afterwards, he finally recovered. One of the most 
remarkable cases of recovery yet reported, is the following, re- 
lated by Dr. W. F. Norris. A druggist, aged nineteen years, 
for the purpose of self-destruction, swallowed seventy-five grains 
of the sulphate of morphia. No marked symptoms appeared 
for an hour and a half afterwards, when he began to feel sleepy, 
and had a staggering gait. Soon after this, emetics were given 
with the effect of producing free emesis. The patient then be- 
came unconscious, the pupils contracted to the size of a pin’s 
point, the pulse soft and frequent, and the respiration slow and 
labored; but under the active use of remedies, including extract 
of belladonna, the cold douche and galvanism, he was quite well 
on the second day after the occurrence. (Amer. Jour. Med. 
Sci., Oct., 1862, p. 395.) 
The external application of morphine to abraded surfaces, as 
well as its use in the form of enema, has in several instances 
keen followed by serious, and even fatal results. A quantity of 
the alkaloid, perhaps about one grain, applied to a blistered 
surface on the back of the neck of an aged lady, produced, in 470 
MORPHINE. 
the course of about two hours, convulsive agitations, cold sweats, 
extreme prostration, and threatened suffocation, from which the 
patient, under active treatment, only slowly recovered. (Amer- 
ican Medical Intelligencer, vol. ii, p. 13.) In a case quoted by 
Dr. A. Stille (Mat. Med., vol. i, p. 676), a lady affected with 
cancer of the uterus was dangerously narcotised by less than 
one-sixteenth of a grain of chloride of morphine applied to the 
denuded skin of the epigastrium. 
An enema containing ten grains of sulphate of morphia, 
prescribed in mistake for quinine, was administered to a child 
five years old, who was laboring under intermittent fever. 
Within ten minutes, the child became sleepy, and shortly after- 
wards it was seized with violent convulsions; various remedies 
were now employed, but death speedily ensued. (Med.-Chir. 
Rev., vol. xv, p. 551.) In another instance, reported by Dr. 
Anstie, three grains of the alkaloid given inadvertently as an 
injection caused death in about sixteen hours. (Amer. Jour. 
Med. Sci., April, 1863, p. 520.) The age of the patient in 
this case is not stated; but it would seem that the person was 
an adult. 
The Treatment and Post-mortem Appearances in poisoning 
by morphine and its salts, are the same as in poisoning by 
opium, already described. 
Chemical Properties 
General Chemical Nature.—Morphine, in its pure state, 
crystallises in the form of short, colorless, odorless, rectangular 
prisms, which contain two equivalents of water of crystallisa- 
tion (C 3Og, 2 Aq.). The exact forms of these crystals, 
however, are subject to considerable variation, depending some- 
what upon the method employed for their preparation and the 
strength of the solution from which they were separated, and 
even upon the quantity of the solution employed. When gently 
heated, the crystals part with their water of crystallisation and 
become opake; at a little higher temperature, they fuse to a 
brownish liquid, which, if the heat be increased, evolves dense 
white fumes, then turns black, and is finally consumed. Morphine SOLUBILITY. 
471 
lias a very bitter taste, and strong basic properties. It com- 
pletely neutralises diluted acids forming salts, most of wliicb 
are crystallisable. It is readily decomposed by concentrated 
nitric acid, and by hot sulphuric acid; but not by the cold 
caustic alkalies. 
Solubility. 1. In Water.—When excess of pure, powdered 
morphine is frequently agitated for twelve hours with water 
at the ordinary temperature, and the solution then filtered, the 
filtrate leaves on spontaneous evaporation a crystalline residue 
indicating that the alkaloid requires about 4,166 times its weight 
of this menstruum for solution. It is much more freely soluble 
in hot water. 
2. In Chloroform.—Under the conditions just stated, one 
part of morphine requires about 6,550 parts by weight of this 
fluid for solution. 
3. Ether.—Under similar conditions, one part of the alkaloid 
requires 7,725 parts of absolute ether for solution. Commercial 
ether of specific gravity 0’733, dissolved one part of the alka- 
loid in 4,225 parts of the liquid. 
If an aqueous solution of a salt of morphine be decomposed 
with slight excess of carbonate of soda, and the mixture • allowed 
to repose for a little time so that the liberated alkaloid may de- 
posit in its crystalline state, and the whole be then agitated 
with a large quantity of absolute ether, this liquid will take up 
only a mere trace of the alkaloid, the proportion being even 
much less than that stated above. If, however, immediately 
after the addition of the carbonate of soda, the mixture be agi- 
tated with ether, this fluid will dissolve a much larger propor- 
tion of the alkaloid than above stated: under these conditions, 
one part of morphine was taken up by 2,500 parts of abso- 
lute ether. 
4. Alcohol.—When excess of finely-pulverised morphine is 
digested, with frequent agitation, for ten hours in alcohol of 98 
per cent., the filtered liquid leaves on spontaneous evaporation, 
a crystalline residue indicating that one part of the alkaloid had 
dissolved in 148 parts of the liquid. It is still more freely 
soluble in hot alcohol; but on cooling, the liquid deposits the 
greater part of the excess, in its crystalline state. A cold, 472 
MORPHINE. 
saturated, alcoholic solution of the alkaloid, has a well-marked 
alkaline reaction. 
5, Alcoholic-ether.—When twenty-five fluid-grains of an 
aqueous solution containing 10-100ths of a grain of morphine 
in the form of acetate, is treated with slight excess of carbonate 
of soda, and the whole violently agitated with five volumes of a 
mixture consisting of two parts of absolute ether and one part 
of pure alcohol, this mixture takes up 9-100ths of a grain of the 
liberated alkaloid, which on spontaneous evaporation it leaves in 
the form of brilliant crystals. When a mixture of this kind is 
agitated, in the proportions just mentioned, the alcoholic-ether 
takes up about one-third of the aqueous liquid, the original 
volume of the latter being reduced to about two-thirds. 
6. Amylic-alcohol.—When excess of the powdered alkaloid 
is digested in pure amylic-alcohol, with frequent agitation, for 
four hours at the ordinary temperature, one part is taken up 
by 133 parts of the menstruum. % 
On decomposing twenty-five grain-measures of an aqueous 
solution containing 10-100ths of a grain of morphine as acetate, 
with carbonate of soda, and agitating the mixture with two 
volumes and a half of amylic-alcohol, this liquid extracted the 
whole of the alkaloid, excepting the 1-200 th of a grain. 
7. Pure Acetic-ether, when kept in contact with large excess 
of powdered morphine for several hours, at the ordinary tem- 
perature and with frequent agitation, dissolves one part in 1,030 
parts of the liquid. On allowing the solution to evaporate spon- 
taneously, the alkaloid is left in its crystalline state. In com- 
mercial acetic-ether, which usually contains alcohol and more 
or less free acetic acid, the alkaloid is much more freely soluble, 
even, sometimes, to the extent of one part in 75 parts of the fluid. 
When half a grain of morphine, in the form of sulphate, was 
dissolved in fifty grains of pure water, the solution rendered 
slightly alkaline by carbonate of potash, and the mixture thor- 
oughly agitated with three volumes of pure acetic-ether, in two 
separate portions, this liquid extracted only the o‘oB of a grain 
of the liberated alkaloid. 
The alkaloid is readily soluble in solutions of the fixed caus- 
tic alkalies; but only sparingly soluble in diluted aqua ammonia. SPECIAL CHEMICAL PROPERTIES. 
473 
The salts of morphine, for the most part, are readily soluble 
in water, especially if the liquid be slightly acidulated; they 
are also soluble in diluted alcohol, but insoluble in chloroform, 
ether, amylic-alcohol, and pure acetic-ether: they are, there- 
fore, not extracted from their aqueous solutions by either of the 
four last-named liquids. Their aqueous solutions, when pure, 
are colorless, and have the bitter taste of the alkaloid. 
Special Chemical Properties.—lf a few crystals of pure 
morphine be added to a drop or two of concentrated sulphuric 
acid, they slowly dissolve without change of color, or at most 
yield a faint pinkish solution. If a crystal of bichromate of 
potash be now stirred in the solution, it slowly yields green 
oxide of chromium; under the same circumstances, a crystal 
of nitrate of potash produces a dark-brown, muddy mixture. 
When a little of the alkaloid or any of its salts is dissolved by 
the aid of heat in a small quantity of concentrated sulphuric 
acid* and the solution, after cooling, diluted with a little water, 
and then a crystal of chromate of potash added, the liquid ac- 
quires an intensely mahogany-brown color (Otto). Under this 
treatment, the merest fragment of morphine will yield a very 
satisfactory coloration. 
Concentrated nitric acid causes the alkaloid to assume a 
beautiful orange-red color, and dissolves it, with the evolution 
of binoxide of nitrogen, to a solution of the same hue, which 
slowly fades to yellow. (See post.) The color of the nitric 
acid solution, is not affected by chloride of tin. Hydrochloric 
acid slowly dissolves the alkaloid, without change of color. 
In the following investigations in regard to the reactions of 
morphine when in solution, pure aqueous solutions of both the 
sulphate and acetate were employed. The fractions indicate 
the fractional part of a grain of anhydrous morphine in solution 
in one grain of the liquid. When not otherwise stated, the 
results refer to the reaction of one grain of the solution. 
1. Potash and Soda. 
The fixed caustic alkalies, when added in limited quantity, 
throw dowm from concentrated neutral solutions of salts of 474 
MORPHINE. 
morphine, a white, amorphous precipitate of the anhydrous 
alkaloid, which in a little time, appropriating two equivalents 
of water, becomes crystalline. From more dilute solutions, the 
precipitate does not appear until after some time, and it then 
separates in its crystalline form. From such solutions, the for- 
mation of the precipitate is much hastened by stirring the mix- 
ture with a glass rod. The precipitate is readily soluble in 
excess of the precipitant, and in free acids, even acetic acid; 
its nitric acid solution has an orange-red color. 
1. jwo grain of morphine, in one' grain of water, yields with a 
small drop of the reagent, after a few moments, a crystal- 
line precipitate, which in a little time, increases to a quite 
copious deposit, Plate YI, fig. 6. If on the addition of the 
reagent, the mixture be stirred with a glass rod, it imme- 
diately yields streaks of crystals along the path of the rod, 
over the bottom of the watch-glass containing the mixture, 
and in a few moments, there is a very copious crystalline 
deposit. Since the precipitate is readily soluble in the 
fixed caustic alkalies, care should be taken to avoid the 
addition of much excess of the reagent, otherwise no de- 
posit will form. 
2. two grain, yields after a little time, by stirring the mixture, 
a very good deposit. 
3. 170 0-0 grain: when the least possible quantity of reagent is 
employed, the mixture yields after a time, a quite satis- 
factory, granular precipitate. 
These reagents also produce in solutions of most of the other 
alkaloids, white, crystalline precipitates; but the crystalline 
form of the morphine deposit, when from not too dilute solu- 
tions, is somewhat peculiar. Its true nature may be fully 
established by its behavior with nitric acid or some of the 
other tests mentioned hereafter. 
2. Ammonia. 
Ammonia produces with neutral solutions of salts of mor- 
phine, much the same results as the fixed alkalies; but the 
precipitate is not so readily soluble in excess of the precipitant. NITRIC ACID TEST. 
475 
From dilute solutions, therefore, it is much more easy to obtain 
precipitates by this reagent than by either potash or soda. If 
a drop of a solution of the alkaloid be exposed to the vapor of 
a drop of ammonia, suspended on a glass rod, it yields after a 
little time, a white, crystalline deposit. This is much the best 
method for obtaining precipitates from very dilute solutions of 
the alkaloid. 
The alhaline carbonates, also, throw down from normal solu- 
tions of salts of morphine a white precipitate of the alkaloid, 
which is only very sparingly soluble in large excess of the pre- 
cipitant. If, however, large excess of the reagent be added at 
first, the formation of the precipitate is partially or entirely pre- 
vented. The limit of the reaction of these reagents is the same 
as that of the caustic alkalies.- 
3. Nitric Acid. 
When somewhat strong solutions of salts of morphine are 
treated with large excess of concentrated nitric acid, the mix- 
ture slowly acquires a lemon-yellow or orange-red color, its 
exact tint depending upon the relative proportion of acid and 
morphine present. 
1. Yo~o grain of morphine, in one grain of water, yields, with a 
few drops of the acid, a yellow solution, which very soon 
acquires an orange color, then a deep orange-red, after 
, which the liquid slowly becomes again yellow. 
2. ytttoT) grain: the mixture slowly acquires a lemon color, which 
after some minutes becomes light orange. 
3. j,Toii grain: after some minutes, the mixture assumes a quite 
perceptible lemon hue, which is best seen over a white 
ground. 
The reaction of this test is much more satisfactory and deli- 
cate when a small portion of the acid is applied to the alkaloid, 
or any of its salts, in the dry state. 
1. jTo grain of morphine—in the form of sulphate or acetate, 
as left upon evaporating one grain of its aqueous solution 
to dryness—when touched with a small drop of nitric acid, 
almost immediately assumes a fine orange-red color, and 476 
MORPHINE. 
dissolves to a solution of the same tint, Avhich slowly fades 
to yellow. 
2. rrcToo grain: at first the deposit assumes a yellow color, 
which however soon changes to a bright, brownish-orange, 
and dissolves to a fine orange solution. 
3. grain: the residue assumes a very distinct brown color, 
and dissolves to a faint brownish solution. 
4. roTcrro grain, when touched with a very minute quantity of 
the acid, after a little time acquires a very faint brown- 
ish hue. 
Brucine, and strychnine containing this alkaloid, immedi- 
ately strike a deep blood-red or bright red color when treated 
with strong nitric acid. This color, however, upon the addition 
of a solution of protochloride of*tin, is changed to bright pur- 
ple ; whereas, that produced from morphine is unaffected, or, at 
most, is changed to yellow by this reagent. Nitric acid also 
produces a more or less red coloration with certain volatile oils 
and resinous substances, but none of these are crystallisable, in 
which respect they differ from morphine. 
4. lodic Acid. 
When a tolerably strong solution of a salt of morphine, or 
the alkaloid or any of its salts in the dry state, is treated with 
a strong solution of iodic acid, the latter is decomposed with the 
elimination of free iodine, which falls as a brown or reddish- 
brown precipitate, and the mixture emits the odor of iodine. 
If a freshly prepared solution of starch-paste be now added, the 
mixture acquires a blue color, due to the formation of iodide of 
starch. For the production of this blue color, however, it is 
necessary, as pointed out by M. Duprd (Chemical News, Dec., 
1868, p. 267), that the proportions of iodic acid and starch 
employed, be within certain limits, since the color is destroyed 
by large excess of iodic acid, and also by large excess of the 
starch solution. 
1. Y6 0- grain of morphine, in one grain of water, when treated 
in the above manner, yields a blue precipitate and imparts 
a deep blue color to the liquid. SESQUICHLORIDE OF IRON TEST. 
477 
2. grain, yields a brownish liquid, and a quite distinct blue 
precipitate. 
3. jjp grain: the mixture assumes a slight brownish color, 
but it fails to yield a precipitate. 
This reaction is much more delicate when applied to mor- 
phine or any of its salts, in the solid state. For this purpose, 
as advised by M. Duprd, the morphine or its solution is first 
treated with a drop of starch solution; the mixture is then 
carefully evaporated to dryness, and the residue, after cooling, 
moistened with a solution of iodic acid. In this manner, a res- 
idue containing only the 10,000 th part of a grain of the alka- 
loid, will yield a. quite distinct blue color. 
The reactions of this test are common to many other sub- 
stances, some of which, like morphine, are crystallisable. 
M. Lefort has recommended to treat the mixture of mor- 
phine and iodic acid, with ammonia, instead of starch, by which 
the yellow color of the mixture is changed to deep brown or 
yellowish-brown. In applying this method to dilute solutions of 
the alkaloid, the iodic acid mixture should be allowed to stand 
some minutes before the ammonia is added, since otherwise the 
coloration may be entirely prevented. 
This method, when applied to solutions, is much more deli- 
cate than the starch process before described; and, moreover, 
it is said, that the yellow color produced by iodic acid with 
most other substances capable of reducing this acid, is dis- 
charged by ammonia, whereby morphine may be distinguished 
from such substances. For the detection of morphine in highly 
diluted solutions, the author of this method advises to moisten 
slips of unsized paper repeatedly with the alkaloidal solution, 
carefully drying them between each immersion, and then apply 
the iodic acid solution and ammonia to the paper thus prepared. 
5. Sesquichloride of Iron. 
Concentrated solutions of salts of morphine, as well as the 
alkaloid or any of its salts in the solid state, strike with a neu- 
tral solution of sesquichloride of iron or of persulphate of this 
metal, providing no free acid is present, a deep blue color, 478 
MORPHINE. 
which is discharged by free acids, the caustic alkalies, and by 
heat. On the addition of nitric acid, the blue mixture acquires 
an orange-red color. 
1. grain of morphine, in solution in one grain of water, 
yields with a drop of the reagent, a quite good, ink-blue 
2. xoir grain: after a few minutes, the reaction is evident, but 
coloration. 
not satisfactory. 
Sesquichloride of iron also occasions with tannic and gallic 
acids, a blue color, which is changed to reddish-yellow by nitric 
acid. When either of these vegetable acids is treated with 
nitric acid alone, it yields a yelloiv solution; in this respect they 
differ from morphine. There are also some few vegetable infu- 
sions, which, when treated with a per-salt of iron, give rise to 
a more or less blue coloration. On the other hand, it should be 
borne in mind that, the blue color produced by morphine may 
not make its appearance if the alkaloid be mixed with certain 
foreign substances. 
6. lodide of Potassium, 
This reagent produces in somewhat concentrated neutral so- 
lutions of salts of morphine, especially if the mixture be stirred 
or allowed to stand some time, a white, crystalline precipitate, 
which is readily soluble in acids, even acetic acid. This reac- 
tion is readily interfered with by the presence of foreign sub- 
stances. 
1. y4tt grain of morphine, in one grain of water, yields, after 
a little time, a quite copious deposit of large groups of 
crystalline needles, Plate VII, fig. 1. The precipitate 
from a solution of the sulphate of morphia, is more prompt 
in forming, and somewhat more abundant, than that ob- 
tained from the acetate. 
2. xihr grain, yields, after some minutes, a very good, granular 
deposit. 
This reagent also produces white crystalline precipitates 
with several of the alkaloids, but the forms of these in most 
instances differ widely from those obtained from morphine. 479 
CHLORIDE OF GOLD TEST. 
7. Chromate of Fotash. 
Protochromate of potash throws down from strong neutral 
solutions of salts of morphine, a yellow, crystalline precipitate, 
which is very readily soluble in free acids. 
1. tout grain of morphine, yields, in a very little time, espe- 
deposit, having the forms illustrated in Plate VII, fig. 2. 
2. i7o“oi) grain, yields after some time, a slight, granular pre- 
cially if the mixture be stirred, a very copious, crystalline 
Bichromate of potash produces in one drop of a 100 th solu- 
tion of the alkaloid, a yellow, amorphous precipitate, which 
after a time becomes granular. In solutions but little more 
dilute than this, the reagent fails to produce a precipitate. 
cipitate. 
8. Ter chloride of Gold. 
Solutions of salts of morphine, yield with terchloride of gold, 
a bright-yellow, amorphous precipitate, which almost immedi- 
ately begins to darken, becoming bluish and finally dirty green 
or nearly black. Solutions of the sulphate of morphia do not 
seem to undergo this change as rapidly as those of the acetate. 
The precipitate is partially soluble in acetic and nitric acids. 
If the precipitate, as first produced, be treated with a solution 
of potash, it immediately darkens, and the mixture becomes 
bluish, purplish or nearly black, its exact color depending upon 
the relative quantity of reagent employed. 
1* To o' grain of morphine, in one grain of water, yields a very 
copious, yellow deposit, which undergoes the changes above 
described. 
2. Tooo grain, yields, after a few moments, a very good, yellow 
precipitate, which slowly darkens. When treated with 
a drop of potash solution, the precipitate dissolves, and 
the mixture, in a very little time, becomes purplish or 
nearly black. 
ttVcTo grain: after a little time, a good precipitate, which 
is readily soluble, to a clear solution, in potash. After 480 
MORPHINE. 
some minutes, however, the potash mixture deposits small, 
4. 25,111) grain, yields, after standing some time, a quite dis- 
black flakes. 
tinct turbidity. 
If the precipitate from ten or fifteen grains of a I,oooth or 
stronger solution of the alkaloid be boiled in the mixture, the 
deposit, without dissolving, assumes a brown or dark color, due 
to its partial decomposition; the deposit from a 2,500 th solu- 
tion, readily dissolves upon heating, and the mixture on cooling, 
immediately darkens, from the presence of small, black flakes, 
which after a time adhere to the sides of the tube; the precip- 
itate from a 5,000 th solution, readily dissolves by heat, yielding 
a yellow solution, which undergoes but little change, even after 
several hours. 
Besides morphine, tannic and gallic acids and certain other 
organic substances, have the property of precipitating and re- 
ducing solutions of salts of gold. With the aid of potash, most 
organic compounds precipitate the metal in the form of a black 
powder; and even a mixture of chloride of gold and potash 
alone, may after a time, yield black flakes. 
9. Bichloride of Platinum. 
This reagent throws down from concentrated neutral solu- 
tions of acetate of morphia, a yellow, granular precipitate, 
which is very readily soluble in acids, even acetic acid. 
One grain of a 100 th solution of the alkaloid, yields, espe- 
cially if the mixture be allowed to stand some time, a quite 
good, yellow deposit, Plate VII, fig. 8. Solutions but little more 
dilute than this, fail to yield a precipitate. 
10. lodine in lodide of Potassium. 
A solution of iodine in iodide of potassium produces in solu- 
tions of salts of morphine, even when highly diluted, a reddish- 
brown amorphous precipitate, which is but slowly soluble in 
acetic acid, but dissolves readily, to a clear solution, in caustic 
potash; it is also soluble in alcohol. Unless large excess of the CARBAZOTIC ACID TEST. 
481 
reagent be added, the precipitate after a time partially or en- 
tirely disappears. 
1. yo"o grain of morphine, in one grain of water, yields a very 
copious deposit. 
2. x.itoo grain: a very good, reddish-brown precipitate. 
'B* ttmToo grain: an immediate turbidity, and in a little time, a 
very fair, brownish-yellow deposit. 
4. xotWo grain, yields a very satisfactory turbidity. 
Although the reaction of this reagent is common to a large 
class of organic substances, yet it is often useful as a prelimi- 
nary test; should it, when applied to a suspected solution, under 
proper conditions,, fail to produce a precipitate, it is quite cer- 
tain that the other reagents for the alkaloid, would also fail. 
11. Bromine in Bromohydric Acid. 
Neutral solutions of salts of morphine, when treated with a 
solution of bromohydric acid saturated with bromine, yield a 
yellow, amorphous precipitate, which after a time dissolves, but 
is reproduced upon further addition of the reagent. The pre- 
cipitate is soluble in acetic acid and in alcohol. 
1. txo grain of morphine, yields a very copious precipitate, 
which remains amorphous. 
2. r,Wo grain: a quite good deposit. 
3. x,~5 0~0 grain, yields a slight turbidity. 
This reagent also produces similar precipitates with various 
other organic substances. 
12. Carbazotic Acid. 
An alcoholic solution of carbazotic acid produces in aqueous 
solutions of salts of morphine a bright yellow, amorphous pre- 
cipitate, which is readily soluble in alcohol, but only slowly 
soluble in acetic acid. The precipitate remains amorphous. 
Tiro grain of morphine, in one grain of water, yields a very 
copious deposit. 
2* ttt grain, yields a quite distinct precipitate. 
°m TToVo grain : no indication. 
31 482 
MORPHINE. 
This reaction is common to a great number of organic sub- 
stances, but with several of the other alkaloids, it produces a 
crystalline precipitate. 
18. Chlorine and Ammonia. 
When a strong solution of a salt of morphine is treated with a 
stream of chlorine gas, it acquires a deep yellow color, which upon 
the addition of ammonia, is changed to deep brown. This color 
is not affected by large excess of ammonia nor by acetic acid. 
1. 100 th solution of morphine: ten grains of this solution yield 
2. I,oooth solution: chlorine imparts to the liquid a yellow tint, 
which is changed to a quite distinct brownish hue by 
ammonia. 
results similar to those just described. 
Solutions but little more dilute than the last-named, show 
no change when treated with these reagents. 
Other Reagents.—lodohydrargyrate of potassium, or a solu- 
tion of corrosive sublimate containing just sufficient iodide of 
potassium to redissolve the precipitate first produced, produces 
in solutions of salts of morphine, even when highly diluted, a 
white, flocculent precipitate of the double iodide of morphine 
and mercury, which is only very sparingly soluble in diluted 
acetic and hydrochloric acids, but readily soluble in large ex- 
cess of alcohol. The production of a white precipitate by this 
reagent is common to a large class of organic principles; in 
some instances, however, as in the case of strychnine, the pre- 
cipitate is more or less crystalline. 
Tannic acid throws down from somewhat strong, neutral 
solutions of salts of the alkaloid a white, flocculent precipitate, 
which is readily soluble in acids and in the fixed caustic alkalies. 
Chloride of palladium produces in similar solutions, a yellow, 
amorphous precipitate, which is also readily soluble in acids. 
When a few drops of a strong solution of a salt of morphine 
are treated with a strong solution of nitrate of silver, the latter 
salt, especially if the mixture be gently heated, is sooner or 
later decomposed, with the production of a shining, crystalline MECONIC ACID. 
483 
precipitate of metallic silver; at the same time, the mixture 
acquires a more or less yellow hue, due to the action of the 
eliminated nitric acid upon the alkaloid. (J. Horsley, Chem. 
News, July 5, 1862, p. G.) One grain of a 100 th solution of 
morphine, when treated after this method, yields a very satis- 
factory deposit. How far this reaction is common to other 
substances, we are not prepared to say. 
Sulphocyanide of potassium, ferrocyanide and ferricyanide 
of potassium, acetate of lead, and chloride of barium fail to 
produce a precipitate, even in concentrated solutions of salts of 
morphine, at least so far as the alkaloid itself is concerned. 
Among the tests now described for the detection of mor- 
phine, the reaction of no one of them taken alone, as already 
intimated, is peculiar to the alkaloid. But by the concurrent 
action of two or more of them, especially the nitric acid and 
sesquichloride of iron tests, the true nature of even exceedingly 
minute quantities of the alkaloid may be fully established, more 
particularly if it be in its crystalline state. It must be ad- 
mitted, however, that in regard to delicacy of reaction, the 
tests at present known for the identification of morphine, are 
inferior to those for many of the other alkaloids ; and, moreover, 
as will be seen hereafter, this alkaloid is more difficult than most 
others to separate from foreign organic substances. 
111. Meconic Acid. 
History.—Meconic acid was discovered, in 1804, by Ser- 
tiirner. In its pure state, it crystallises in the form of colorless 
plates, either singly or in groups; its composition in this form, 
18 3HO ; CI4HOn, 6 Aq. In nature, it has been found only in 
Ike poppy tribe, in which it exists as meconate of morphia. Of 
good Smyrna opium, it forms about six per cent. ; its propor- 
tion, however, varies in different samples of the drug,, and it is 
oven said to be sometimes altogether absent, but this statement 
is exceedingly doubtful. 
Preparation.—Various methods have been proposed for the 
preparation of meconic acid, but we have found the following 484 
MECONIC ACID. 
to be one of the most simple, at least if only a small quantity 
of the substance be desired. A strong, filtered, aqueous solu- 
tion of opium is treated with excess of acetate of lead, and the 
impure meeonate of lead thus produced collected on a filter and 
washed, as long as the washings become colored. It is then 
diffused in a small quantity of water and treated with excess of 
sulphuretted hydrogen gas, whereby the lead is precipitated as 
sulphuret, while the liberated meconic acid enters into solution. 
The liquid is now filtered and evaporated on a water-bath at a 
very moderate heat, until a drop of it removed to a watch-glass, 
cooled, and stirred with a drop of hydrochloric acid, yields a 
crystalline precipitate. The liquid is then allowed to cool, and 
strongly acidulated with pure hydrochloric acid, when after a 
time, the meconic acid, being insoluble in diluted hydrochloric 
acid, will separate in the form of shining plates and crystalline 
groups. Should the crystals not be entirely colorless, they may 
be redissolved in a small quantity of hot water, and the cooled 
solution again strongly acidulated with hydrochloric acid. 
Physiological Effects.—Meconic acid, when taken into the 
system, seems to be inert. At least, it has repeatedly been 
administered to inferior animals in doses of several grains, and 
taken by man in similar quantities, without producing any ap- 
preciable effect. . 
General Chemical Nature.—As usually found in the shops, 
meconic acid is in the form of crystalline scales, having a more 
or less reddish color, due to the presence of foreign matter. It 
has an acid, astringent taste, and strongly acid properties, read- 
ily uniting with basic oxides, forming salts, called meconates. 
It, like phosphoric and arsenic acids, is tribasic, or capable of 
uniting with three equivalents of base. When the crystallised 
acid is heated, it first parts with its six equivalents of water of 
crystallisation, then fuses, emits dense white fumes, and finally 
takes fire, burning with a yellow flame. If the acid be mod- 
erately heated in a reduction-tube, it sometimes yields a subli- 
mate of crystalline needles. 
Solubility.—Meconic acid is soluble in about one hundred 
and fifteen times its weight of pure water, at a temperature of 
60° F,, forming a strongly acid solution. It is much more freely SPECIAL CHEMICAL PROPERTIES. 
485 
soluble in liot water, from which, however, much of the excess 
separates, in the crystalline form, as the solution cools. In 
water containing free hydrochloric acid, meconic acid is very 
much less soluble than in pure water. Alcohol dissolves it 
rather freely, and leaves it, on spontaneous evaporation of the 
liquid, in the form of beautiful groups of crystals. It is only 
very sparingly soluble in absolute ether, requiring about 2,150 
parts by weight of this liquid for solution; and it is almost 
wholly insoluble in chloroform. The salts of this acid, except- 
ing those of the alkalies, which are freely soluble, are, for the 
most part, insoluble in water. They are also insoluble, or very 
nearly so, in alcohol. 
Special Chemical Properties.—Meconic acid, in its solid 
state, is unchanged in color by cold sulphuric, nitric, and hy- 
drochloric acids. On the application of a very gentle heat, it 
dissolves quietly to a clear solution in the first two of these 
mineral acids, but it is insoluble in hydrochloric acid; at a little 
higher temperature, it is readily decomposed, by the mineral 
acids, with effervescence. When heated to a temperature of 
about 300° F., solid meconic acid, parting with its water of 
crystallisation, is resolved into carbonic acid gas and a new, 
bibasic acid, named commie, thus : 3HO ; CI4HOu _ 2 HO; 
cl 2h2o8 + 2 C02. At a somewhat higher temperature, comenic 
acid in its turn is resolved into carbonic acid gas and pyrome- 
conic acid, which is monobasic: 2 HO; Cl 2H208 = HO, ClOH3O5 + 
2 C02. Both these new acids, like the meconic, strike a deep 
blood-red color with solutions of persalts of iron. The conver- 
sion of meconic into comenic acid is also effected by boiling an 
aqueous solution of the acid, the change being much facilitated 
by the presence of a free mineral acid. When boiled with an 
aqueous solution of either of the fixed caustic alkalies, meconic 
acid is resolved into carbonic and oxalic acids and a dark color- 
ing matter. 
In the following examination of the tests for meconic acid 
when in solution, pure aqueous solutions of the free acid 
were employed, it being dissolved when necessary by the aid 
°f a very gentle heat. The fractions indicate the amount of 
crystallised acid present in one grain of the fluid. Unless 486 
MECONIC ACID. 
otherwise indicated, the results refer to the behavior of one 
grain of the solution. 
1. Sesquichloride of Iron. 
Solutions of sesquichloride and of persulphate of iron strike 
with solutions of meconic acid, as well as with the acid and 
its salts in the solid state, a deep blood-red color, which is 
not discharged by either corrosive sublimate or chloride of 
gold, but readily disappears upon the addition of a solution 
of protochloride of tin. The red coloration manifests itself 
in the presence of even large excess of either of the free 
mineral acids. 
1. yo or grain of meconic acid, in one grain of water, yields with 
a drop of the reagent a deep reddish-brown coloration, 
which requires several drops of either of the concentrated 
mineral acids for its discharge, but it is unaffected, further 
than by dilution, by several drops of a strong solution of 
either corrosive sublimate or chloride of gold. 
2. rroro grain, yields a very good, red coloration. 
3. rorWo grain : the mixture acquires a very distinct purplish- 
4. 2"076U"0 grain, yields a just perceptible red tint. In several 
red color. 
drops of this solution, the red coloration is quite distinct. 
If the meconic acid solution be evaporated by a very gen- 
tle heat to dryness, and a drop of the reagent applied to the 
residue:— 
1. rorWo grain; the deposit assumes a deep blood-red color. 
2. 5-07V00 grain, yields a very distinct red coloration. 
3. txiuTo grain : the residue acquires a just perceptible red hue. 
This is the most characteristic test yet known for the iden- 
tification of very minute quantities of meconic acid, yet it is 
open to some few fallacies j but these may be readily guarded 
against. They are as follows : 
a. The alkaline sidphocyanides and free hydrosulphocyanic 
acid yield with persalts of iron a red coloration not to be dis- 
tinguished, in appearance, from that occasioned by meconic acid. 
This color, however, unlike that from meconic acid, is quickly IRON TEST. 
487 
discharged by a solution of corrosive sublimate. This latter 
reagent, therefore, serves to readily distinguish between these 
substances. It is frequently stated that the red color produced 
by a sulphocyanide is readily discharged by a solution of chlo- 
ride of gold, but this is not the case. 
Another method of distinguishing between the red color pro- 
duced by these ditferent substances, as first proposed by Dr. 
Percy, is to place in the colored mixture a piece of pure zinc, 
and then add a drop of sulphuric acid, when in the case of 
meconic acid, the color is slowly discharged with the evolution 
of pure hydrogen gas, whereas the color of a sulphocyanide 
is destroyed with the evolution of sulphuretted hydrogen gas, 
which may be recognised by its peculiar odor, and by its black- 
ening a piece of paper moistened with a solution of acetate of 
lead and suspended over the mixture. This method is not as 
simple as the preceding; and, moreover, if the zinc should con- 
tain sulphur, as is frequently the case, the mixture will evolve 
sulphuretted hydrogen, even in the absence of a sulphocyanide. 
Human saliva has not unfrequently the property of striking 
a red color with persalts of iron, due to the presence of a sulpho- 
cyanide; and Dr. Pereira states (Mat. Med., vol. ii, p. 1,033) 
that he has on several occasions obtained the same results from 
the liquid contents of the stomach of subjects in the dissecting- 
room. However, in the preparation of the contents of this 
organ for the detection of meconic acid, as pointed out here- 
after, any sulphocyanide present would be separated with the 
foreign matter, when this objection would no longer hold. If 
in any case there is any doubt as to the true nature of the red 
coloration, this, of course, may be removed by the application 
of a solution of corrosive sublimate. 
h. Strong solutions of acetic acid and of its neutral salts 
yield with the iron reagent a more or less red coloration, which, 
like that from meconic acid, is unaffected by corrosive sublimate 
and chloride of gold. This color is more readily affected by 
free mineral acids than that from the opium compound. Solu- 
tions of acetic acid and of its salts differ from those of me- 
conic acid, in that they fail to yield a precipitate with acetate 
°f lead. 488 
MECONIC ACID. 
c. Persalts of iron also strike with a concentrated decoction 
of white mustard a red color, which, however, is immediately 
discharged by corrosive sublimate, but not by chloride of gold. 
Besides the substances now mentioned, a strong infusion of 
Iceland moss, and of some few other rare substances, as first 
pointed out by Dr. Pereira, will also yield a more or less red 
coloration with the iron reagent; but these substances are 
uncrystallisable, and, like those before mentioned, would be 
removed from the liquid during its preparation for the appli- 
cation of the test for meconic acid. The color produced from 
Iceland moss has a purplish hue, and is unaffected by corrosive 
sublimate, but it is immediately destroyed by chloride of gold. 
2. Acetate of Lead. 
This reagent throws down from solutions of free meconic 
acid and of its soluble salts, a yellowish or yellowish-white, 
amorphous precipitate of meconate of lead (3 PbO; CI4HOn, 
2 Aq.), which is insoluble in large excess of acetic acid, but 
readily soluble, to a clear solution, in diluted nitric acid. If the 
precipitate be treated with a drop of sesquichloride of iron solu- 
tion, the mixture acquires a red color. 
1. ywo grain of meconic acid, in one grain of water, yields a 
very copious, yellowish deposit. 
2. rroVo grain: a copious, yellowish-white precipitate. 
3. rorWo grain, yields a very distinct deposit. 
4. a-oTQiro grain; after a few minutes, a quite distinct opales- 
cence appears, and then, little whitish flakes. 
Acetate of lead also produces precipitates with many other 
substances, but in these cases the deposit has always, unless 
foreign matter be present, a pure white color. Among these 
substances may be mentioned:— 
a. Sulphocyanides, which yield a white precipitate which, 
like that from meconic acid, is reddened by persalts of iron ; 
but it is readily soluble in acetic acid, and when from strong 
solutions, insoluble in diluted nitric acid; when from dilute solu- 
tions, however, it is readily soluble in the latter acid, to a clear 
solution. When treated with metallic zinc and sulphuric acid, CHLORIDE OF BARIUM TEST. 
489 
sulphocyanide of lead undergoes decomposition with the evolu- 
tion of sulphuretted hydrogen; whereas, the meconate of lead, 
as already stated, yields pure hydrogen gas. h. Chlorine yields 
with the reagent a white precipitate, which when from chloride 
of sodium is readily soluble in excess of the precipitant, and in 
acetic and nitric acids; but when due to free chlorine, it is only 
sparingly soluble in these acids, c. Sulphuric acid, either free 
or combined, yields a precipitate which is insoluble in acetic 
acid, and only sparingly soluble in nitric acid. d. Soluble car- 
bonates occasion a precipitate that is readily soluble with effer- 
vescence in acetic acid. e. Phosphates and oxalates, also, yield 
precipitates which are insoluble in acetic acid, but readily sol- 
uble in nitric acid. So, also, the reagent produces white pre- 
cipitates with various organic principles; but these deposits are 
readily distinguished from the meconic acid compound, in not 
being reddened by persalts of iron. 
3. Chloride of Barium. 
Strong aqueous solutions of meconic acid and of its alkaline 
salts, yield with chloride of barium a white crystalline precipi- 
tate of meconate of baryta, wdiich is insoluble in acetic and 
diluted nitric acids, and also in caustic ammonia. 
1* two grain of meconic acid: in a few moments, crystals be- 
gin to appear, and in a very little time, there is a quite 
copious, crystalline deposit, of the peculiar forms illus- 
trated in Plate VII, fig. 4. If on the addition of the 
reagent, the mixture be stirred, it immediately yields a 
copious crystalline deposit. 
grain : after a little time, especially if the mixture be 
stirred, there is a quite satisfactory deposit, consisting 
principally of little masses of aggregated granules. 
tttoo grain: after some time, the mixture yields small, mi- 
croscopic granules. 
Although this reagent also produces white precipitates in 
solutions containing sulphuric, phosphoric, and several other 
acids, yet the crystalline form of the meconic acid deposit is 
peculiar. 490 
MECONIC ACID. 
4. Hydrochloric Acid. 
This acid, in its free state, produces in aqueous solutions of 
meconic acid and of its soluble salts, when not too dilute, a 
white precipitate of free meconic acid, due to the insolubility 
of the latter in the presence of a limited quantity of the re- 
agent. This precipitate is in the form of transparent crystal- 
line plates, which, for the most part, are arranged in beautiful 
groups, and many of which, when examined by transmitted 
light under the microscope, appear beautifully colored. The 
formation of the precipitate, is much facilitated by stirring the 
mixture with a glass rod. 
1. grain of meconic acid, in one grain of water, when 
treated with a drop of concentrated hydrochloric acid; 
almost immediately crystals begin to form, and in a little 
time, there is a quite copious deposit, Plate VII, fig. 5. 
2. Too" grain: after some minutes, providing very large excess 
of hydrochloric acid be not employed, the mixture throws 
down a very satisfactory, crystalline precipitate. 
Hydrochloric acid also produces white precipitates in solu- 
tions containing silver, lead, antimony, and sub-combinations of 
mercury. But the silver, mercury, and antimony deposits are 
amorphous, and that from lead, is in the form of crystalline 
needles; whereas, the meconic acid precipitate, even from com- 
plex organic mixtures, is always in the form of crystalline plates. 
It need hardly be remarked that, the meconic acid precipitate 
also differs from these fallacious substances in striking a red 
color with persalts of iron. 
5. Nitrate of Silver. 
This reagent produces in aqueous solutions of the organic 
acid an amorphous precipitate of meconate of silver, which is 
readily soluble in ammonia and in nitric acid, but insoluble in 
acetic acid. The color of this precipitate depends somewhat 
upon the relative quantity of reagent employed: when the lat- 
ter is in excess, the deposit has a yellow color; whilst, if there CHLORIDE OF CALCIUM TEST. 
491 
is excess of meconic acid present, the precipitate is white. 
The yellow deposit is said to consist of the tribasic meconate of 
silver (3 AgO; CI4HOn); while the white, is a bibasic salt of 
the metal (2 AgO ; CI4HOn). 
1. y-J-Q- grain of meconic acid, in one grain of water, yields a 
very copious, pale yellow or yellowish-white, gelatinous 
precipitate, which after a time acquires a pure yellow 
color. If several drops of the solution be precipitated by 
excess of the reagent, the deposit has at once a rather 
bright yellow hue. 
2. y-yoij grain: a good, flocculent precipitate, having only a 
just perceptible yellow tint. 
3. ro7«nro grain: after a time, a quite distinct, flaky deposit. 
Nitrate of silver also produces yellow or yellowish-white pre- 
cipitates in solutions containing phosphoric, arsenious, and silicic 
acids; but neither of these acids strikes a red color with per- 
mits of iron. 
6. Ferricyanide of Potassium. 
Strong aqueous solutions of meconic acid and of its alkaline 
salts, when treated with this reagent, yield, especially if the 
mixture be stirred and allowed to stand, a crystalline precipi- 
tate, which is only slowly soluble in acetic acid. 
One grain of a 100 th solution of the free acid, yields after 
a little time, large groups of hair-like crystals, Plate VII, fig. 
3 ; after about half an hour, the mixture becomes converted 
mto an almost solid crystalline mass. Solutions but little more 
dilute than this, altogether fail to yield a precipitate. The 
crystals produced by this reagent are quite characteristic. 
7. Chloride of Calcium. 
This reagent produces in concentrated solutions of the alka- 
line meconates a white or yellowish-white precipitate of meco- 
ftate of lime. One grain of a 100 th solution of the free acid 
yields no immediate precipitate, but after a little time, large 
groups of colorless, transparent crystals separate from the 492 
MECONIC ACID AND MORPHINE. 
mixture, Plate YIII, fig. 1. The precipitate is insoluble in large 
excess of acetic acid; its formation is much facilitated by agi- 
tating the mixture. 
Other Reagents.—Sulphate of copper throws down from strong 
aqueous solutions of meconic acid, a greenish-blue, amorphous 
precipitate of the meconate of copper, which is soluble in acetic 
acid and in ammonia. Ammonio-sulphate of copper fails to 
produce a precipitate, even in concentrated solutions of the 
free acid. 
Saturated aqueous solutions of the free acid fail to yield a 
precipitate with either of the following reagents: chloride of 
gold, ferrocyanide of potassium, carbazotic acid, bichloride of 
platinum, corrosive sublimate, iodine in iodide of potassium, bro- 
mine in bromohydric acid, tannic acid, and chromate of potash. 
Separation of Meconic Acid and Morphine from Solutions 
of Opium and Complex Organic Mixtures. 
The presence of opium may be established, as already stated, 
by showing the presence of meconic acid and morphine. In 
fact, this may be done by simply proving the presence of me- 
conic acid 5 yet, when possible, it is always advisable to also 
prove the presence of morphine. Should there be a failure to 
detect either of these substances, it is pretty certain that there 
would also be a failure to discover any of the other principles 
peculiar to the drug. This arises from the fact that the methods 
at present known for the separation of these latter substances 
from complex organic mixtures, are much less delicate than 
those for the recovery at least of meconic acid. In their pure 
state, however, some of these principles may be identified in 
even smaller quantity than the organic acid. Before proceed- 
ing to the preparation of a suspected mixture for the application 
of chemical tests, it should be carefully examined for the odor 
of opium; this, however, may not be recognised, even when 
the drug is present in quite notable quantity. 
Suspected Solutions and Contents of the Stomach.—If 
the liquid presented for examination appears to be a simple 493 
SEPARATION FROM ORGANIC MIXTURES. 
aqueous solution of opium or laudanum, as is sometimes the 
case, it is slightly acidulated with acetic acid, and evaporated 
at a low temperature, on a water-bath, to a small volume, then 
filtered, and the filtrate examined in the manner hereafter di- 
rected. When, however, the suspected mixture is of a complex 
nature and contains organic solids, these are cut into very small 
pieces, the mass, if not already sufficiently liquid, treated with 
pure water and a little alcohol, and the whole distinctly acidu- 
lated with acetic acid. It is then very moderately heated, with 
frequent stirring, for half an hour or longer, allowed to cool, 
the liquid strained through muslin, and the solid residue on the 
strainer well washed with strong alcohol and strongly pressed, 
the washings being collected with the first liquid. The united 
liquids are now concentrated to a very small volume, on a water- 
hath at a temperature not exceeding IGO° F., and then, after 
cooling and dilution with water if necessary, filtered through 
paper previously moistened with water. Any solid matter thus 
separated, is washed with a little diluted alcohol, and the wash- 
ings added to the first filtrate. If during the concentration of 
the liquid, much solid matter separates, it should be removed 
fiy a muslin strainer. 
The clear filtrate thus obtained, is treated with slight excess 
of acetate of lead, by which any meconic acid present will be 
precipitated as meconate of lead, together with more or less 
foreign matter ; at the same time, any morphine and other 
opium principles present, will remain in solution. Should the 
liquid contain a sulphocyanide, this will also remain in solution, 
Slnce, as already pointed out, these salts are not precipitated in 
the presence of free acetic acid, by the lead reagent. When 
Hie precipitate has completely subsided, the mixture is trans- 
ferred in small portions to a small moistened filter, and the solid 
residue left on the filter washed with a little pure water, this 
being collected with the first filtrate. The analysis now divides 
fiself into two branches : 
Ist. Contents of the filter.—While the filter is still moist, its 
lower end is pierced with a glass rod, and the contents carefully 
hashed, by a jet of water from a wash-bottle, into a tall test- 
tube, and then allowed to completely subside. After, if thought 494 
MECONIC ACID AND MORPHINE. 
best, decanting a portion of the clear supernatant liquid, the 
precipitate is diffused in the remaining fluid and treated with a 
stream of sulphuretted hydrogen gas, as long as a precipitate 
is produced. By this treatment, any meconate of lead present 
will be decomposed, the metal being thrown down as black sul- 
phuret, while the liberated meconic acid will enter into solution. 
The liquid is then filtered, and the filtrate concentrated at a 
moderate temperature on a water-bath, when the excess of sul- 
phuretted hydrogen present will be dissipated. If the liquid 
contains a quite notable quantity of meconic acid, it will now 
usually have a more or less reddish or brownish color. 
After the solution thus obtained has cooled, a drop of it is 
removed to a watch-glass, and tested with a persalt of iron; 
if this indicates the presence of meconic acid in quite notable 
quantity, the remaining liquid is examined by some of the other 
tests for the organic acid. Should, however, the iron-test fail 
to yield positive results or indicate the presence of the acid in 
only minute quantity, the remaining fluid is carefully concen- 
trated to a very small volume, and consecutive drops examined 
by sesquichloride of. iron, hydrochloric acid, and chloride of 
barium or ferricyanide of potassium. Should, in any case, the 
iron-test fail, it is quite certain that the other tests mentioned 
would also fail, since the former is much the more delicate in 
its reactions. If the concentrated liquid contains much foreign 
matter, this may very much interfere with the normal reactions 
of the tests. Under these circumstances, the liquid may be 
evaporated at a very gentle temperature to dryness, the residue 
extracted with a small quantity of strong alcohol, the filtered 
alcoholic extract evaporated to dryness, and the residue thus 
obtained dissolved in a very small quantity of warm water and 
the solution then tested. In some instances, however, it will be 
found best, for the separation of foreign matter, to reprecipitate 
the meconic acid by acetate of lead, and then treat the precip- 
itate in the manner above described. 
By the method now described, the 100 th part of a grain of 
meconic acid in solution in twenty-five grains of wTater, may be 
precipitated and recovered, without any appreciable loss. So, 
also, an alcoholic solution of one grain of opium mixed with SEPARATION FROM ORGANIC MIXTURES. 
495 
foreign organic matter, when treated after this method and the 
final solution reduced to four drops, gave with the four reagents 
before named, results somewhat better, in each case, than a 
100 th solution of the pure acid, the last three reagents produc- 
ing copious crystalline precipitates of the forms peculiar to the 
organic acid. 
When a solution has been prepared in this manner, the fal- 
lacies attending the iron-test under certain conditions, do not 
apply. The manner in which any sulphocyanide present would 
be avoided has already been indicated ; and as the acetates are 
all soluble, they also would remain in solution in the filtrate 5 
nor could any of the organic infusions that strike a red color 
with the iron reagent, remain on the filter with the washed 
meconate of lead. 
Another method frequently advised for decomposing the mec- 
onate of lead, for the recovery of the organic acid, is to digest 
it at a moderate heat with diluted sulphuric acid, under the 
action of which it is resolved into insoluble sulphate of lead and 
free meconic acid, which enters into solution. Since, however, 
as already pointed out, meconic acid is prone to undergo decom- 
position in the presence of a free mineral acid, especially if the 
mixture be heated to near the boiling temperature, this method 
may be attended with considerable loss; moreover, the presence 
°f sulphuric acid would interfere with some of the tests for the 
organic acid. 
2d. The filtrate.-^-The above filtrate—which contains the 
morphine in the form of acetate, and some of the other opium 
principles, together with any excess of acetate of lead employed 
m the precipitation of the meconic acid—is treated with excess 
°i sulphuretted hydrogen gas, for the purpose of precipitating 
fhe lead. When the precipitate has completely deposited, which 
may be facilitated by the application of a very gentle heat, the 
liquid is filtered, and the filtrate evaporated on a water-bath to 
firyness ; the residue thus obtained is well stirred with a little 
pure water, and the solution again filtered. A drop of the solu- 
tion may now be tested for morphine by nitric acid, and another, 
V sesquichloride of iron. Whether these tests indicate the 
presence of the alkaloid or not, the remaining liquid, after 496 
MECONIC ACID AND MORPHINE. 
dilution if necessary, is rendered slightly alkaline by a strong 
solution of carbonate of potash, allowed to stand some little 
time, and then agitated with a few volumes of absolute ether. 
This liquid will extract some of the opium principles and more 
or less coloring matter, but leave the liberated morphine in the 
alkaline aqueous fluid. After carefully decanting the ethereal 
liquid, and placing it aside for future examination if necessary, 
the alkaline liquid may be examined by either of the following 
methods. 
a. The liquid is violently agitated for some minutes, with 
from four to five times its volume of a mixture consisting of two 
parts of absolute ether and one part of pure alcohol, by which 
the alkaloid will be extracted from the aqueous fluid. This 
operation is best performed by placing the alkaline liquid in a 
long, graduated tube, and then adding sufficient of the prepared 
ethereal mixture so that after agitation and repose, the volume 
of the former liquid is slightly diminished. In certain propor- 
tions, the liquids will form a homogeneous mixture, while in 
others, the volume of the aqueous fluid will be augmented, and 
in others still, it will be diminished. If any difficulty is expe- 
rienced in regard to the separation of the liquids, a little pure 
ether should be added. 
The alcoholic-ether is now carefully decanted into a large 
watch-glass, and allowed to evaporate spontaneously, when the 
morphine will usually be left in its crystalline form; when, 
however, there is only a minute quantity of the alkaloid present 
or it is mixed with much foreign matter, it may remain in its 
amorphous state. When the residue has become quite dry, it 
is carefully washed, by gently rotating a few drops of pure 
water over it in the glass and then decanting the liquid. Small 
portions of the residue are now separately examined by nitric 
acid and a persalt of iron, and any remaining portion dissolved, 
by the aid of a trace of acetic acid, in a very small quantity 
of water, and the solution then submitted to some of the liquid 
tests for morphine. By exposing a portion of the aqueous so- 
lution to the vapor of ammonia until it acquires a very slightly 
alkaline reaction, and then exposing it to the air, for sev- 
eral hours if necessary, the alkaloid will be deposited in its SEPARATION FROM ORGANIC MIXTURES. 
497 
crystalline form, even when present in only very minute quan- 
tity. In this manner, we have on several occasions obtained 
very satisfactory crystals, when every other method failed to 
reveal the alkaloid in this form. 
On applying the method now described, for the extraction 
of morphine, to a complex organic mixture containing only one 
grain of opium, the meconic acid having been previously pre- 
cipitated from the aqueous solution by acetate of lead, the 
alcoholic-ether left on spontaneous evaporation, a very line crys- 
talline deposit of the alkaloid. 
h. Another method for the extraction of the morphine, is to 
agitate the alkaline liquid, as first suggested by Uslar and Erd- 
mann (See ants, p. 417), with two or three times its volume of 
hot amylic-alcohol, in which, as already shown, the alkaloid is 
rather freely soluble. When the fluids have completely sep- 
arated, the upper, or alcoholic, liquid is transferred, by means 
of a caoutchouc-pipette, to a watch-glass j the aqiieous fluid is 
then washed with a fresh portion of the hot alcohol, and this 
transferred to the watch-glass containing the liquid first em- 
ployed. In the absence of a caoutchouc-pipette, the alkaline 
liquid may be removed from the alcoholic, by closing the upper 
end of an ordinary pipette with the finger and passing the open 
end to the bottom of the fluid mixture, when upon removing 
the finger, the aqueous liquid will be forced into the tube, and 
may thus be removed. The employment of the ordinary suc- 
tion-pipette, on account of the injurious action of the alcohol 
on the respiratory organs, is inadmissible. 
The amylic-alcohol is now evaporated, at a very gentle heat 
on a water-bath, to dryness, when the alkaloid may be left in 
its crystalline form; but it is much less apt to be left in this 
form, under these circumstances, than when separated by spon- 
taneous evaporation from the above ethereal mixture. Should 
the residue be amorphous, it may be re-dissolved in a small 
quantity of diluted, ordinary alcohol, and the liquid allowed to 
evaporate spontaneously. The residue is then examined in the 
ordinary manner. 
In the application of this method for the recovery of minute 
quantities of morphine from complex mixtures containing known 
32 498 
MECONIC ACID AND MORPHINE. 
quantities of opium, we have obtained very satisfactory results; 
and on the whole, perhaps, this process is preferable to the 
ether method before described. 
c. A third method that may be employed for the extraction 
of the alkaloid, from the foregoing alkaline solution, is by means 
of acetic-ether, as recently advised by M. Alfred Valser. (Chem. 
News, 1864, vol. ix, p. 289; from Jour. Pharm. et Chimie, 
xliii, 49, 63.) The operation may be conducted in much the 
same manner as when amylic-alcohol is employed, and the liquid 
allowed to evapoi-ate spontaneously. If this method be adopted, 
it should be borne in mind that morphine is much less soluble 
in pure acetic-ether than in either amylic-alcohol or a mixture 
of alcohol and ether; and, therefore, that a correspondingly 
larger proportion of this liquid will be required for the extrac- 
tion of a given quantity of the alkaloid. On the other hand, 
this liquid, when pure, has a much less solvent action upon 
foreign organic matter than either of the other liquids named, 
particularly a mixture of alcohol and ether; at the same time, 
it is more likely than amylic-alcohol, on evaporation, to leave 
the alkaloid in the crystalline form. It may here be remarked, 
that acetic-ether, as found in the shops, not unfrequently con- 
tains so much alcohol as to cause it to mix in all proportions 
with water, when agitated with this liquid. 
The absolute ether with which the alkaline solution was 
washed, previous to the extraction of the morphine, contains 
narcotine and some other opium principles, together with more 
or less foreign organic matter. When evaporated spontaneously, 
it usually leaves, if there is not much foreign matter present, a 
transparent amorphous residue, which when treated with a drop 
of concentrated sulphuric acid, dissolves to a blood-red solu- 
tion ; if a small crystal of nitrate of potash be stirred in this 
mixture, the color of the latter is changed to brownish or 
purplish. These results, however, being due tp the combined 
action of several different substances, are subject to consider- 
able variation. 
Porphyroxin.—For the detection of small quantities of opium, 
Merck advises to take advantage of the property possessed by 
porphyroxin, one of the constituents of the drug, of being SEPARATION FROM ORGANIC MIXTURES. 
499 
reddened when heated with hydrochloric acid. For this pur- 
pose, the opium solution is rendered alkaline by caustic potash 
and agitated with pure ether, in which this principle is soluble. 
A strip of white bibulous paper is then repeatedly dipped into 
the decanted ethereal liquid, the paper being dried between 
each immersion ; the paper is now moistened with hydrochloric 
acid, and exposed to the vapor of boiling water, when it will 
acquire, especially after drying, a more or less rose-red color. 
On following these directions, for the examination of solutions 
containing very notable quantities of opium, we failed to obtain 
very satisfactory results; with larger quantities of the drug, 
however, the red coloration was well marked. 
According to Merck, porphyroxin, in its pure state, may be 
obtained by the following process. Powdered opium is ex- 
hausted by boiling ether, then made into a pulp with water, 
slight excess of carbonate of potash added, the mixture agitated 
with ether, the ethereal liquid evaporated to dryness, the resi- 
due thus obtained dissolved in a small quantity of very dilute 
hydrochloric acid, and the solution rendered slightly alkaline by 
ammonia, by which the porphyroxin, together with paramor- 
phine, will be precipitated. On dissolving the precipitate in 
ether, and allowing the liquid to evaporate spontaneously, the 
former of these principles is left in the form of a resin, while 
the latter is deposited in the crystalline form. They may now 
be separated by cautiously treating the mixture with alcohol, 
m which the porphyroxin is soluble ; the alcoholic solution is 
then evaporated to dryness at a low temperature. Porphyroxin 
is described as a neutral substance, which crystallises in brill- 
iant needles, is readily soluble in alcohol and in ether, but insol- 
uble in water. It is but proper to add, that the existence of 
this substance, as a distinct opium principle, has been doubted 
by several experimentalists. 
Examination for Morphine alone.—When there is reason to 
suspect that morphine, or one or other of its salts, is present in 
its free state, the same method of analysis may be followed as 
for its recovery from organic solutions containing opium, ex- 
cepting that the use of acetate of lead is omitted. Thus, the 
mixture, slightly acidulated with acetic acid, is digested at a 500 
MECONIC ACID AND MORPHINE. 
moderate temperature with diluted alcohol, allowed to cool, the 
liquid strained, then concentrated on a water-bath to a small 
volume, filtered, and the filtrate evaporated to dryness. The 
residue, thus obtained, is treated with a small quantity of water, 
the solution filtered, the filtrate rendered slightly alkaline with 
carbonate of soda, washed with absolute ether, and the alka- 
loid, if present, extracted by either of the methods heretofore 
described. 
It rarely happens, under these circumstances, that the ana- 
lyst is able to determine the acid with which the morphine was 
combined. Should, however, the mixture be not too complex, 
it may be concentrated on a water-bath to a very small volume, 
then gently warmed with a little concentrated alcohol, and the 
filtered liquid allowed to evaporate spontaneously, when the 
morphine salt may be deposited in its crystalline state. A por- 
tion of any deposit of the salt thus obtained, is dissolved in a 
small quantity of pure water, and the nature of the acid de- 
termined by appropriate tests. 
From the Tissues.—Thus far, with very few exceptions, 
there seems to have been an entire failure to recover the poison 
from the tissues, in poisoning by opium, and its active alkaloid. 
And in the examination of the liver of two different animals 
poisoned by the drug, we met with similar results. If it be 
desired to examine the tissues for the absorbed poison, the solid 
organ, as a portion of the liver, cut into very small pieces and 
triturated in a mortar, is made into a thin paste with water con- 
taining a little alcohol, then acidulated with acetic or sulphuric 
acid, and the whole digested, with frequent stirring, at a mod- 
erate heat for about an hour. When the mass has cooled, the 
liquid is strained through muslin, and the solids upon the 
strainer well washed with diluted alcohol, and strongly pressed. 
The mixed liquids may then be examined after the manner 
already described. 
From the Blood.—Among various methods pursued for the 
recovery of minute quantities of meconic acid and morphine, 
when purposely added to healthy blood, the following gave the 
best results. The fluid, acidulated with acetic acid in the 
proportion of about eight drops of the concentrated acid for RECOVERY FROM THE BLOOD. 
501 
each fluid ounce of blood, is thoroughly agitated, best in a tol- 
erably wide-mouthed bottle, with an equal volume of strong 
alcohol, and the mixture gently heated in a porcelain dish on a 
water-bath, until the albuminous matter has collected into little 
flakes. The cooled mass is thrown on a wet linen strainer, 
and the solids well washed with alcohol, and strongly pressed. 
These are again thoroughly mixed with fresh alcohol, gently 
warmed, and the liquid strained as before. The united strained 
liquids are now concentrated on a water-bath to a small volume, 
again strained, and then filtered. If during the concentration 
of the liquid, much solid matter separates, as is usually the 
case, it is removed by a strainer. 
The filtered liquid thus obtained, is evaporated to dryness 
on a water-bath, the residue digested with a small quantity of 
nearly absolute alcohol, the solution filtered, and the filtrate 
evaporated to dryness. This residue is gently warmed with a 
small quantity of water, and the liquid filtered. On now treat- 
ing the filtrate with acetate of lead, any meconic acid present 
will be precipitated as meconate of lead: it should be borne in 
mind that under these circumstances, the lead reagent not un- 
frequently produces a yellowish-white precipitate, even in the 
absence of meconic acid. Any precipitate thus obtained, is 
separated by a filter and examined in the usual manner for the 
organic acid, while the filtrate is tested for morphine. 
The repeated digestions with alcohol, in the above process, 
are rendered necessary on account of the extreme tenacity with 
which these opium principles,' especially the meconic acid, ad- 
here to the albuminous matter of the blood. In fact, this organic 
acid forms with albumen a precipitate, which is almost insoluble 
111 water, and only slowly yields the acid to alcohol. 
In operating on a fluid ounce of blood, according to this 
method, the smallest quantities of meconic acid and morphine 
from which we succeeded in recovering crystals of both sub- 
stances, were the twentieth part of a grain of each. In one of 
these instances, the final morphine solution being concentrated 
to three drops, two of the drops gave respectively with nitric 
acid and sesquichloride of iron, very satisfactory evidence of 
the presence of the alkaloid, while the third, when exposed to 502 
MECONIC ACID AND MORPHINE. 
the vapor of ammonia, and then to the air for several hours, 
deposited four comparatively large groups of crystals of the 
pure alkaloid. In the same case, the evidence of the presence 
of the meconic acid, was about equally satisfactory. 
With mixtures containing smaller quantities of the opium 
principles, the final solutions, even when only the 100 th part of 
a grain of each substance had been added, gave results that no 
doubt were due to the presence of these principles; yet the 
reactions were by no means conclusive. On examining for only 
one of these substances, crystals may be obtained from a some- 
what smaller quantity of either than before stated. 
On applying the foregoing method to the examination of the 
blood of eight different dogs and cats poisoned by opium, the 
final solutions in some instances gave results, which there is 
little doubt were due to the presence of meconic acid and mor- 
phine ; while in others, they failed to reveal the presence of a 
trace of either of these substances. In no instance, however, 
were crystals obtained or were the results, with perhaps a 
single exception, such as would have been satisfactory in an 
unknown case- 
in the exception just mentioned, two grains of morphine in 
solution, had been given to a large cat; an hour afterwards, an 
ounce of laudanum was administered, and in another hour, an 
ounce more. In an hour after the last dose, the animal was 
killed by a blow on the head, and four ounces of blood were care- 
fully taken from the body. On treating the whole of the fluid 
after the manner before shown, and concentrating the final solu- 
tion supposed to contain meconic acid, to two drops, and testing- 
one of these directly with sesquichloride of iron, and evaporat- 
ing the other to dryness and testing the residue in the same 
manner, both gave results identical with those occasioned by 
minute traces of the organic acid. So, also, the morphine solu- 
tion, when reduced to two drops and these tested separately by 
nitric acid and a persalt of iron, gave equally distinct evidence 
of the presence of the alkaloid. 
Bearing in mind, that at most only a minute quantity of the 
organic poisons enter the blood, the great loss attending the 
separation of the opium principles from this fluid, and the want FAILURE TO DETECT. 
503 
of delicacy and precision of the tests under these circumstances, 
we Avere not much disappointed in the results of the foregoing 
experiments. 
The Urine.—According to M. Bouchardat, morphine when 
taken either in its free state or under the form of opium, speed- 
ily appears in the urine 5 and may he detected by the liquid 
yielding a reddish-brown precipitate with a solution of iodine 
in iodide of potassium. Since, however, as we have already 
seen, this reagent also produces similar precipitates with most 
of the other alkaloids and with certain other organic substances, 
this reaction in itself could by no means be regarded as direct 
proof of the presence of this alkaloid. Moreover, we find that 
the reagent not unfrequently throws down a precipitate from 
what may be regarded as normal urine5 while on the other 
hand, it sometimes fails to produce a precipitate, even Avhen 
comparatively large quantities of the alkaloid have been pur- 
posely added to this liquid. 
Failure to detect the Poison.—lt has not unfrequently 
happened, that there was a failure to detect a trace of either 
meconic acid or of morphine in any part of the alimentary canal, 
even when large quantities of the poison had been taken, and 
the conditions for its detection Avere apparently very favorable. 
Thus, in a case related by Dr. Christison, he failed to obtain 
any direct evidence of the presence of the poison in the con- 
tents of the stomach of a young woman who died in five hours 
after taking not less than tAvo ounces of laudanum. In another 
case, the contents of the stomach evacuated two hours after 
seven drachms of laudanum AArere SAvalloAved, had no odor of 
opium, nor did they reveal the presence even of meconic acid. 
Since the tests and methods for separating meconic acid from 
foreign substances are someAvhat more satisfactory than those 
for morphine, the acid has sometimes been detected Avhen there 
Was a failure to detect the alkaloid. 
On the other hand, the poison has been detected, even Avhen 
taken in comparatively only small quantity and death Avas de- 
layed for several hours. In a case related by Dr. Skae, in 
which not more than half an ounce of laudanum had been taken, 
and death did not occur until thirteen hours afterwards, the 504 
NARCOTINE. 
contents of tlie stomach furnished evident indications of the 
presence of morphine, and faint evidence of rneconic acid. It 
need hardly he remarked, that since opium or its active alka- 
loid is so frequently administered medicinally, the detection of 
mere traces of the poison in the dead body would not in itself 
be positive proof that it was the cause of death. 
Quantitative Analysis.—For the purpose of estimating the 
quantity of morphine present in an aqueous solution of any of 
its salts, the somewhat concentrated solution may be slightly 
supersaturated with pure aqua ammonia, and allowed to stand 
quietly in a cool place for about twenty-four hours. The alka- 
loid, with the exception of the merest trace, will now be pre- 
cipitated in its crystalline form. The crystals are then care- 
fully separated from the liquid, washed with absolute ether, 
dried at the ordinary temperature, and weighed. One hundred 
parts by weight of the pure crystallised alkaloid represent 123*8 
parts of crystallised chloride of morphine, C 34 HCI, 6 
Aq.; 125 parts of the crystallised sulphate, C 34 HO, S03, 
5 Aq.; or 118*8 of the acetate of morphia, C 34 HO, 
c4h303. 
The quantity of opium or morphine found in the stomach, 
in poisoning by one or other of these substances, is usually too 
minute to admit of a direct quantitative analysis. Under these 
circumstances, the quantity may sometimes be estimated with 
considerable accuracy by observing the intensities of the reac- 
tions of the reagents applied, and comparing these with the 
reactions of known quantities of the poison. 
IV. Narcotine. 
History.—The existence of narcotine was first pointed out, 
in 1803, by Derosne, but Robiquet, in 1817, Avas the first to 
indicate its chemical nature. Blyth, in 1844, assigned to it the 
formula C 46 The more recent investigations of Messrs. 
Matthiessen'and Foster, led them to adopt the formula 
N014. (Jour. Chera, Soc., 1863, p. 342.) Wertheim has de- 
scribed three homologous forms of narcotine in opium, ha\fing CHEMICAL PROPERTIES. 
505 
the formulae C 46 and C4BH27N014, which he 
named, respectively, methylo-, ethylo-, and propylo-narcotine, 
from the fact that when passed over soda-lime, they yield meth- 
ylamine, ethylamine and propylamine. The investigations of 
Matthiessen and Foster, as well as those of Dr. Anderson, how- 
ever, render the existence of these varieties very doubtful. 
Narcotine usually constitutes from six to eight per cent, of 
good Smyrna opium; but in some varieties of the drug, it forms 
only about one per cent. As this substance may be extracted 
from the drug by ether, without the addition of either an alkali 
or an acid, it would appear that it exists principally in its free 
state. It has only feebly basic properties. 
Preparation.—This substance may be obtained, either by 
adding ammonia to the mother-liquor from which chloride of 
morphine has been prepared, or by digesting the insoluble part 
of opium in acetic acid, and precipitating by ammonia. The 
impure narcotine is purified by digesting its hot alcoholic solu- 
tion with animal charcoal, and recrystallising (Gregory). 
Physiological Effects.—Much discrepancy has existed among 
experimentalists in regard to the action of narcotine upon the 
animal system, some observers considering it as almost inert, 
whilst others attribute to it narcotic properties. These narcotic 
effects, however, may have been due to the presence of mor- 
phine in the preparation employed. Recently, Dr, O’Shaugh- 
nessy, of Calcutta, has attributed to it powerful antiperiodic 
properties, and has used it, he states, with great success in the 
treatment of intermittent fever. He prescribed it in doses of 
three grains, three times a day. 
Chemical Properties. —ln its pure state, narcotine crys- 
tallises in the form of transparent, colorless, rhombic prisms, 
which contain one equivalent of water, C 44 Aq.; some- 
times, however, it appears in the form of oblong plates, and at 
others, as a granular powder. In its solid state, it is nearly 
destitute of taste, but when in solution, it has an intensely bit- 
ter taste, even exceeding that of morphine. When moderately 
heated, it parts with its water of crystallisation and fuses to a 
colorless liquid; at higher temperatures, it takes fire, burning 
with a smoky flame. Under the action of oxidising agents, 506 
NARCOTINE. 
narcotine is readily decomposed, giving rise to a variety of new 
compounds, among which is opianyl, one of the other opium 
principles. The pure alkaloid, when in solution, has little or 
no action upon reddened litmus-paper, in which respect it dif- 
fers from morphine 5 so, also, unlike morphine, it fails to strike 
a blue color either with a persalt of iron, or a mixture of iodic 
acid and starch. 
Narcotine fails to neutralise diluted acids, but it readily 
unites with them, forming salts, which, for the most part, are 
uncrystallisable. Concentrated sulphuric acid slowly dissolves 
the alkaloid to a yellow solution, which when stirred with a 
crystal of nitrate of potash, acquires a deep blood-red color. 
When the simple acid solution is moderately heated, it acquires 
a purplish color, even when only a very minute quantity of the 
alkaloid is present. When the acid solution is stirred with a 
crystal of bichromate of potash, the results depend much upon 
the relative quantity of the salt employed (see post). Concen- 
trated nitric acid also dissolves the alkaloid to a more or less 
yellow solution; hydrochloric acid dissolves it without change 
of color. It is slowly soluble in large excess of concentrated 
acetic acid, but insoluble in the diluted acid. 
When large excess of powdered narcotine is digested for 
twenty-four hours, at the ordinary temperature, with pure water, 
this liquid fails to dissolye even the 20,000 th part of its weight 
of the alkaloid. Absolute ether, under similar circumstances, 
takes up one part of the alkaloid in 208 parts of the liquid. 
Narcotine is soluble in all proportions in chloroform, and dis- 
solves readily in alcohol, but is insoluble in the caustic alkalies. 
The salts of the alkaloid, are, for the most part, readily soluble 
in water and in alcohol. 
Narcotine and morphine may be separated from each other 
by agitating the mixture with chloroform or ether, which will 
dissolve the former but not the latter; so, also, these substances 
may be separated by a solution of either of the fixed caustic 
alkalies or by diluted acetic acid, which will take up the mor- 
phine but not the narcotine. 
Narcotine may be readily separated from aqueous solutions 
of its salts by treating the solution with slight excess of a free BEHAVIOR WITH THE ALKALIES. 
507 
alkali, and agitating the mixture with chloroform or ether. 
Upon spontaneous evaporation, the extracting liquid will usu- 
ally leave the alkaloid in the form of beautiful groups of brill- 
iant crystals, similar to those of the crystallised acetate (Plate 
VIII, fig. 3). 
In the following examination of the reactions of narcotine 
when in solution, the pure alkaloid was dissolved in water by 
the aid of the least possible quantity of hydrochloric acid. The 
fractions employed, indicate the amount of pure alkaloid in so- 
lution in one grain of water; and, unless otherwise intimated, 
the results refer to the behavior of one grain of the solution. 
1. The Alkalies and their Carhondtes. 
Caustic potash, soda, and ammonia, as well as their carbon- 
ates, produce in aqueous solutions of salts of narcotine a white 
precipitate of the free alkaloid, which is insoluble in even large 
excess of the precipitant and in diluted acetic acid, but readily 
soluble in hydrochloric and nitric acids. After a little time, 
the precipitate becomes crystalline. 
1. ywo grain of narcotine, in one grain of water, yields a very 
copious, amorphous deposit, and very soon, the mixture 
becomes a nearly solid crystalline mass. 
2. yirg-o grain, yields an immediate precipitate, which in a little 
time becomes converted into beautiful, and somewhat char- 
acteristic, crystalline tufts, Plate VIII, fig. 2. 
3. ro7o o o grain: an immediate cloudiness, and in a few mo- 
ments crystals appear; after a little time, there is a quite 
good crystalline precipitate, the crystals having the forms 
just illustrated. 
d. Totqwo grain: if only a very minute trace of the reagent be 
employed, the mixture soon becomes opalescent, and after 
a little time, especially when examined by the microscope, 
yields a very satisfactory deposit of crystalline needles. 
This precipitate fails to appear in the presence of even 
very slight excess of the reagent. 
If a drop of an aqueous solution of a salt of narcotine be 
exposed to the vapor of ammonia, it soon becomes covered with 508 
NARCOTINE. 
a white crystalline film, even when it contains only the 5,000 th 
part of its weight of the alkaloid. 
2. Sulphuric Acid and Nitrate of Potash. 
If a solution of narcotine or of any of its salts be evaporated 
to dryness, the residue dissolved in a small quantity of concen- 
trated sulphuric acid, and then a small crystal of nitrate of 
potash or a trace of free nitric acid be stirred in the mixture, 
the latter quickly acquires a deep blood-red color, even if only 
a minute quantity of the alkaloid be present. This color is 
discharged by large excess of free nitric acid. 
1. x"5~o grain of narcotine, when dissolved in a single drop of 
the concentrated acid, and a small crystal of nitre added, 
yields a deep red coloration. If the nitre be first dis- 
solved in the acid and the mixture then allowed to flow 
over the narcotine deposit, the latter immediately assumes 
a deep red color, and slowly dissolves to a solution of the 
2. r.Wo grain: if the acid mixture be flowed over the deposit, 
the latter becomes blood-red, and soon dissolves to a yel- 
same hue. 
3- roT5“o“o grain: the deposit acquires a red color, and very 
low solution. 
soon dissolves to a faintly yellow solution. 
This is one of the most characteristic tests yet known for 
the detection of narcotine. Under its action, the true nature of 
the precipitate produced by the caustic alkalies or their carbon- 
ates, may be fully established. For this purpose, the precipi- 
tate is washed, dried, then dissolved in a drop of sulphuric acid, 
and a small crystal of nitre stirred in the solution. 
When a solution of narcotine in concentrated sulphuric acid 
is stirred with a very small crystal of bichromate of potash, the 
fluid acquires a beautiful wine color, which remains unchanged 
for many days. If, however, an excess of the potash salt be 
used, the liquid passes through several colors, and ultimately 
becomes either green or blue, the final color depending upon 
the relative amount of salt employed. The permanent color is 
readily obtained by stirring the potash salt in the acid solution ACETATE OF POTASH TEST. 
509 
until it imparts the desired tint, and then removing the crystal 
from the mixture. The color may thus be obtained from even 
a very minute quantity of the alkaloid. 
3. Acetate of Potash. 
A solution of acetate of potash produces in aqueous solutions 
of salts of narcotine a white precipitate of the acetate of narcot- 
ine, which is insoluble in large excess of the precipitant, but 
readily soluble in most free acids, and in excess of the narcot- 
ine solution. If, therefore, the solution contain a free acid, .or 
if excess of the reagent be not added, the mixture may fail to 
yield a precipitate. The formation of the precipitate from dilute 
solutions, is much facilitated by stirring the mixture. 
1. you- grain of narcotine, in one grain of water, yields a very 
copious, amorphous deposit, which after a time, becomes 
converted into beautiful groups of crystals, Plate VIII, 
fig. 3. 
2. y;xoi> grain: an immediate cloudiness, and soon, a quite good 
crystalline deposit. 
3. stxoo grain, yields, after a little time, a good deposit of crys- 
4. roJoU'o grain: after a few minutes, crystals appear. 
5. 2~u,0 o o grain: after several minutes, crystalline needles ap- 
talline needles. 
pear along the edge of the drop, and after a time, there 
is a very satisfactory deposit. 
The same precipitate is thrown down from solutions of salts 
of narcotine by other acetates, such as the acetate of baryta, 
zinc, and of lead; but the reactions of these, especially the last 
mentioned, are not quite so delicate as that of the potash salt. 
The production of a precipitate by the neutral alkaline ace- 
tates is rather characteristic of narcotine, since it is the only 
substance, except solutions of salts of silver and suboxide of 
mercury, with which they produce a precipitate, at least in the 
form of an acetate. In solutions containing silver or mercury, 
however, the reagent fails to produce a precipitate unless the 
solution be quite concentrated and a corresponding solution of 
the reagent be employed. 510 
NARCOTINE. 
As the acetates thus serve for the detection of narcotine, so 
on the other hand, solutions of salts of the alkaloid, serve for 
the precipitation of combined acetic acid, for which heretofore we 
had no ready precipitant. However, as the acetate of narcot- 
ine is readily soluble in excess of a soluble salt of the alkaloid, 
the latter is not so delicate a test for the acetates as these are 
for narcotine. 
4. Chromate of Potash. 
Protochromate of potash throws down from aqueous solutions 
of salts of narcotine a yellow amorphous precipitate, which after 
a time becomes crystalline. The precipitate is readily soluble 
in acids, even acetic acid. 
1. grain of narcotine, in one grain of water, yields a very 
copious deposit, which slowly assumes the crystalline form. 
2. rrrou grain: a quite good precipitate, which soon yields crys- 
talline tufts of the same form as produced by the caustic 
alkalies (Plate VIII, tig. 2). 
3. rroVo grain: much the same as 2. The formation of the 
crystals is much facilitated by stirring the mixture. 
4. xoßTui) grain, yields in a very little time, especially by stir- 
ring, a good crystalline deposit. 
5. xarlnro grain: after a few minutes, a very satisfactory de- 
posit of crystalline needles and tufts. 
The forms of the crystals produced by this reagent are 
somewhat peculiar to solutions of narcotine. 
Bichromate of potash produces in somewhat strong solutions 
of salts of the alkaloid a yellow amorphous precipitate, which 
after a time becomes granular. One grain of a 100 th solution of 
the alkaloid yields a copious deposit; and a similar quantity of 
a 500 th solution, a quite fair, light yellow precipitate; but a 
I,oooth solution fails to yield any visible change. 
5. Sulphocyanide of Potassium. 
This reagent occasions in solutions of salts of narcotine a 
white precipitate, which is insoluble in the alkalies, but readily 
soluble in acids, even acetic acid. lODINE TEST. 
511 
1. yiro grain of narcotine, yields a very copious deposit, which 
soon becomes a mass of crystals of the same form as those 
produced by the caustic alkalies. 
2. r,iroi) grain: an immediate precipitate, which soon becomes 
crystalline. 
3- totUo grain: after a little time, especially if the mixture be 
stirred with a glass rod, it yields a very satisfactory crys- 
talline deposit. 
4. Tiriroo grain: after a time, a quite satisfactory deposit of 
crystalline needles. 
This reagent produces no precipitate in solutions of salts of 
morphine. 
6. Ter chloride of Gold. 
Terchloride of gold produces in solutions of salts of narcot- 
ine a bright yellow, amorphous precipitate, the color of which 
is permanent, even upon the addition of caustic potash : in this 
respect narcotine differs from morphine. Upon heating the 
mixture, the precipitate dissolves, but it is reproduced as the 
solution cools. The precipitate is but very sparingly soluble in 
large excess of acetic acid. 
1. yUf grain of narcotine, in one grain of water, yields a very 
copious precipitate. 
2. yy-00- grain: a very good deposit, which is insoluble in sev- 
eral drops of a strong solution of caustic potash. 
B. yorhro grain, yields a very satisfactory precipitate. 
4. yO7WO grain: after a little time, a quite perceptible de- 
posit. 
5. tot'oTjt grain, yields a perceptible turbidity. 
7. lodine in lodide of Potassium, 
A solution of iodine in iodide of potassium throws down 
from solutions of salts of narcotine a reddish-brown, amorphous 
precipitate, which is nearly insoluble in the caustic alkalies, and 
only very sparingly soluble in acetic acid, 
k TTo grain of narcotine, yields a very copious deposit, 
k rroVo grain: a copious precipitate. 512 
NARCOTINE. 
3. TotVoo grain, yields a quite good precipitate, which is readily 
soluble to a clear solution in caustic potash. 
4. grain : a brownish-yellow deposit. 
5. ywoVcTo grain, yields a very perceptible turbidity 
8. Bromine in Bromohydric Acid 
A solution of bromohydric acid saturated with bromine, 
produces in solutions of salts of narcotine a bright yellow, amor- 
phous precipitate, which is insoluble in large excess of the pre- 
cipitant, and only sparingly soluble in acetic acid. Upon the 
addition of caustic potash, the precipitate acquires a white 
color, except when produced from very dilute solutions, when 
it dissolves to a clear liquid. 
1. Yo? grain of narcotine, yields a very copious precipitate, 
which after a time dissolves, but it is reproduced upon 
further addition of the reagent. 
2. i7ctols grain; a copious precipitate, which is soluble in caus- 
tic potash, but is almost immediately replaced by a white 
deposit. 
B. TutVuTi grain: a quite good deposit, which when dissolved in 
potash, yields a slight, white precipitate. 
4. rtuoiro grain, yields a quite distinct, yellowish precipitate. 
5. rroVoo grain: a quite distinct cloudiness. 
9. Ferrocyankle of Potassium. 
This reagent produces in aqueous solutions of salts of nar- 
cotine a dirty-white, amorphous precipitate, which is very read- 
ily soluble in acetic acid, but insoluble in large excess of the 
precipitant. 
1. yoo" grain of narcotine, in one grain of water, yields a quite 
copious deposit. 
2. r,Wo grain: a very good precipitate. 
3. rovWu grain, yields a quite strong turbidity. 
Ferricyanide of 'potassium throws down from quite strong 
solutions of narcotine a yellow, amorphous precipitate, which is 
readily soluble in excess of the precipitant, and in acetic acid. CODEINE. 
10. Carhazotic Acid. 
An alcoholic solution of carhazotic acid throws down from 
solutions of salts of narcotine a bright yellow, amorphous pre- 
cipitate, which is slowly soluble in large excess of the precip- 
itant, and also in large excess of acetic acid. 
1. xw grain of narcotine, yields a very copious precipitate, 
2. j J 0-q grain : a very good deposit. 
which remains amorphous. 
3. jo;Vu o grain, yields a quite obvious precipitate. 
Bichloride of Platinum produces in somewhat strong solu- 
tions of salts of narcotine, a light-yellow amorphous precipitate, 
which is sparingly soluble in acetic acid. One grain of a 100 th 
solution of the alkaloid, yields a very copious precipitate, and 
the same quantity of a I,oooth solution, a quite fair deposit; 
but a 2,500 th solution yields no indication. Chloride of palla- 
dium produces similar results. Tannic acid and corrosive subli- 
mate throw down from concentrated solutions of the alkaloid, 
white amorphous precipitates. 
When somewhat strong solutions of salts of narcotine are 
treated with a stream of chlorine gas, the liquid quickly assumes 
a yellow color, which soon changes to reddish-brown; on now 
adding a solution of ammonia, the mixture acquires a deep 
brown color. Ten grains of a 100 th solution of the alkaloid, 
will yield these results. A similar quantity of a I,oooth solution, 
when treated with the gas, acquires a distinct yellow tint, which 
lfs changed to reddish-brown by ammonia. In these reactions, 
narcotine closely resembles morphine. 
V. Codeine. 
History.—Codeine, or codeia, as it is frequently called, was 
first discovered, in 1832, by M. Robiquet. It exists in opium 
ln combination with meconic acid, and usually forms consider- 
ftbly less than one per cent, of the crude drug. The formula 
f°r codeine, in its anhydrous state, according to Grerhardt, is 
33 514 
CODEINE. 
C 36 in its crystalline form, it usually contains two equiv- 
alents of water of crystallisation. It has a bitter taste, and 
strong alkaline properties, quickly restoring the blue color of 
reddened litmus-paper. 
Preparation.—Codeine may be obtained, according to Dr. 
Gregory, by concentrating the mother-liquor from which mor- 
phine has been precipitated, when, after a time, a mixture of 
the chlorides of codeine and morphine will be deposited. This 
deposit is dissolved in a little hot water, and the solution treated 
with excess of potash, which precipitates the codeine, partly in 
the form of crystals, and partly as a viscid mass, which soon 
becomes solid and crystalline; at the same time, most of the 
morphine present remains in solution in the alkaline liquid. 
The precipitate is then treated with ether or with water, either 
of which will dissolve the codeine, while any morphine present 
will remain undissolved. The ethereal solution, upon spontane- 
ous evaporation, leaves the alkaloid in the form of beautiful an- 
hydrous prisms; while the aqueous solution deposits it in the 
form of octahedral crystals, containing two equivalents of water 
of crystallisation. 
Physiological Effects.—The statements in regard to the effects 
of codeine, when taken into the stomach, have been quite con- 
tradictory. According to the results of some observers, it has 
strong narcotic properties, similar to those of morphine, only 
that it has to be given in larger quantity, and never induces 
the unpleasant after-effects so frequently witnessed in the ad- 
ministration of that alkaloid. Dr. Gregory observed that in 
some instances it excited a sense of intense itching of the entire 
skin, and states that probably the itching caused in some per- 
sons by opium and some of the salts of morphine may be due 
to the action of codeine, this substance being not unfrequently 
present in some of the preparations of morphine. On the other 
hand, other observers were led to conclude that codeine was 
nearly or entirely destitute of narcotic properties. Dr. Wood 
is of the opinion, that it is among the principles upon which 
opium depends for its peculiar properties. 
Chemical Properties.—Codeine is a wdiite, crystallisable, 
and strongly basic substance, precipitating the oxides of many CHEMICAL PROPERTIES. 
515 
of the metals from solutions of their salts, but in its turn being 
precipitated by the caustic alkalies. It is readily distinguished 
from morphine by not striking a blue color with a persalt of 
iron. When heated, it first parts with its water of crystallisa- 
tion, and at about 800° F., fuses to a colorless liquid, which at 
higher temperatures takes fire, burning with the evolution of 
dense fumes. 
Codeine completely neutralises diluted acids, combining with 
them to form salts, most of which are readily crystallisable. 
Concentrated sulphuric acid slowly dissolves the pure alkaloid 
without change of color; if a solution of this kind be heated 
on a water-bath, it acquires a beautiful purple color, even when 
only a minute quantity of the alkaloid is present: this result, 
however, is somewhat influenced by the amount of acid and 
heat employed. A small crystal of nitrate of potash stirred in 
the cold acid solution, yields a faint greenish, then reddish col- 
oration ; while a crystal of bichromate of potash, yields a green 
color, due to the formation of sesquioxide of chromium. Con- 
centrated nitric acid, it is said, produces no change of color 
with codeine 5 but the few samples we have examined became 
more or less orange-yellow, and dissolved to a yellow solution, 
when treated with this acid, especially when a not inconsider- 
able quantity of the alkaloid was employed. Similar results 
have also been obtained by various other observers. Chloride 
°f tin added to the nitric acid solution, causes it to undergo 
little or no change. Hydrochloric acid readily dissolves the 
alkaloid to a colorless solution, which remains unchanged upon 
the application of heat. 
When excess of finely-powdered codeine is digested with 
pure water at the ordinary temperature, with frequent agitation, 
for twenty-four hours, the solution then filtered, and the filtrate 
evaporated to dryness, it leaves a crystalline residue indicating 
that one part of the alkaloid had dissolved in 128 parts of the 
fluid. It is much more freely soluble in hot water, from which, 
however, much of the excess separates as the solution cools. 
Absolute ether, under the foregoing conditions, dissolves one 
part of the alkaloid in 55 parts of the liquid. Chloroform, un- 
der similar conditions, takes up one part in 21-5 parts of fluid. 516 
CODEINE. 
The alkaloid is also freely soluble in alcohol, and somewhat sol- 
uble in solutions of the caustic alkalies, but less so than in pure 
water. The salts of codeine are, for the most part, readily 
soluble in water, and in alcohol; but they are nearly or alto- 
gether insoluble in ether, and in chloroform. 
Aqueous solutions of codeine, when not too dilute, have a 
strongly alkaline reaction and a very bitter taste. The alkaloid 
may be extracted from its aqueous solution by agitation with 
ether; but as codeine is not very much less soluble in water 
than in ether, repeated agitations with the latter are required 
for the complete separation of the alkaloid. It is much more 
readily extracted by chloroform. By either of these liquids, it 
may be separated from morphine. The alkaloid may, of course, 
be extracted in a similar manner from aqueous solutions of its 
salts, by first treating them with slight excess of a free min- 
eral alkali. 
The codeine employed in the following investigations, was 
prepared by E. Merck, of Darmstadt; it was in the form of 
large, colorless crystals, and apparently perfectly pure. Its so- 
lutions were prepared in the form of the acetate. The fractions 
indicate the fractional part of a grain of the pure alkaloid in 
solution in one grain of water ,• and, unless otherwise stated, 
the results refer to the behavior of one grain of the solution. 
1. Potash and Ammonia. 
The fixed caustic alkalies and ammonia throw down from 
concentrated aqueous solutions of salts of codeine a white amor- 
phous precipitate of the pure alkaloid, which is readily soluble 
in free acids. 
One grain of a 100 th solution of the alkaloid, yields a quite 
good deposit, which remains amorphous. On account of the 
solubility of codeine in water, solutions but little more dilute 
than that just mentioned fail to yield a precipitate with either 
of these reagents. 
Since tile alkaloid is less soluble in alkaline solutions than 
in pure water, it is partly precipitated from its pure aqueous 
solutions, when not too dilute, by the caustic alkalies. lODINE AND BROMINE TESTS. 
517 
2. lodine in lodide of Potassium. 
A solution of iodine in iodide of potassium produces in solu- 
tions of salts of codeine a reddish-brown precipitate, which is 
readily soluble to a colorless solution in caustic potash ; it is 
also soluble in acetic acid. 
1. ytht grain of codeine, in one grain of water, yields a very 
copious precipitate, which after a time becomes more 
or less crystalline, Plate VIII, tig. 4. The precipitate 
is readily soluble in alcohol, from which after a time it 
separates in the form of crystalline plates, Plate VIII, 
fig. 5, which are especially beautiful under polarised light. 
Solutions but little more dilute than this, fail to yield 
crystals. 
2. grain, yields a copious deposit. 
roTSWo grain: a very good, reddish-yellow precipitate. 
4. sir;Wo grain: a yellowish deposit. 
5. ro'oLoiro grain: a quite perceptible precipitate. 
6* yo'oVo'o grain, yields a distinct turbidity. 
This reagent also produces crystalline precipitates with some 
of the other opium principles ,* but the deposits produced by the 
reagent from most other substances remain amorphous. 
3. Bromine in Bromohydrie Acid. 
A solution of bromohydrie acid saturated with bromine throws 
down from solutions of salts of codeine a yellow amorphous pre- 
cipitate, which after a time dissolves, but it is reproduced upon 
further addition of the reagent. 
To~o grain of codeine, yields a very copious, bright-yellow 
deposit. 
2. ytctoo grain: a copious precipitate. 
3. 1075-00 grain: a fair, yellow deposit. 
4. 2 5.0d0 .grain, yields a quite perceptible cloudiness. 
The reaction of this reagent is common to solutions of most 
of the alkaloids, and also to other organic principles. 518 
CODEINE. 
4. Sulphocyanide of Potassium. 
This reagent occasions in somewhat strong solutions of salts 
of codeine a white crystalline precipitate of the sulphocyanide 
of codeine, which, according to Anderson, has the composition 
C 36 C2XS2, Aq. The precipitate is readily soluble in 
acetic acid. 
1. jinr grain of codeine: after some minutes, crystalline needles 
begin to separate, and after a little time, there is a copious 
crystalline deposit, Plate VIII, fig. 6. If the mixture be 
stirred, it immediately yields crystals, and very soon the 
drop becomes a mass of crystalline groups. 
2. tto grain: by stirring the mixture, crystals soon appear, 
and after a time, there is a very satisfactory deposit. 
This reagent also produces crystalline precipitates with solu- 
tions of several of the other alkaloids. 
5. Bichromate of Potash. 
Bichromate of potash produces in quite strong solutions of 
salts of codeine a yellow crystalline precipitate, which is readily 
soluble in acetic acid. Very concentrated solutions of the alka- 
loid yield beautiful groups of bold, red crystals. 
One grain of a 100 th solution yields no immediate precipi- 
tate, but after standing some time, crystalline tufts separate, 
and the mixture ultimately becomes a nearly solid mass of crys- 
tals, Plate IX, fig. 1. The formation of the precipitate is much 
facilitated by stirring the mixture. 
Protochromate of potash produces with very strong solutions 
of the alkaloid, a yellow precipitate of crystalline plates and 
prisms. 
6. Chloride of Gold. 
Terchloride of gold throws down from solutions of salts of 
codeine a reddish-brown amorphous precipitate, which when 
treated with caustic potash yields a dark bluish mixture. 
1. Yinr grain of codeine, yields a very copious precipitate: after CARBAZOTIC AND NITRIC ACID TESTS. 
519 
standing some time, the supernatant fluid acquires a blu- 
ish color. 
2. rrsVo grain, yields a very good, yellow deposit. 
3. rrcTo-o grain, yields a very distinct cloudiness. 
7. Bichloride of Platinum. 
This reagent precipitates from strong solutions of salts of 
codeine a yellow amorphous deposit, which is readily soluble in 
acetic acid, but unchanged by caustic potash. 
1. grain of codeine, yields a copious deposit, which after a 
time becomes more or less granular. 
2. yyt grain, yields after several minutes, a partly granular 
precipitate. 
8. Garhazotic Acid. 
An alcoholic solution of carbazotic acid produces in solu- 
tions of salts of codeine, a bright yellow, amorphous precipitate. 
1. yto grain of codeine, yields a very copious deposit. 
2. ytot grain: a quite good precipitate. 
3. yxoo grain, yields, after a little time, a quite distinct 
cloudiness. 
9. Nitric Acid and Potash. 
When a small quantity of codeine, in its solid state, is added 
to a drop of concentrated nitric acid, it dissolves with the evo- 
lution of hyponitric acid, yielding an orange-yellow solution, 
which when evaporated to dryness on a water-bath, leaves a 
yellow" residue. If this residue be treated wdth a drop of caus- 
tic potash, it acquires a beautiful orange color, and partially 
dissolves to a solution of the same hue, which is permanent. 
1. ys"o grain of codeine, yields the results just described. 
2. rioo grain; the nitric acid solution leaves a slightly yellow 
residue, which with potash yields a good orange-colored 
mixture. 
'3. TO7WO grain: the slightly yellow residue left by the acid, is 
but little changed by the potash ; but if this mixture be 520 
NARCEINE. 
evaporated, it leaves a yellowish-orange deposit, mixed 
with crystals of the nitrate of potash: a drop of water 
readily dissolves these crystals, and yields a yellow-orange 
mixture, the color of which is permanent. 
lodide of Potassium produces in concentrated solutions of 
salts of codeine, especially upon stirring the mixture, a crystal- 
line precipitate of tufts of needles, Plate IX, fig. 2. 
Corrosive sublimate, ferro-, and ferri-cyanide of potassium, 
sulphate of copper, and nitrate of silver produce no precipitate, 
at least immediately, in a 100 th solution of salts of codeine. 
VI. Narceine. 
History.—Narceine, which is said to form from six to twelve 
per cent, of Smyrna opium, was discovered, in 1832, by Pelle- 
tier. Its formula, according to Dr. Anderson, is C 46 It 
seems to be a neutral substance, yet it will unite with acids to 
form salts, all of which have an acid reaction. The statements 
of observers in regard to the constitution and properties of nar- 
ceine have been very conflicting, and it is probable that two or 
perhaps three different substances have been described under 
this name. 
Preparation.—This substance may be obtained, according to 
Dr. Anderson (Quart. Jour. Chem. Soc., vol. v, p. 257), from 
the mother-liquor of chloride of morphine by diluting it with 
water, filtering, and then adding ammonia as long as a precip- 
itate is produced. Narceine and meconin remain in solution, 
while narcotine, resin, and small quantities of papaverine and 
thebaine are deposited. The filtered liquid is treated with ex- 
cess of acetate of lead, the dirty-brown precipitate produced 
removed by a filter, the excess of lead separated from the fil- 
trate by sulphuric acid, and the liquid saturated with ammonia, 
then evaporated at a moderate temperature to a syrup, when it 
is allowed to stand some days. The precipitate then formed, is 
collected on a cloth and washed with water, then boiled with a 
large quantity of water and the hot solution filtered. On cool- 
ing, the liquid becomes filled with fine silky crystals of narceine, CHEMICAL PROPERTIES. 
521 
which are separated from traces of sulphate of lime by solution 
in alcohol, and further purified by boiling with animal charcoal 
and recrystallisation from water. 
Physiological Effects. Experiments upon inferior animals 
indicate narceine to be an inert substance. 
Chemical Properties.—Narceine crystallises in beautiful, 
colorless, delicate needles, which when dry form an exceedingly 
light, spongy mass. It is unchanged by persalts of iron. At 
a moderate heat it fuses to a clear liquid, and at higher temper- 
atures burns like a resin. 
The narceine used in the present investigations was pre- 
pared by E. Merck; it was in the form of very delicate, color- 
less, silky needles. 
Concentrated sulphuric acid causes the alkaloid to assume a 
reddish-brown color, and dissolves it to a reddish or yellowish- 
red solution, which upon the application of a moderate heat ac- 
quires an intense red color, and at higher temperatures darkens. 
These results, however, are much influenced by the amount of 
acid and heat employed. In no instance, with the single speci- 
men examined, did we obtain the green color described by 
Anderson (Quart. Jour. Chem. Soc., vol. v, p. 259), nor, with 
the diluted acid, the blue color obtained by other observers. 
A crystal of nitrate of potash stirred in the cold acid solution, 
yields a reddish-brown, violet or purple coloration, according to 
the relative quantities of the different substances present: the 
color is discharged by heat. Bichromate of potash produces 
with the acid solution, a dirty-red color, which on the applica- 
tion of heat is changed to green, due to the production of ses- 
quioxide of chromium. 
When treated with concentrated nitric acid, narceine assumes 
an orange-red color and dissolves to a more or less yellow solu- 
tion, which suffers little or no change by a moderate heat. The 
solution is unaffected by chloride of tin, even upon the applica- 
tion of heat. The sample under consideration, when dropped into 
concentrated hydrochloric acid, became blue, and dissolved to a 
perfectly colorless solution. Pelletier described this reaction as 
characteristic of narceine, while Anderson failed to obtain a blue 
color from samples which he considered pure. 522 
NARCEINE. 
When excess of narceine is digested, with frequent agita- 
tion, for twenty-four hours in water at the ordinary temperature, 
it requires 1,660 parts of the liquid for solution. It is much 
more soluble in hot water, from which the excess slowly sepa- 
rates as the solution cools. One part of the alkaloid dissolves 
in five hundred parts of water as soon as the mixture is brought 
to the boiling temperature *, this solution may then be exposed 
for half an hour or longer to a temperature of 60°, before crys- 
tals begin to separate. A concentrated aqueous solution of 
narceine has no action upon reddened litmus. Absolute ether, 
under the foregoing conditions, dissolved one part of narceine 
in 4,066 parts of the liquid. Chloroform, under similar circum- 
stances, dissolved one part in 7,950 parts of liquid. It is much 
more soluble in alcohol than in water, and is also somewhat sol- 
uble in dilute solutions of the caustic alkalies. 
In the following investigations, the 100 th solutions were ob- 
tained by the aid of hydrochloric acid and a gentle heat 5 the 
more dilute solutions were prepai'ed by dissolving the narceine, 
when necessary by the aid of heat, directly in distilled water. 
A 100 th solution of narceine in the form of chloride, unless 
maintained at a gentle temperature, soon becomes filled with a 
network of long, delicate crystalline needles. 
1. lodine in lodide of Potassium. 
A solution of iodine in iodide of potassium produces in solu- 
tion of narceine a reddish-yellow precipitate, which almost im- 
mediately becomes crystalline. The precipitate is slowly soluble 
in large excess of acetic acid. 
1. ywo grain of narceine, in one grain of water, yields a very 
copious deposit, which very soon becomes a mass of crys- 
talline needles and tufts; at the same time, the mixture 
acquires a blue color. The precipitate is readily soluble 
in alcohol, from which it soon again separates in the crys- 
talline form. 
2. ytcToo grain, yields a copious precipitate, which soon changes 
to exceedingly delicate crystalline tufts, Plate IX, fig. 3. 
After a time, the mixture acquires a more or less blue color. GOLD AND PLATINUM TESTS. 
3. grain, after a time, yields some few crystalline tufts, 
of the forms just illustrated. 
The production of these crystalline tufts is quite peculiar to 
solutions of narceine. 
2. Bromine in Bromohydric Acid. 
A solution of bromine in bromohydric acid throws down from 
solutions of narceine, a bright yellow, amorphous precipitate, 
which after a time dissolves, but is reproduced upon further 
addition of the reagent. The precipitate is soluble in acetic 
acid and in alcohol.1 
1. Yinr grain of narceine, in one grain of water, yields a very 
copious precipitate. 
2. iToiro grain : a copious deposit 
3- io, o 0~0 grain, yields after a very little time, a quite fair, yel- 
low precipitate. 
3. Chloride of Gold. 
Terchloride of gold occasions in solutions of narceine, a yel- 
low flocculent precipitate, which remains unchanged in color. 
The precipitate is soluble in the mixture upon the application 
of heat, and reproduced unchanged as the solution cools. It is 
readily soluble to a clear solution in caustic potash. 
1. xiTo grain of narceine, yields a very copious deposit. 
2. ttitoo grain : a very good precipitate. 
3. jo,ob ii grain, yields after a little time, a perceptible turbid- 
ity, which soon becomes quite well marked. 
4. Bichloride of Platinum. 
This reagent precipitates from solutions of narceine a yellow 
flocculent deposit, which is readily soluble in acids. After a 
time, the precipitate yields granules and crystalline needles. 
1. ifo grain of narceine, yields a very good deposit. 
2. two grain: a very fair precipitate. 
3. r.Foo grain: no indication. 524 
OPIANYL. 
5. Carhazotic Acid. 
An alcoholic solution of carhazotic acid causes in solutions 
of narceine, a yellow amorphous precipitate, which is readily 
soluble in acetic acid. 
1. grain of narceine, yields a copious deposit. 
2. r,“oVo grain: a good precipitate. 
3. sTtroo grain, yields after a little time, a quite satisfactory 
deposit. 
6. Bichromate of Potash. 
Bichromate of potash produces in strong solutions of nar- 
ceine a yellow amorphous precipitate, which soon becomes crys- 
talline. 
1. yyij grain of narceine, yields a very copious precipitate, which 
almost immediately becomes a mass of crystals. 
2. mTo grain, yields a very good crystalline deposit, Plate 
IX, fig. 4, 
Protochromate of potash produces, in solutions of the alka- 
loid, much the same results as the bichromate. 
lodide of potassium, sulphocyanide of potassium, corrosive 
sublimate, ferro-, and ferri-cyanide of potassium produce no 
precipitate in even saturated aqueous solutions of narceine. 
VII. Opianyl 
History.—Opianyl, or Meconine, as it was formerly named, 
was discovered, in 1826, by M. Dublanc, but first described by 
M. Couerbe, in 1832. It is a neutral, crystallisable substance, 
and forms less than one per cent, of opium. Its formula, as 
first determined by Couerbe, and afterwards confirmed both by 
Regnault and by Anderson, is C2oHIOOB. It, therefore, differs 
from the alkaloids in not containing nitrogen. 
Preparation.—Opianyl may be obtained from the mother- 
liquor from which narceine has been prepared, by agitating it 
with successive portions of ether, as long as this liquid becomes CHEMICAL PROPERTIES. 
525 
colored. The united ethereal solutions are then evaporated, and 
the brown syrup treated with dilute hydrochloric acid, which 
dissolves the papaverine, while the opianyl, together with some 
resin, remains. The opianyl is then crystallised several times 
from boiling water, with the addition of animal charcoal, when 
it finally separates in colorless needles. It may also be obtained 
by acting upon narcotine with nitric acid. 
Physiological Effects.—From the few experiments made with 
this substance, it would seem to be inert. 
Chemical Properties.—Opianyl readily crystallises in the 
form of long, colorless, six-sided prisms, or as delicate needles; 
it has a somewhat bitter taste. At a moderate heat, it fuses to 
a colorless liquid, which upon cooling, solidifies to a radiated 
crystalline mass; at higher temperatures, it is dissipated in the 
form of white fumes. When cautiously heated in a glass tube, 
it sublimes in beautiful crystals (Anderson). Although a per- 
fectly neutral body, it is soluble in acids. 
The following observations are based upon the examination 
of a single specimen of opianyl, prepared by E. Merck. It 
was in the form of delicate, snow-white crystals. 
Concentrated sulphuric acid dissolves it to a colorless solu- 
tion, which when heated acquires either a beautiful blue or 
purple color, the hue depending upon the relative quantity of 
acid employed (see post) ; the cooled mixture, upon the addition 
of water, becomes reddish-brown and yields a brownish precip- 
itate. Nitric acid also dissolves it to a colorless solution, which 
on being heated acquires a more or less yellow color, and on 
evaporation leaves a colorless crystalline residue. It is also sol- 
uble in concentrated hydrochloric acid without change of color, 
even upon the application of heat. 
When excess of opianyl is digested in water for several 
hours, with frequent agitation, at a temperature of about 60° F., 
one part dissolves in 515 parts of the liquid. According to 
Couerbe, it dissolves in 265 parts of cold water; while Ander- 
son states that at 60°, it requires 700 parts of this liquid for 
solution. It is much more freely soluble in hot water, but much 
of the excess separates in its crystalline state as soon as the 
solution begins to cool. When excess of opianyl is boiled with 526 
OPIANYL. 
water, it melts under the liquid ; yet, according to Anderson, 
when in its dry state, it requires a temperature of 230° F. for 
its fusion. Absolute ether, when in contact with excess of 
opianyl for several hours, at the ordinary temperature, dissolves 
one part in 186 parts of the liquid. Chloroform dissolves it in 
all proportions. It is also readily soluble in alcohol; but it is 
not more soluble in solutions of the caustic alkalies than in 
pure water. 
In the following investigations, the opianyl was dissolved, 
when necessary by the aid of a very gentle heat, in pure water. 
1. lodine in lodide of Potassium. 
A solution of iodine in iodide of potassium produces in aque- 
ous solutions of opianyl, a yellowish-brown amorphous precip- 
itate, which quickly becomes quite dark-brown, and then changes 
to a mass of yellow crystals, which in their dry state resemble 
spangles of gold-dust. The precipitate is readily soluble in 
alcohol. 
1- s'To grain of opianyl, in one grain of water, yields a very 
copious precipitate, which very soon becomes converted 
into yellow crystals, Plate IX, fig. 5. 
2. r,Wo grain: a good, yellowish-brown deposit, which soon 
darkens. 
6* 27V0U grain, yields after a little time, a slight cloudiness, fol- 
lowed by the precipitation of dark-colored granules. 
The reaction of this reagent is quite peculiar to solutions of 
opianyl. 
2. Bromine in Bromohydric Acid. 
This reagent precipitates from solutions of opianyl a deposit 
of short needles, and groups of hair-like crystals. The precip- 
itate is insoluble in acetic acid, and but slowly soluble in large 
excess of alcohol. 
1. grain: after a few moments, crystals begin to form, and 
soon there is a quite copious deposit, Plate IX, fig. 6; 
after a time, the mixture becomes a colorless mass of 
crystals. SULPHURIC ACID TEST. 
527 
2. y,ooo grain : in a very little while, a quite good crystalline 
deposit. 
3. 2,t00 grain, yields after a little time, a very satisfactory 
crystalline precipitate. 
acteristic of opianyl. 
The production of this crystalline precipitate is quite char- 
3. Sulphuric Acid and Heat. 
When a small quantity of opianyl in its solid state, is heated 
with a very minute portion of concentrated sulphuric acid, it 
yields an intense blue color, which, as the heat is increased, 
changes to purple ; when a larger quantity of acid is employed, 
the heated mixture acquires a transient blue color, which passes 
to purple ; while with a still larger quantity, the mixture, when 
heated, assumes at once a beautiful purple color. This experi- 
ment may be performed in a thin, annealed watch-glass. 
1. y-Jro grain of opianyl, when moistened with a very small 
quantity of the acid, and heated, yields an intense blue 
coloration. 
2. x75~0~0 grain: much the same as 1. For the success of this 
reaction it is essential that the least possible quantity of 
acid be employed. This is best attained by touching the 
deposit with a glass rod moistened with the acid; the mix- 
ture is then heated over the flame of a spirit-lamp, until 
it begins to assume a blue color—which does not usually 
occur until vapors of the acid are evolved—when the heat 
is withdrawn. 
8. ro7<roo grain, when treated as just described, yields very 
satisfactory results. 
4. jsyro'o grain: if the deposit be not distributed over a large 
space, it yields a very distinct blue coloration. 
With a very small quantity of the acid, a blue color may be 
obtained from a much less quantity of opianyl than will yield a 
purple color with a larger quantity of the acid. The produc- 
tion of this blue coloration is quite characteristic of opianyl. 
Nai-cotine when heated with a small quantity of sulphuric acid 
yields a purple mixture, which darkens as the heat is increased. 528 
OPIANYL 
So, also, a sulphuric acid solution of codeine, when heated, 
acquires a purple color. 
A sulphuric acid solution of opianyl, when stirred with a 
few crystals of nitrate of potash, yields a yellow mixture, soon 
changing to a beautiful scarlet-orange color, which but slowly 
fades. Almost the least visible quantity of the substance when 
treated in this manner, with a very small quantity of the acid 
and nitre, yields' very satisfactory results. On heating the mix- 
ture, the orange color is changed to yellow. In these reactions, 
opianyl somewhat resembles narcotine. 
As opianyl forms no definite combinations with acids nor 
metallic oxides, it is not precipitated by the ordinary reagents. 
According to Couerbe, it yields a crystalline precipitate with 
basic acetate of 16ad; but, like Anderson, we failed to obtain 
a precipitate by this reagent. NUX VOMICA. 
529 
CHAPTER 111. 
NUX VOMICA, STRYCHNINE, BRUCINE. 
I. Nux Vomica. 
History and Composition.—Nux vomica is the seed of the 
Strychnos nux vomica, a tree found native in the East Indies, 
and the island of Ceylon. The seeds are flat, nearly round, 
and something less than an inch in diameter, being slightly 
concave on one side, and convex on the other, and covered 
with short, silky, greyish or yellowish hairs, which are attached 
to an investing membrane, and incline towards the circumfer- 
ence of the seed. The seeds are very hard, difficult to pul- 
verise, and when chewed have an intensely bitter taste, but 
they are destitute of any well-marked odor. In its powdered 
state, nux vomica has a yellowish-grey color, and a peculiar 
odor, not very unlike that of liquorice. 
Nux vomica possesses powerful poisonous properties, due to 
the presence of the alkaloids, strychnine and brucine, which 
exist in the seed in combination with a peculiar organic acid, 
known as strychnic, or igasuric acid. The seeds also contain, 
according to the analysis of Pelletier and Caventou, yellow 
coloring matter, gum, a waxy substance, starch, a concrete oil, 
woody fiber, and earthy salts. A third alkaloid, under the name 
of igasui'ine, has more recently been described by M. Desnoix. 
The powdered seeds yield their active properties to water, but 
much more freely to alcohol. Poisoning by this substance, has 
been of quite frequent occurrence. 
Symptoms.—The symptoms produced by poisonous doses of 
nux vomica, or either of its active alkaloids, are very uniform 
m their nature, and quite peculiar. There is at first, a sense 
of numbness in the extremities, with more or less trembling of 
34 530 
NUX VOMICA. 
the muscles, and a feeling of great anxiety. These effects are 
soon succeeded by violent muscular contractions, in which the 
limbs are extended and perfectly rigid, the head thrown back, 
the jaws fixed, the face livid, and the respiration apparently 
suspended. After a little time, varying from a few moments to 
some minutes, the convulsive paroxysm subsides, and the patient 
then feels much exhausted, and is usually extremely sensitive to 
external impressions. This condition, however, is usually of 
short duration, the convulsions being succeeded by others, which 
increase in violence, and speedily run to a fatal termination. In 
some instances, death takes place during a paroxysm, but more 
generally, from extreme exhaustion. The intellectual faculties 
usually remain unaffected, even up to the time of death. The 
time within which the symptoms first manifest themselves, is 
subject to considerable variation, they occurring in some in- 
stances almost immediately, and in others being delayed for 
even more than an hour. 
The following case, reported by Mr. Ollier, and quoted by 
most toxicological writers, well illustrates the usual effects of 
mix vomica. A young woman purposely swallowed, in suspen- 
sion in water, about three drachms of the powder. When seen 
about half an hour afterwards, she was calm and quite well. 
But in about ten minutes more, she was seized with a convulsive 
fit, and in a few minutes afterwards, had another, which was 
soon succeeded by a third: the duration of these paroxysms 
was about two minutes each. During the attacks, the whole 
body was extended and rigid, the legs widely separated, the 
face and hands livid, and the muscles of the former violently 
convulsed: no pulse or breathing could be perceived. In the 
intervals, she was quite sensible; complained of being sick, and 
made many attempts to vomit; had incessant thirst, a very 
quick and feeble pulse, and perspired freely. A fourth attack 
soon followed, in which the whole body was extended to the 
utmost and rigidly stiff. She now fell into a state of asphyxia, 
relaxed her grasp, white foam issued from her mouth, the 
expression of the countenance became most frightful, and death 
ensued in about an hour after the poison had been taken. 
(London Med. Repository, vol. xix, p. 448.) PERIOD WHEN FATAL. 
531 
In a non-fatal case, related by Dr. Basedow, of Merseburg, 
the following symptoms were observed. A young lady took, 
by mistake, a tablespoonful of the powdered drug. She was 
almost instantly deprived of the power of walking, and fell 
down, but still retained her consciousness. When first seen by 
Dr. Basedow, almost immediately afterwards, her countenance 
was pale, and exhibited alternately an expression of indifference 
and anxiety; the eyes were wide open, and the pupils con- 
tracted. The respiration was irregular and short ; the pulse 
irregular and small, and the skin cool. The forearms were 
constantly in a half bent position, and the hands and fingers 
affected with convulsive twitches • but the legs were motionless, 
and rigid, all the muscles being hard and tetanically contracted. 
The patient had not the slightest pain or sickness; but her 
breathing became every moment more difficult, and she com- 
plained of impending suffocation. An emetic was now adminis- 
tered, and its action followed by the exhibition of small doses 
of a mixture of oil of turpentine and sulphuric ether. The 
dyspnoea gradually subsided, and in about six hours after the 
poison had been taken, the tetanic spasms of the muscles of the 
legs, as well as the convulsive movements of the hands, had 
ceased, and the respiration was free; but the patient complained 
of a sense of bruising over the whole body, and pain in the 
limbs, for some days afterwards. (New York Med. and Phys. 
Journal, No. xxx, p. 448.) 
In some few of the recorded cases of poisoning by this sub- 
stance, the first symptoms observed were nausea and vomiting; 
while in others, the tetanic symptoms were followed by purging, 
and inflammation of the stomach and bowels. 
Period when Fatal. —ln fatal poisoning by mix vomica, 
death usually takes place within a very few hours after the 
poison has been taken; but life has been prolonged for some 
days. In a case cited by Dr. Christison, in which a man swal- 
lowed an unknown quantity of the powder, mixed with beer, 
death occurred in fifteen minutes after the poison had been 
taken. (On Poisons, p. 686.) Several instances are related in 
which death took place in from one to two hours. On the other 
hand, in a case cited by Orfila (Toxicology, vol. ii, p. 605), a 532 
NUX VOMICA. 
man swallowed a considerable quantity of the powder, and 
almost immediately was seized with violent convulsions j yet 
death did not occur until the fourth day. 
Fatal Quantity.—ln a case quoted by Dr. Christison, an old 
woman, who was using an alcoholic extract of nux vomica for 
palsy, took an overdose of three grains, which soon produced 
violent tetanic spasms, followed by an attack of inflammation of 
the stomach and intestines, and death on the third day. The 
quantity of the crude powder represented by the extract taken 
in this case, is quite uncertain. The same writer cites another 
instance, related by Hoffmann, in which thirty grains of the 
crude powder, taken in two equally divided doses, caused death. 
(On Poisons, p. 689.) Dr. Taylor mentions two cases, in each 
of which fifty grains of the powder proved fatal: in one of 
these, death took place in an hour, (On Poisons, p. 767.) In 
another instance, two drachms caused death in about two hours. 
Recovery has not unfrequently taken place after large quanti- 
ties of nux vomica had been swallowred; and Prof. G. B. Wood 
states that fifty grains have been given with little or no effect. 
Treatment. The stomach should be emptied as speedily 
as possible, either by means of the stomach-pump or the ad- 
ministration of an emetic. Since the poison, when taken in the 
form of powder, sometimes adheres tenaciously to the walls of 
the stomach, the use of the pump, or the action of the emetic, 
should be continued for some time. Various chemical antidotes 
have been advised, but none of these are reliable. After the 
contents of the stomach have been evacuated, vegetable astrin- 
gents or a solution of iodine in iodide of potassium, might be 
found useful, for the purpose of neutralising any remaining por- 
tions of the poison. Other methods of treatment will be re- 
ferred to hereafter, when considering the antidotes for poisoning 
by strychnine. 
Post-mortem Appearances.—Nux vomica may occasion 
death without leaving any well-marked morbid change in any 
part of the body. In Mr. OlliePs case, before cited, in which 
death took place in an hour, five hours after death, the body 
was as straight and stiff as a statue, so if one of the hands 
was moved the whole body moved with it. On dissection, the CHEMICAL PROPERTIES. 
533 
stomach was found nearly natural, the hlood-yessels of the brain 
congested, and the heart of a pale color, empty, and flaccid. 
In another case, in which about an ounce of the poison had 
been taken and proved rapidly fatal, large quantities of a san- 
guinolent fluid were found in the cavities of the brain, and 
between its membranes; and the lungs, as well as the heart, 
were highly gorged with black fluid blood. The stomach was 
healthy, except a patch of the mucous membrane in the larger 
curvature of the organ, which was evidently inflamed, and of a 
deep red color, the intensity diminishing from the circumference 
to the centre. * 
In the case cited from Orfila, in which death did not take 
place until the fourth day, the following appearances were ob- 
served forty-eight hours after death. The body was consider- 
ably rigid, and of a violet hue. The lateral ventricles of the 
brain, and the cavity of the arachnoid membrane, contained 
large quantities of serum; but no appreciable alteration was 
detected either in the meninges or cerebral substance. The 
internal surface of the stomach presented at different points, a 
color which varied from red to deep black ; and the duodenum 
and upper portions of the small intestines were manifestly in- 
flamed. The lungs were gorged with blood; the heart was 
natural. 
Chemical Properties. 
The physical properties of mix vomica, when in its solid 
state, readily distinguish it from all other substances. If a small 
portion of the powdered seed be moistened with a drop of water, 
and examined under a low power of the microscope, the broken 
fibrous hairs may be readily distinguished, they apparently 
forming a large portion of the powder. The hairs acquire a 
yellow color upon the addition of a solution of iodine in iodide 
of potassium j when the crude powder is thus treated, it assumes 
a deep brown color. When touched with a drop of concentrated 
nitric acid, the powder acquires a deep orange-red color, which 
is slowly discharged by a solution of protochloride of tin. Con- 
centrated sulphuric acid causes it, like most vegetable powders, 
to assume a brownish, then black color. Hydrochloric acid 534 
STRYCHNINE. 
produces little or no change. When moderately heated, the 
powder evolves dense white fumes, having a peculiar odor; at 
higher temperatures, it becomes ignited. 
When powdered nux vomica is macerated in water or diluted 
alcohol, the liquid takes up the strychnine and brucine, as salts 
of their peculiar acid, and more or less coloring matter; this 
extraction is much facilitated by a moderate heat. The solu- 
tion thus obtained, has an intensely bitter taste, strikes a red 
color with nitric acid, and yields a copious reddish-brown pre- 
cipitate with a solution of iodine in iodide of potassium. It 
acquires a greenish hue when treated with a solution of a per- 
salt of iron; amraonio-sulphate of copper produces a somewhat 
similar coloration, and, after a time, a greenish-white precipi- 
tate. Tannic acid throws down from the solution, a copious, 
dirty-white precipitate. 
It is obvious that there can be no chemical test by which 
the presence of nux vomica as a whole, when in a complex or- 
ganic mixture, can be directly shown; but this may be inferred 
by proving the presence of one or more of its peculiar princi- 
ples. Of these principles, strychnine is usually much the most 
easy of detection. Since, however, this alkaloid is so frequently 
met with in its pure state, or that of some of its salts, its mere 
detection would not, independent of other circumstances, prove 
the presence of nux vomica. The methods for the separation 
of strychnine and brucine from organic mixtures of the crude 
drug, are the same as those for their recovery from organic 
mixtures in general, as will be pointed out hereafter under the 
special consideration of these alkaloids. 
11. Strychnine. 
History.—Strychnine, or strychnia, was discovered, in 1818, 
by Pelletier and Caventou, both in the seed of Strychnos nux 
vomica and the St. Ignatius’ hean, .which latter is the seed of 
the Strychnos Ignatii. Thus far it has only been found in five 
species of the Strychnos genus plants, and in most of these 
it is accompanied by brucine. Several of the species of this 
genus of plants contain neither strychnine nor brucine. The PREPARATION. 
composition of strychnine, in its anhydrous state, according 
to Regnanlt, and since confirmed by Nicholson and Abel, is 
C 42 According to most analysts, it forms something 
less than one-half per cent, by weight of mix vomica; more 
recently, however, Mr. Horsley states that he obtained about 
one per cent, of the alkaloid from that substance. From the 
St, Ignatius’ bean, Pelletier and Caventou obtained from one to 
two per cent, of the alkaloid. 
Preparation.—Strychnine may be obtained from nux vomica 
by the following process. The rasped seeds are digested for 
twenty-four hours in water acidulated with hydrochloric acid, 
the decoction then strained through linen, the strained liquid 
concentrated to a small volume, and then precipitated with milk 
of lime ; the precipitate thus produced is collected on a cloth, 
washed with cold water, then dried, and the pulverised mass 
exhausted with successive portions of alcohol, until deprived of 
its bitterness. The mixed alcoholic liquids are concentrated on 
a water-bath, and then treated with water containing a little 
sulphuric acid, by which the strychnine will be dissolved in the 
form of sulphate. This solution is boiled with animal charcoal, 
filtered, concentrated to a small volume, and the alkaloidal sul- 
phate allowed to separate by crystallisation. The crystals may 
now be dissolved in pure water, and the alkaloid precipitated 
by slight excess of ammonia, then collected on a filter, washed 
with cold water, and allowed to dry. As thus obtained, strych- 
nine usually contains more or less brucine. 
Mr. Horsley’s method for preparing the alkaloid consists in 
first exhausting powdered nux vomica by repeated extractions 
with water strongly acidulated with acetic acid. The united 
acid liquids are then filtered, and the filtrate evaporated to a 
syrupy consistency. The cooled residue is diluted with water, 
slight excess of ammonia added, and the mixture allowed to 
repose for one or two days. Any crystals thus obtained, are 
washed, dried, then redissolved in Avater containing acetic 
acid, and the solution filtered. The liquid is now treated 
Avith a solution of chromate of potash, by which the alkaloid 
is precipitated as chromate of strychnia. This is collected, 
Avashed, then digested in a solution of ammonia, when, the 536 
STRYCHNINE. 
chromic acid uniting with the ammonia, the strychnine sepa- 
rates in its pure state. 
Strychnine is one of the most virulent poisons known. It is 
found in the shops both in its free state and in the form of some 
of its salts; its principal salts are the sulphate, chloride, or mu- 
riate, and the acetate. The ordinary medicinal dose of strych- 
nine, or of any of its saline combinations, is about one-sixteenth 
of a grain. 
Symptoms.—These are the same in kind as those produced 
by nux vomica, but they usually manifest themselves even more 
promptly. The first symptoms are usually a sense of oppres- 
sion and great anxiety, with quivering and spasmodic move- 
ments of the muscles of the extremities. These effects are 
sooner or later succeeded by violent muscular convulsions, in 
which the head is thrown back, the whole body rigidly stiff, 
the extremities extended, the hands firmly clenched, and the 
feet arched. In this state, the jaws are usually firmly closed, 
the face livid, the eyes prominent, the pupils dilated, and often 
foam issues from the mouth j the muscles of the chest and dia- 
phragm are also strongly contracted, and the respiration appar- 
ently arrested; the pulse is either very rapid or altogether 
imperceptible. In a little time, varying from less than a minute 
to several minutes, this tetanic condition usually entirely disap- 
pears, and there is a state of calm. During this state the 
patient feels extremely weak, usually experiences great thirst, 
and is sometimes inclined to sleep. After a little time, how- 
ever, the system again becomes excited, the special senses being 
exceedingly acute, and frequently there is a sense of impending- 
death. A second paroxysm may now be induced by very slight 
causes, or it may appear without any apparent cause. Not 
unfrequently the patient is perfectly conscious of the approach 
of the attack, and desires to be held or rubbed. After a suc- 
cession of attacks, varying from two to several, death takes 
place either during a paroxysm from asphyxia, or, more fre- 
quently, soon after from complete exhaustion. The interval 
between the paroxysms has varied from a few minutes to more 
than half an hour. The intellect usually remains clear up to 
the time of death. PHYSIOLOGICAL EFFECTS. 
537 
In a case reported by Dr. Blumhardt, in which a young 
man, for the purpose of self-destruction, swallowed forty grains 
of strychnine, the following symptoms were observed. The pa- 
tient soon experienced great anxiety and agitation, and after 
the lapse of fifteen minutes, an emetic having been adminis- 
tered, but with the effect of producing only slight vomiting, he 
lay stiff upon his back, with the head somewhat bent backwards; 
the lower extremities were perfectly stiff, but the upper still 
free; the countenance was pale and haggard ; the pulse quick 
and contracted. He still spoke with a firm voice and in a col- 
lected manner, but trismus was evidently commencing. The 
attacks soon became more violent, and the spasms extended to 
the muscles of the chest; the thorax appeared compressed, and 
the respiration was impeded. The paroxysms were now re- 
peated, at intervals of about a minute, for a short time, when 
the whole body became affected, and as stiff as a board. The 
suffocation was now extreme ; the jaws firmly locked together; 
the upper extremities firmly flexed at the elbow-joints and ap- 
plied across the chest; the lower extremities extended and stiff, 
and the soles of the feet concave. By degrees the respiration 
became more unequal, and finally ceased; the pulse became 
imperceptible; the skin of a dusky blue color; the face deep 
purple; the eyes prominent, and the pupils dilated and insensi- 
ble. All signs of consciousness soon disappeared, and the patient 
lay for a few minutes without motion, in a state of universal 
tetanus. A remission of the convulsions now suddenly mani- 
fested itself; the limbs became relaxed, and after a long deep- 
drawn inspiration the pulsations of the heart and arteries were 
again perceptible ; consciousness and the power of speech were 
also restored, but the articulation was imperfect. After about 
fifteen minutes, the patient was again seized with a shivering 
fit, followed by general tetanus, which soon terminated in a 
state of asphyxia, and death took place an hour and a half 
after the poison had been taken. (American Medical Intelli- 
gencer, vol. ii, p. 28.) 
The time within which the symptoms first manifest them- 
selves has varied from a few minutes to some hours; but they 
do not often appear much before fifteen minutes, nor are they 538 
STRYCHNINE. 
often delayed much beyond half an hour. In a recent case, 
reported by Dr. G. F. Barker, a young, healthy, married woman 
had administered to her with criminal intent, not exceeding six 
grains of strychnine, and violent symptoms were present in 
three minutes afterwards; these were succeeded by several con- 
vulsive paroxysms, and death during a paroxysm in thirty min- 
utes after the poison had been taken. (Amer. Jour. Med. Sci., 
Oct., 1864, p. 899.) In this instance, the strychnine was taken 
in its dry state into the mouth, and washed down with water. 
This is, perhaps, the most rapid case, in regard to the appear- 
ance of the symptoms, yet recorded. In the case of Dr. 
Warner, of Vermont, who, by mistake, took, it is believed, 
something less than half a grain of the well-marked 
symptoms were present within five minutes, and death occurred 
in about eighteen minutes. 
On the other hand, Dr. H. G. Thomas, of Alliance, Ohio, 
has reported a case in which a man swallowed five grains of 
strychnine, and one hour and three-quarters elapsed before any 
symptoms manifested themselves; and, under the use of emetics, 
the patient recovered. One of the most remarkable cases of 
this kind yet recorded, is the following, reported by Dr. T. 
Anderson. A gentleman took by mistake, believing it to be 
a salt of morphine, three grains and a half of strychnine, and 
experienced no particular symptoms until two hours and a half 
afterwards, when he suddenly fell backwards, but on being 
immediately raised, he was able to walk home, although ex- 
ceedingly nervous and alarmed. He soon felt better, and in 
five hours after taking the dose, he again took a similar quan- 
tity. In less than ten minutes after taking the last dose, 
he was seized with violent tetanic spasms, which continued, 
with the usual intermissions, for several hours, after which he 
entirely recovered. (Amer. Jour. Med. Sci., April, 1848, p, 
562.) The form in which the poison is taken, and the condi- 
tion of the stomach, may to some extent determine the time at 
which the symptoms first appear; but several instances are 
recorded in which the symptoms were delayed much beyond 
the ordinary period, even under conditions apparently the most 
favorable for their development. EFFECTS OF EXTERNAL APPLICATION. 
539 
It need hardly be remarked that the effects of strychnine 
may be much modified by the presence of another poison. A 
case of this kind, in which three grains of strychnine and one 
drachm of opium were taken and no serious symptoms appeared 
for nearly twelve hours, has already been mentioned. (Intko- 
duction, p. 40.) The following somewhat similar case, may 
also be cited. A young druggist, with suicidal intent, swal- 
lowed, at half-past eight o’clock in the evening, between eight 
and ten grains of nitrate of strychnia in an ounce of bitter- 
almond water. A little later, he took an additional dose of 
twelve grains of strychnia. Feeling nothing peculiar, he took 
at nine o’clock, ten.grains of acetate of morphia dissolved in an 
ounce of bitter-almond water, and then lay down in bed. Ten 
minutes later, to hasten his death, he poured some chloroform 
on his pillow. Partial insensibility now manifested itself, and 
continued for about an hour and a half, when he was seized 
with violent cramps and cessation of respiration, but without 
pain. Loss of consciousness then supervened, but he soon 
revived, and had another attack of convulsions. Emetics, and 
tannic acid were now administered; and in two days after- 
wards, no trace of the poisoning remained. (Amer. Jour. Med. 
Sci,, Jan., 1863, p. 259.) Recovery in this case has been 
ascribed to the fact that the patient, before taking the poison, 
had partaken freely of a soup made with flour and a species 
of cranberries. These latter contain tannin, an agent which is 
said to neutralise strychnine; and the farinaceous matters, by 
enveloping the poison, may have prevented its absorption. 
The external application of strychnine may be attended with 
serious, and even fatal consequences. In a case related by Dr. 
Schuler, something less than the twelfth of a grain of pure 
strychnine was introduced into the corner of the eye of a man 
affected with amaurosis. In less than three or four minutes, the 
patient’s face became livid, and he was seized with spastic 
yawnings and vertigo. These symptoms increased, and loss of 
speech and pulse, with convulsive respiration and violent tetanic 
shocks ensued. Death seemed inevitable, but, under the action 
of remedies, all the symptoms passed off in less than half an 
flour. (Amer. Jour. Med. Sci., Oct., 1861, p. 573.) 540 
STRYCHNINE. 
It was formerly believed that strychnine, when given in 
frequently repeated small doses, never accumulates in the sys- 
tem; but these results have occasionally been observed. Thus, 
Dr. Dutgher relates a case in which he administered to a 
middle-aged woman, affected with partial paralysis of the mus- 
cles of deglutition, the fifth of a grain of strychnine daily, in 
divided doses, for nine days, without any effect other than a 
gradual improvement of the paralytic condition. But on the 
morning of the tenth day, the patient was seized with pretty 
severe tetanic spasms, which continued, at intervals of about 
twenty minutes, for several hours, when they ceased, and the 
patient recovered, without any vestige of the paralysis remain- 
ing. (Med. and Surg. Reporter, Philadelphia, July, 1865, p. 2.) 
It will be observed, that the entire quantity of strychnine taken 
in this case, did not exceed two grains. 
A fatal case apparently of this kind was communicated, by 
Mr. Cooper, to the late Dr. Pereira (Mat. Med., vol. ii, p. 548). 
A Swede, affected with general paralysis, was given one-eighth 
of a grain of strychnine three times a day for several weeks. 
The dose was then increased to one-quarter of a grain, and 
afterwards to half a grain, with the same frequency for many 
days, without any marked effect. But one morning, the patient 
was found insensible, the face and chest of a deep purple color; 
the respiration had ceased, and the whole body was in a state 
of tetanic spasm and rigid. These symptoms passed off, and 
the man became apparently sensible; but another paroxysm 
soon occurred, and proved rapidly fatal. 
In regard to the diagnosis of strychnine poisoning, the only 
disease with which its symptoms could be confounded is tetanus 
arising from ordinary causes. But there is rarely any difficulty 
in determining the true nature of the case. Thus, in poisoning 
the symptoms appear suddenly in a violent form; the muscles 
of the hands are the first, and those of the jaws the last to 
become affected; there is usually a complete intermission in the 
symptoms; and they rapidly run their course, rarely lasting- 
over a few hours at most. On the other hand, in the disease 
the symptoms are slowly developed; the muscles of the jaws 
are the first, and those of the hands the last to become involved; PERIOD WHEN FATAL. 
541 
there is at most only a remission of the rigid state of the sys- 
tem; and death rarely occurs within twenty-four hours, the 
case often being protracted for several days. 
Period when Fatal.—A case is recorded, in which a young 
man, through the ignorance of a druggist, took one grain and 
two-thirds of strychnine with the same quantity of nux vomica, 
and “he very soon afterwards complained of some extraordinary 
sensations, and almost immediately expired.” (Amer. Jour. Med. 
Sci., April, 1854, p. 537.) In a case privately communicated 
to Dr. Taylor, ten grains of strychnine, given in mistake for 
sulphate of quinine, proved fatal in ten minutes. (On Poisons, 
p. 781.) In the of Dr. Warner, already mentioned, death 
occurred in about eighteen minutes after the poison had been 
taken. Dr. Geoghegan, of Dublin, relates an instance in which 
five grains proved fatal in from twenty to twenty-five minutes; 
and in Dr. Barker’s case, already cited, six grains caused death 
in about thirty minutes. In a case described by Dr. Theinhart, 
in which nearly thirty grains of the poison were taken, violent 
symptoms appeared in about fifteen minutes, and, after four 
convulsive paroxysms, death occurred in half an hour. (Amer, 
Jour. Med. Sci., Jan., 1848, p. 308.) 
On the other hand, in the well-known case of Cook, poisoned 
by Palmer, the symptoms were delayed for nearly an hour, and 
death occurred in about an hour and a quarter after the poison 
had been taken. We have elsewhere recorded a case in which 
a man, named Freet, took an unknown quantity of the poison, 
and violent symptoms appeared in about half an hour, but death 
did not take place until an hour later.* In a case described by 
Dr. Steiner—that of Dr. Gardiner, of Washington City—death 
did not occur until after the lapse of three hours and a half, 
although violent symptoms were present shortly after the poison 
had been taken. (Report on Strychnia, Philadelphia, 1856.) 
A still more protracted case has recently been reported by Dr. 
Paley, in which death did not occur until after the lapse of 
about five hours. (Brit, and For. Med.-Chir. Rev., Oct., 1860, 
* For the details of this case, as also an elaborate review of the legal bearings 
of poisoning, by Hon. Judge Wm. Lawrence, see Ohio Medical and Surgical 
Journal, March and May, 1864, pp. 95, 190. 542 
STRYCHNINE. 
p. 382.) And Dr. J. J. Reese, of Philadelphia, reports the 
case of a woman, in which death was delayed for from five to 
six hours. (Amer. Jour. Med. Sci., Oct., 1861, p. 409.) At a 
subsequent trial of this case, as personally informed by Win. 
H. Miller, Esq., who was engaged in the trial, it fully appeared 
in evidence that the deceased had taken from five to six grains 
of the poison, and death was delayed something over six hours. 
Fatal Quantity.—There seems to be much difference in the 
susceptibility of different persons to the action of strychnine. 
Dr. Wood mentions an instance in which a lady was thrown 
into violent and even alarming spasms, almost threatening suffo- 
cation, by one-twelfth of a grain of strychnine. (Therapeutics, 
vol, i, p. 834.) In a case related by M. Duriau, one-sixth of 
a grain, taken by a woman, aged twenty-eight years, produced 
in ten minutes afterwards violent tetanic convulsions, in which 
the whole body became rigid; similar attacks ensued, at inter- 
vals of a few minutes between each, and these were succeeded 
by a sense of burning in the epigastrium and pharynx, and 
great irritability of the stomach, which lasted for not less than 
six weeks. (Amer. Jour. Med. Sci., Oct., 1862, p. 562.) In 
the case of Dr. Warner, it is believed that not over half a 
grain of sulphate of strychnia had been taken. This seems to 
be the smallest quantity that has yet proved fatal to an adult. 
In a case reported by Dr. Ogston, three-quarters of a grain 
destroyed the life of a man, in three-quarters of an hour; and 
Dr. Watson relates an instance in which a similar quantity 
caused the death of a girl, aged twelve years, in about one 
hour. Mr. Bennett describes a case in which one grain and a 
half caused the death of a girl, aged thirteen years, in two 
hours and a half (Lancet, Aug., 1850, p. 462); and Dr. Pereira 
(Mat. Med., vol. ii, p. 549) cites the instance of a lady, who 
died in less than two hours from the effects of between two and 
three grains. 
Recovery has not unfrequently taken place after compara- 
tively large quantities of strychnine had been taken. A case 
of this kind in which five grains, and another in which seven 
grains, taken in two doses of three and a half grains each at an 
interval of five hours, have already been cited. Wharton and ANTIDOTES. 
543 
Stille quote three instances of recovery in each of which four 
grains of the poison had been swallowed (Med. Jur., p. 624); 
and a fourth case of this kind is reported by Dr. Lescher, of 
Illinois, and a still more recent case by Dr. Waller (Med. and 
Surg, Reporter, Philadelphia, Oct., 1865, p. 277). In another 
instance, related by Dr, Givens, a young man swallowed, with 
suicidal intent, two large pills containing not less than ten or 
twelve grains of strychnine. Violent tetanic spasms soon en- 
sued, and continued for five hours. In seven hours, the spasms 
entirely subsided, leaving the patient quite prostrated, with 
much distension and tenderness of the epigastrium, and stricture 
and soreness of the throat, and of the muscular system in gen- 
eral. These effects gradually passed off, and in less than a 
week the patient was nearly well. Soon after the patient had 
taken the poison, vomiting occurred, but it is not certainly 
known that the pills were ejected. (Brit, and For. Med.-Chir. 
Rev., April, 1857, p. 502.) In a case recently reported by Dr. 
Wilson (Am. Jour. Med. Sci., July, 1864, p. 70), a young man 
twenty-two years of age, recovered in about fifteen hours, 
although it is believed that he had taken forty grains of strych- 
nine. There is, however, in this instance, much uncertainty as 
to the quantity of poison really taken; and, moreover, there 
seems to have been very early vomiting. In a still more recent 
case, reported by Dr. Clark, a man laboring under delirium 
tremens, swallowed over twenty grams of the poison, and eight- 
een hours afterwards he was convalescent. (Buffalo Med. and 
Surg. Jour., Nov., 1866, p. 135.) Jn this case, also, there was 
early vomiting. After the action of the emetics, the patient 
was kept under the influence of chloroform for eight consec- 
utive hours, during which time all attempts to suspend its use 
were attended with a recurrence of the convulsions. 
Treatment.—This consists in the speedy administration of 
an emetic or the employment of the stomach-pump. As an 
emetic, finely-powdered mustard or sulphate of zinc may be 
employed. The action of the emetic should be aided by the free 
use of warm demulcent drinks. On account of the difficulty of 
swallowing or the rigid state of the jaws, it is sometimes impos- 
sible to resort to the use of emetics or the stomach-pump. Of 544 
STRYCHNINE. 
the various remedies that have been proposed, the internal ad- 
ministration of chloroform, as first employed by Dr. Dresbach, 
of Tiffin, Ohio, seems to be much the most efficient. In a case 
in which a man had by mistake swallowed a solution of three 
grains of strychnine, and most violent symptoms were present 
in twenty minutes, Dr. Dresbach administered two drachms of 
chloroform, and there was complete relief in less than twenty 
minutes afterwards. (Amer. Jour, Med. Sci., April, 1850, p. 
546.) In another instance, related by Dr. J, R. Smith, the 
inhalation of the vapor of chloroform was attended with similar 
results. (Ibid., July, 1860, p. 278.) Another case of this kind, 
in which four grains of strychnine had been taken, is reported 
by Dr. Bly. (New York Jour, of Med., Nov., 1859, p. 422.) 
So, also, in a case communicated to Dr. Wood, in which a 
robust young man had taken four grains of the poison and was 
seized with the most violent tetanic spasms, complete recovery 
took place under the use of chloroform, given both internally 
and by inhalation. (U, S. Dispensatory, 1865, p. 1357.) In 
this case, it is stated that it was necessary to keep the patient 
under the influence of the chloroform for thirteen consecutive 
hours, during which two pounds were consumed by inhalation. 
Two drops were given every five minutes, by the stomach, 
when the mouth could be opened. 
As a chemical antidote, tannic acid has been strongly ad- 
vised ; and Dr. Kurzak, of Vienna, has recently performed a 
series of experiments upon inferior animals, from which it would 
appear that this substance, if administered early, has the prop- 
erty of suspending the action of the poison. He states that 
about twenty-five parts of tannin are required for one part of 
strychnine. In the absence of tannin in its pure form, a strong 
infusion of powdered gall-nuts or of green tea might be exhib- 
ited. (North American Med.-Chir. Rev., July, 1860.) The 
utility of this acid is supposed to depend upon its uniting with 
the poison to form tannate of strychnia, which is insoluble in 
water, but readily soluble in acids. M. Bouchardat recommends, 
as an antidote, a solution of iodine in iodide of potassium. The 
precipitate produced by this mixture, is somewhat less soluble 
in diluted acids than that occasioned by tannic acid. It need ANTIDOTES. 
545 
hardly be remarked that neither of these substances should be 
relied on to the exclusion of emetics, or the stomach-pump. 
Among the other substances that have been recommended as 
antidotes, may be mentioned chlorine, bromine, animal charcoal, 
camphor, and lard, or fat. A case in which four grains of 
strychnine had been taken and recovery took place under the 
use of emetics and camphor, is related by Dr. Rochester (Buf- 
falo Medical Journal, March, 1856). 
Upon physiological grounds, Professor Houghton was led to 
believe that strychnine and nicotine (the active principle of 
tobacco) might be mutually antidotal, and he cites a few experi- 
ments on frogs in support of this view. And Dr. O’Eeilly, of 
St. Louis, has related an instance in which, acting upon this 
suggestion, he administered, in divided doses, an infusion of an 
ounce and a quarter of tobacco to a man who had taken six 
grains of strychnine, and the patient recovered. (Brit, and For. 
Med.-Chir. Review, Oct., 1859, p. 887.) Since, however, in 
this instance, previous to the administration of the alleged anti- 
dote, an emetic had been given and operated, it is not certain 
that the recovery was in any way due to the effects of the 
tobacco. Another instance in which an infusion of tobacco was 
employed, and the patient recovered has very recently been 
reported by Dr. Chevers, of Calcutta. (Ibid., Jan., 1867, p. 
248.) But in this instance, also, there seems to have been vom- 
iting prior to the administration of the tobacco; and, moreover, 
it appears that the patient, a girl aged eleven years, had swal- 
lowed only a comparatively small quantity, perhaps very much 
less than one grain, of the poison. 
For the purpose of testing the antidotal properties of nicot- 
ine, we administered to each of thirteen healthy cats, half a 
grain of pure strychnine, the poison being passed in solution 
into the stomach by means of a stomach-tube. In some in- 
stances, as soon as symptoms of the poison appeared, an infusion 
of twenty grains of tobacco-leaves was administered, in the same 
manner as the poison; whilst in others, the tobacco-infusion 
was given along with the strychnine, the two solutions being 
thoroughly mixed. In some few cases, the dose of tobacco was 
repeated. As the result of these experiments: one of the 
35 546 
STRYCHNINE. 
animals, which had taken the mixed solutions, immediately fell 
prostrate, breathed with difficulty, in three minutes voided urine, 
in eight minutes vomited a frothy mucus, and in ten minutes 
was able to run, with, however, a stiff gait; after an hour, the 
animal appeared perfectly well, excepting a slight stiffness in 
walking. With this single exception, all the animals died, and 
in most instances within the usual period; one of them, how- 
ever, that had taken the mixed solutions, manifested no symp- 
tom whatever for thirty-five minutes. In some instances, the 
strychnine symptoms appeared to be not in the least affected by 
the tobacco; but in others, they were of a compound nature. 
Several of the animals vomited. Before performing these ex- 
periments, it was ascertained that an infusion of twenty grains 
of tobacco, given alone, would produce serious symptoms ; but 
in no instance, in six experiments, did it cause death. 
Post-mortem Appearances. The most constant appear- 
ances in death from strychnine are, engorgement of the lungs, 
and fullness of the blood-vessels of the brain and its membranes, 
with a fluid condition and dark color of the blood. The heart 
is generally empty and flaccid. In some instances there is 
more or less redness of the mucous membrane of the stomach. 
Congestion of the liver, spleen, and kidneys has also been ob- 
served. The body usually presents a more or less livid appear- 
ance. One of the most striking characters in death from this 
substance, is the rigid condition assumed by the body soon after 
death. In this state, the joints are fixed, the abdomen hard 
and tense, legs extended, feet arched, fingers firmly closed, and 
the head thrown back. In a case recently reported by Dr. 
Paley, of Peterborough, death took place during a paroxysm, 
and the tetanic rigidity continued for some time afterwards, the 
arms being crossed and forcibly bent over the chest, the hands 
rigidly closed, and the legs perfectly stiff; but in twenty-three 
hours, there was no unusual rigidity about the limbs. (Brit, 
and For. Med.-Chir. Pev., Oct., 1860, p. 384.) In all the ani- 
mals we have killed with this poison, the bodies were flaccid at 
the time of death, but they soon became rigid. 
In the case reported by Dr. Theinhart, in which death took 
place in half an hour, the tongue, gums, and lips, as also the PATHOLOGICAL EFFECTS. 
547 
fingers and toes, were of a violet color; the fingers were closed, 
and the toes drawn in; and the whole body was as rigid as a 
stick of wood, and slightly bent upon itself. In Dr. Blumhardt’s 
case, in which forty grains of strychnine had been taken and 
death occurred in an hour and a half, twenty-four hours after 
death the skin was found of a dark color, and the body excess- 
ively rigid. On opening the vertebral canal, a large quantity 
of thick fluid blood escaped. The plexuses of the spinal veins 
and the pia mater were highly congested. The upper part of 
the spinal marrow was exceedingly soft, but the lower portion 
hard. The substance of the brain was slightly congested, but 
the membranes were healthy. The stomach was nearly normal, 
and contained a slimy mucus. 
In the case of Freet, already mentioned, forty hours after 
death, the skin was livid, the body rigid, the hands clenched, 
and the toes drawn upwards. The lower extremities were stiff, 
but the arras relaxed. The pyloric end of the stomach was 
somewhat reddened j and the liver and lungs were gorged with 
dark liquid blood. The blood throughout the body was of a 
dark color and fluid. The brain was healthy, but its vessels 
were nearly destitute of blood. The kidneys and bladder were 
normal. In Dr. Steiner’s case, eighteen hours after death, the 
body was extremely rigid, and the face, neck, and back, livid. 
The scalp and membranes of the brain were highly congested 
with dark liquid blood 5 but the substance of the brain and spi- 
nal marrow presented nothing abnormal. The heart was small, 
contracted, and contained no blood. The liver, spleen, and 
pancreas were natural, but the kidneys were highly congested. 
In the case described by Dr. Reese, six weeks after death, the 
body was found very rigid, and in a good state of preservation 5 
the heart was healthy, and contained a considerable quantity of 
blood. In Dr. Raley’s case, in which life was prolonged for 
about five hours, the only abnormal appearances found in the 
body twenty-three hours after death, were slight traces of inflam- 
mation of the lining membranes of the stomach and ilium, and 
a generally congested state of the thoracic and abdominal or- 
gans • the heart was nearly empty, and the blood of a dark 
color and fluid. 548 
STRYCHNINE. 
The following recent case, in which a large quantity of the 
poison had been taken and proved rapidly fatal, is reported by 
Dr. Buck (Araer, Med. Times, Oct., 1863, p. 205). Four hours 
after death: the body was still warm, the face livid, eyes open, 
pupils natural, jaws firmly closed, lips slightly parted, and frothy 
matter was escaping from the mouth. The muscles of the neck 
were relaxed, the arms rigid, and the elbows fixed at right an- 
gles, with the forearms across the chest; the fingers were semi- 
flexed, and when forcibly extended, would fly back—the same 
was true of the elbow. The legs were rigidly extended, the 
feet arched, and the great toes were drawn in. In twenty-four 
hours after death : the neck, back, left arm, right shoulder, and 
hip-joints were relaxed; but the other parts of the body were 
in the same condition as before. On opening the cranium, a 
large quantity of blood escaped from that cavity. The mem- 
branes of the brain were congested, but the brain and spinal 
marrow were healthy. The lungs, lining membrane of the tra- 
chea, and muscles in front of the neck were congested. The 
heart was firmly contracted, the ventricles empty, and only a 
very little blood in the auricles. The mucous membrane of the 
cardiac portion of the stomach was congested; all the other or- 
gans of the abdomen were healthy. A chemical examination 
of the contents of the stomach, by Dr. A. A. Hayes, of Boston, 
revealed the presence of a large quantity of strychnine. 
Chemical Properties. 
General Chemical Nature.—ln its pure state, strychnine 
crystallises in the form of colorless, transparent octahedra or in 
lengthened prisms. When precipitated from complex organic 
solutions, it often appears in the form of minute granules. As 
found in the shops, it is usually in the form of a white or dull- 
white amorphous powder, but it is frequently met with in the 
form of well-defined crystals. Strychnine has a most intensely 
bitter taste, but it is destitute of odor. It is not decomposed 
either by the cold concentrated mineral acids or the caustic 
alkalies. When gradually heated, it fuses to a brownish liquid, 
then undergoes decomposition with the evolution of dense white SOLUBILITY. 
549 
fumes; when heated in the flame of a spirit-lamp, it takes fire 
and burns with a yellowish smoky flame. It can not be vola- 
tilised unchanged. 
Strychnine has strong basic properties, and readily unites 
with acids to form salts, most of which are easily crystallisable. 
The salts of strychnine, except when containing a colored acid, 
are colorless; they have the intensely bitter taste of the pure 
alkaloid, and are equally poisonous. The neutral sulphate of 
strychnia crystallises in the form of transparent, colorless, four- 
sided prisms, which contain seven equivalents of water of crys- 
tallisation ; on exposure to the air, the crystals become opake, 
from loss of water of crystallisation. The chloride, or hydro- 
chlorate, forms slender crystalline needles, which, according to 
Nicholson and Abel, contain three equivalents of water. The 
nitrate and acetate appear in the form of beautiful silky needles; 
the latter of these salts, however, crystallises with difficulty. 
Solubility. 1. In Water.—When excess of pure powdered 
strychnine is digested at the ordinary temperature for twenty- 
four hours, with frequent agitation, in distilled water, the solu- 
tion then filtered, and the filtrate evaporated to dryness at a 
moderate temperature, it leaves a crystalline residue indicating 
that one part of the alkaloid had dissolved in 8,333 parts of 
the liquid. It is usually stated that strychnine dissolves in 
C,G67 parts of water at the ordinary temperature, but the above 
is the mean result of several very closely accordant experi- 
ments. Its solubility is much increased by a moderate heat, 
and much of the excess long remains in solution. 
2. In Ether.—Excess of the finely-powdered alkaloid was 
digested at the ordinary temperature for twenty-four hours in 
absolute ether, and the mean of several experiments indicated 
that one part dissolved in about 1,400 parts of the liquid. It 
is somewhat more soluble in ordinary ether. One part of the 
pure alkaloid dissolved in 1,050 parts of commercial ether of 
specific gravity 0‘733. 
3. Chloroform readily takes up one part of the pure alkaloid 
in eight parts of the menstruum. 
4. Absolute alcohol, when kept in contact at the ordinary 
temperature with excess of the alkaloid, with frequent agitation, 550 
STRYCHNINE. 
for four hours, takes up one part in 207 parts of the liquid. 
Under similar conditions, one part of the alkaloid will dissolve 
in about 400 parts of common whisky. 
5. Amyllc-alcohol, when agitated for a few minutes with ex- 
cess of the alkaloid, at the ordinary temperature, dissolves one 
part in 122 parts of the menstruum. 
From the foregoing facts, it is obvious that, other things be- 
ing equal, strychnine is much more completely extracted from its 
aqueous solution or mixture by chloroform than by ether; how- 
ever, the latter liquid will usually answer very well for the 
detection of the poison. The use of chloroform for the extrac- 
tion of the alkaloid from complex organic mixtures has been 
objected to, on the ground that it acts more solvently than 
ether upon foreign matters; but we have not found this objec- 
tion to hold in ordinary practice. The alkaloid is insoluble in 
the fixed caustic alkalies, and only very sparingly soluble in 
ammonia. 
Most of the salts of strychnine are readily soluble in water 
and in alcohol, they being more freely soluble in the latter liquid 
than the pure alkaloid. They are also soluble to an appreciable 
extent in ether. Thus, we find that the acetate dissolves in 
about 10,000 times its weight of this liquid. The insoluble 
salts of the alkaloid are readily soluble in the presence of a free 
acid, even, with very few exceptions, of acetic acid. 
Special Chemical Properties. Concentrated sulphuric 
acid dissolves strychnine, as well as its colorless salts, to a col- 
orless solution, which upon the addition of a crystal of bichro- 
mate of potash, rapidly passes through a highly characteristic 
series of colors (see post, color test). A crystal of nitrate of 
potash stirred in the sulphuric acid solution, produces no visible 
change. Concentrated nitric acid dissolves the alkaloid, and its 
salts, without change of color, even upon the addition of pro- 
tochloride of tin : if the strychnine be contaminated with bru- 
cine, as is frequently the case as met with in commerce, it 
strikes a red or orange-red color with nitric acid. Hydrochloric 
acid, also, dissolves the pure alkaloid to a colorless solution. 
When moistened with a solution of bichromate of potash, strych- 
nine acquires a beautiful golden-yellow color. SPECIAL CHEMICAL PROPERTIES. 
551 
Pure solutions of strychnine, and of its salts, are colorless 
and odorless, and have the bitter taste of the pure alkaloid. 
Upon slow evaporation, they leave the poison in its crystalline 
form. An alcoholic solution of the free alkaloid quickly restores 
the blue color of reddened litmus-paper. This reaction is also 
perceptible in a saturated aqueous solution of the alkaloid. 
The taste of strychnine, under certain conditions, is one of 
its most characteristic properties, and it may be recognised even 
in highly diluted solutions. Thus, a single grain of a 50,000 th 
pure aqueous solution of the alkaloid—equal to the 50,000 th of 
a grain of strychnine—has a quite perceptible bitter taste. A 
similar quantity of a 100,000 th solution has a perceptible taste, 
but this can hardly be said to be bitter. It has been asserted 
that even much less quantities of the poison than the last- 
mentioned, may thus be indicated, but in our own personal 
experience, we have not met with a person whose sense of taste 
extended beyond the quantities just stated. Moreover, the taste 
of these minute quantities is readily disguised by the presence 
of foreign substances. In a droj) of a 10,000 th solution, the 
taste is usually very decided and well-marked, even in the 
presence of a very notable quantity of foreign matter. 
That the taste is equally or even more delicate for the de- 
tection of strychnine than any of the known chemical methods, 
as has been asserted by some writers, is certainly erroneous. 
Nevertheless, this is one of the best corroborative tests yet 
known, and its application should never be omitted. Should it 
fail, under ordinary conditions, it would follow that at most 
there was only a very minute quantity of the alkaloid present. 
On the other hand, it must be remembered that other substances, 
such as quinine, quassia, colocynth, picrotoxin, and morphine, 
possess a somewhat similar bitterness. 
In the following investigations in regard to the action of 
reagents upon solutions of strychnine, the alkaloid was em- 
ployed in the form of a salt, but chiefly as the acetate. The 
fractions employed indicate the fractional part of a grain of the 
anhydrous alkaloid in solution in one grain of pure water. The 
results, unless otherwise indicated, refer to the behavior of one 
grain of the solution. 552 
STRYCHNINE. 
1. Potash and Ammonia. 
The fixed caustic alkalies and ammonia throw down from 
somewhat concentrated solutions of salts of strychnine a white 
amorphous precipitate of the pure alkaloid, which in a little 
time assumes the crystalline form. From more dilute solutions, 
the precipitate does not appear until after a little time, and it 
then separates in its crystalline state. Solutions still more dilute, 
may entirely fail to yield a precipitate. The precipitate is 
insoluble in potash and soda, and only sparingly soluble in am- 
monia, but it immediately disappears upon the addition of almost 
any of the diluted acids. When a somewhat strong solution of 
a salt of the alkaloid is exposed to the vapor of ammonia, it 
immediately becomes covered with a white film, and in a little 
time changes to a nearly solid mass of crystals. 
1. ytto grain of strychnine, in one grain of water, yields, with 
either of the reagents, an immediate, copious precipitate, 
which very soon becomes converted into a mass of crys- 
tals of one or more of the forms illustrated in Plate X, 
fig. 1. If after the addition of the reagent, the mixture 
be allowed to remain very quiet, it yields very beautiful 
compound stellate crystalline groups of the form illustrated 
in the lower part of the figure ; these forms are especially 
apt to be produced if the alkaloid contains a little brucine. 
2. r.Wo grain: after a few moments, crystalline needles and 
groups begin to appear, and in a very little time, there is 
a quite good deposit. If upon the addition of the reagent, 
the mixture be stirred with a glass rod, it almost immedi- 
ately yields a very good amorphous precipitate, which 
very soon changes into short crystalline needles. 
3. aTsVo grain; after a few minutes, a very satisfactory crys- 
talline precipitate has formed. If the mixture be stirred, 
the formation of the precipitate is much facilitated, and it 
is more abundant. 
4. aTowo grain, when treated with a very small quantity of 
reagent, yields, after some minutes, especially if the mix- 
ture be stirred, a very satisfactory crystalline precipitate. COLOR TEST. 
The alkaline carbonates produce, in solutions of salts of 
strychnine, reactions similar to those of the free alkalies. 
It need hardly be remarked that the production of a white 
crystalline precipitate by either of the foregoing reagents, is not 
in itself positive proof of the presence of strychnine. The crys- 
talline forms of this alkaloid, however, are somewhat peculiar. 
The true nature of the precipitate, even when present only in 
the most minute quantity, may be readily established by means 
of the test just to be mentioned. 
2. Color Test. 
This test, which is the most characteristic, and at the same 
time, when applied to the pure alkaloid, one of the most deli- 
cate yet known for the detection of strychnine, is based upon 
the development of a series of colors when a sulphuric acid 
solution of the alkaloid is treated with certain oxidising agents. 
Marchand, in 1843, was the first to point out that when strych- 
nine wras dissolved in sulphuric acid containing a little nitric 
acid, and the mixture stirred with a small quantity of peroxide 
of lead, the liquid immediately acquires a deep blue color, which 
rapidly changes to purple or violet, then gradually to red, which 
very slowly fades. 
This development of colors is due to the action of the nas- 
cent oxygon, evolved by the acids and lead compound, upon 
the strychnine. Any combination that will eliminate oxygen 
will produce these results, providing the substance from which 
it is evolved or some substance evolved along with it from 
the oxidising agent, does not interfere with the action of the 
nascent gas. Mack, in 1846, proposed the use of sulphuric 
acid and binoxide of manganese, and about the same time, 
Otto suggested this acid and bichromate of potash. More re- 
cently, it has been proposed to substitute for these metallic 
combinations various other substances, such as ferricyanide of 
potassium, chromic acid, the alkaline iodates, and permanga- 
nate of potash. Most of these substances were advanced un- 
der the claim, either, that they were more delicate in their 
reaction, or else less subject to interferences, than those that 554 
STRYCHNINE. 
had previously been proposed j but a careful and impartial 
comparative examination shows that at most there is but little 
difference between them in regard to delicacy of reaction, and 
that they are all about equally affected by the presence of cer- 
tain foreign substances. Of these different oxidising substances, 
we prefer, for this purpose, the bichromate of potash ; this salt 
is readily obtained in its pure crystalline state. For the detec- 
tion of very minute traces of the alkaloid, it is better to have 
the color-developing agent in the form of a minute crystal than 
in the state of powder. Binoxide of manganese and peroxide 
of lead dissolve in sulphuric acid without change of color, but 
bichromate of potash and ferricyanide of potassium impart a 
yellowish, while permanganate of potash gives a greenish color 
to the acid. These colors, however, at most undergo but slow 
change, and could not possibly be confounded with the series of 
colors produced by strychnine. 
To apply this test, a small quantity of the alkaloid, or any 
of its salts, in the solid state, is placed on a piece of white por- 
celain or in a watch-glass over white paper, and dissolved in a 
drop of pure concentrated sulphuric acid, in which, if pure, it 
dissolves without change of color. A small crystal of bichro- 
mate of potash, or a small portion of either of the other color- 
developing agents, is now added to the solution and, when 
moistened with the acid, slowly moved around in the liquid 
by means of a pointed glass rod, when either immediately or 
in a few moments, the peculiar succession of colors, beginning 
with a beautiful blue, will manifest itself. The blue color 
quickly passes into purple, this into violet, and this more slowly 
into red, which very slowly fades. The liquid ultimately ac- 
quires either a yellow or greenish color, or becomes entirely 
colorless; but these results are altogether independent of the 
action of the strychnine. An important point to be observed, 
when applying the test to a suspected substance, is the non- 
coloration by the acid alone. 
As the intensity and duration of the colors thus produced, 
depend very much upon the amount of strychnine operated upon, 
as well as the relative quantities of acid and color-developing 
agent employed, and the physical state of the latter, it is COLOR TEST; DELICACY. 
555 
impossible to give any description that will fully meet every 
case ; yet whenever developed, they are so peculiar as to be 
readily recognised, even when only the merest trace of the poison 
is present. With a very minute quantity of the alkaloid, the 
blue color may continue only for a moment, or it may even be 
entirely absent, the mixture developing at first a purple or violet 
color, quickly passing to red. To obtain the best results from 
these minute quantities, the acid should be very concentrated 
and added in only very minute quantity, and only a very small 
fragment of the oxidising agent employed. 
Another method of applying the test, is to place a small 
drop of sulphuric acid by the side of the strychnine, and then 
stir a very small crystal of bichromate of potash in the acid 
until it imparts a slight yellow color to the liquid, when the 
moistened crystal is dragged over the strychnine, by means of 
a pointed glass rod; or, the colored acid may be allowed to flow 
over the alkaloid, by gently inclining the dish. For the recog- 
nition of minute quantities of the poison, this method is even 
more delicate than that just described. Since, however, as we 
shall see hereafter, in examining a suspected deposit, it is fre- 
quently important to know the action of the acid alone, this 
method is not always applicable. The test may also be applied 
to solutions of strychnine, by treating a drop of the liquid with 
a drop or two of concentrated sulphuric acid, and stirring in 
the cooled mixture a small quantity of the color-developing 
agent. This method, however, only applies to somewhat strong 
solutions of the alkaloid, and, even under these circumstances, 
the results are by no means as uniform as when the poison is 
in its solid state. 
Delicacy of the test.—In the following examinations in regard 
to the limit of the reaction of this test, the quantities of strych- 
nine were obtained by evaporating one grain of a corresponding 
solution of a salt of the alkaloid to dryness spontaneously. This 
method of evaporation is much preferable to that on a water- 
bath, since it much more frequently leaves the poison in its 
crystalline state, which is better adapted to the application of 
the test than the amorphous form. The results refer more 
especially to those produced by the bichromate of potash as the 556 
STRYCHNINE. 
oxidising agent, and are based on very frequently repeated 
experiments. 
1. yo~o grain of strychnine, in the form of acetate, when ob- 
tained in the manner just described, forms a very fine 
crystalline deposit, which, when examined by the test, 
yields a magnificent display of colors. 
2. yroo grain, leaves a quite good crystalline residue, which 
yields, with the test, results very similar to those under 1. 
The same quantity of the alkaloid in solution in one grain 
of water, yields very satisfactory results. 
6. royowo grain: the residue consists of a number of well-defined 
crystals, which when treated with the test, yield a per- 
fectly satisfactory succession of colors. The results ob- 
tained from this quaiitity of the alkaloid, when free from 
foreign matter and manipulated with care, are just as sat- 
isfactory, so far as the evidence of the presence of the 
alkaloid is concerned, as those obtained from any larger 
quantity, the only difference being in the duration of the 
different colors. 
4. ro7cro“o grain: the residue usually contains a number of dis- 
tinct microscopic crystals ; when the deposit is moistened 
with a trace of the acid, and treated with a mere frag- 
ment of the potash salt, it yields very satisfactory evidence 
of the presence of the poison. 
5. r0'676~0~5 grain: if the residue is not much distributed, it usu- 
ally contains some few minute crystals, and when treated 
as under 4, yields a very distinct coloration. For the 
success of this reaction, it is essential that the residue be 
deposited within a narrow compass, and that the merest 
trace of the acid and color-developing agent be employed. 
Under these circumstances, it will yield quite satisfactory 
results. The acid is best applied, by moistening the end 
of a small glass rod with the liquid and then drawing it 
over the deposit. 
matter, even a much smaller quantity of the alkaloid than the 
last-mentioned, will yield, under the action of the test, a very 
distinct purplish or violet coloration, especially if the fragment 
When collected at one point, and perfectly free from foreign COLOR TEST: DELICACY.' 
557 
of bichromate of potash be first moistened with the acid, and 
then brought in contact with the poison. The residues obtained 
from solutions of the poison may be collected within a small 
space, by allowing the liquid to evaporate in a very concave 
watch-glass; or, better still, as first advised by Messrs. Rodgers 
and Girdwood, by collecting the solution in a pipette provided 
with a small capillary point, and from this applying a minute 
drop of the liquid to a warmed surface, and repeating the 
operation, as the fluid evaporates, until a sufficient deposit is 
obtained. 
The limit of this test, particularly when bichromate of pot- 
ash is used as the color-developing agent, has been the subject 
of much misapprehension. Thus, under these circumstances, 
in the hands of some experimentalists, the test failed with quan- 
tities of the alkaloid only a little less than the 2,000 th or 
B,oooth part of a grain. But that these failures were not due 
to any want of delicacy on the part of the method itself, is 
quite apparent from the foregoing experiments. So, also, it 
has been claimed, that some of the other oxidising agents are 
more delicate in this respect than the bichromate of potash. 
Since, however, this salt, when properly applied, will produce a 
distinct coloration with the least quantity of the alkaloid visible 
to the naked eye, and under the microscope, with about the 
least crystal visible by this instrument, it is obvious that it 
reaches the possible practical limit of any of the color-devel- 
oping agents. 
It is not thus intended to imply that in regard to delicacy, 
this method is superior to any yet proposed, but only that it is 
not inferior: similar results may be obtained at least from the 
employment of ferricyanide of potassium, as first proposed by 
Dr. E. Davy, and the permanganate of potash, as advised by 
Dr. Guy, and also from the binoxide of manganese. It has 
been stated by some observers, that the colors produced by 
powdered binoxide of manganese and of peroxide of lead, are 
much more intense than those produced by the bichromate 
of potash; but this is only true of given quantities of the 
alkaloid, and depends upon the physical state of these me- 
tallic compounds, similar results being equally produced by 558 
STRYCHNINE. 
finely-powdered bichromate of potash or of ferricyanide of potas- 
sium, as also by powdered permanganate of potash. 
Interferences.—Although this test will serve to reveal the 
nature of the least visible quantity of strychnine when in its 
pure state; yet, the presence of certain foreign substances may 
cause it to entirely fail, even when comparatively large quanti- 
ties of the poison are present. In this respect, the action of 
the different color-developing agents is about equally affected. 
Brieger, in 1850, first announced that the reaction was more 
or less interfered with by the presence of morphine and its salts, 
quinine, and sugar (Chem. Gaz., vol. viii, p. 408) ; and since 
then, it has been asserted that tartar emetic, nitric acid and 
nitrates, common salt, corrosive sublimate, and various other 
substances, had a similar property. Many of these substances, 
however, even when present in relatively large quantity, exer- 
cise but little influence over the test; but others of them may 
entirely prevent its ordinary reaction. 
Morphine belongs to the latter class of these substances. 
The influence of this substance is determined, both by the rela- 
tive and absolute quantity present. Thus, when 100 th part of 
a grain each of strychnine and morphine, or of their salts, are 
thoroughly mixed, by evaporating their mixed solutions to dry- 
ness, they yield, under the action of the test, little or no indi- 
cation of the presence of the strychnine ; whilst, if a mixture 
of I,oooth of a grain each be examined, it yields very satis- 
factory evidence of the presence of that alkaloid. In other 
words, a very minute quantity of a mixture of equal parts of 
the alkaloids, will yield much better results than will be fur- 
nished by a larger quantity of the mixture. When, however, 
the relative quantity of morphine exceeds several times that of 
the strychnine, the reaction of the test may be entirely masked, 
even with very small quantities of the mixture. 
When these alkaloids exist in the same solution, they may 
be separated by rendering the mixture alkaline and agitating it 
with pure chloroform, in which the strychnine is very freely 
soluble, whilst the morphine is almost absolutely insoluble, espe- 
cially in the presence of a free alkali. It is therefore obvious, 
that when strychnine has been exti'acted from organic mixtures COLOR TEST: INTERFERENCES. 
559 
by means of chloroform, in the manner to be pointed out here- 
after, this interference on the part of morphine, to the color- 
test, does not exist. Experiments show that this is even true 
of the extract obtained from a strongly alkaline 100 th solution 
of morphine containing only the 10,000 th of its weight of 
strychnine, and even when several volumes of chloroform are 
employed for the extraction. These facts are equally appli- 
cable when pure ether is employed as the extracting agent, 
especially if after the addition of the mineral alkali, the mix- 
ture be allowed to stand some few minutes, before being agi- 
tated with the liquid. 
For the separation of these alkaloids, it has been proposed 
to precipitate the strychnine by a solution of bichromate of pot- 
ash. But, as this reagent also produces precipitates in strong 
solutions of salts of morphine, especially after standing some 
time, and, also, as the chromate of strychnia is but little less 
soluble in water than the pure alkaloid, it is obvious that we 
might have a mixture of these substances from which the pre- 
cipitate would consist largely, or even entirely, of chromate of 
morphia; and, moreover, that even under the most favorable 
circumstances, a given quantity of the strychnine would remain 
in solution, and thus entirely escape detection. In the presence 
of a free alkali, the bichromate of potash is converted, in part 
at least, into the protochroraate, which is a more delicate pre- 
cipitant of morphine than of strychnine. 
Nitrates, such as the nitrate of potash, interfere with the 
normal reaction of the test to nearly or about the same extent 
as morphine. This interference, like that of morphine, applies 
equally to the different color-developing agents. In regard to 
the influence of tartar emetic, our own observations fully confirm 
those of Mr. Hagen (Chem. Gaz., 1857, p. 397), namely, that 
this substance may be present even in very large excess without 
exerting any very marked influence; yet, when the mixture 
contains twenty or thirty parts of the compound, it may entirely 
disguise the ordinary reaction of the test. These observations 
are equally applicable in regard to the modifying influence of 
sugar. Since the nitrates, tartar emetic, and sugar are insolu- 
ble in chloroform, neither of these substances could be present 560 
STRYCHNINE. 
with strychnine when the alkaloid is extracted from organic 
mixtures by that liquid. 
A much more serious interference, than any yet mentioned, 
to this test, is the presence of certain undefined organic sub- 
stances frequently extracted from complex mixtures by chloro- 
form and by ether. It is no unusual occurrence to thus obtain 
extracts, which fail to reveal the presence of strychnine, even 
when comparatively large quantities of the alkaloid are pur- 
posely added. In fact, this is so frequently the case when only 
a very minute trace of the poison is present, that should a sus- 
pected extract fail to indicate the presence of the poison, before 
concluding that the latter is entirely absent, it is always best 
to add, to a separate portion of the extract, a very minute 
quantity of the pure alkaloid and determine whether the failure 
might not be due to this cause. The best method for separating 
substances of this kind, is to dissolve the chloroform residue in 
a small quantity of acidulated water, treat the solution with 
slight excess of an alkali, and again extract with chloroform 5 
sometimes it may be necessary to repeat all these operations. 
Fallacies.—lt has been objected to this test, that under its 
action various other substances, as aniline, curarine, cod-liver 
oil, pyroxanthine, papaverine, narceine, veratrine, and solanine, 
yield colors somewhat similar or even identical with those pro- 
duced from strychnine. When, however, the test is properly 
applied and observed, these objections have little or no practical 
force. Thus, all these substances, except aniline, unlike strych- 
nine, yield their colors or at least are colored, by sulphuric acid 
alone; and, furthermore, none of them, except curarine and 
cod-liver oil, even by the conjoined action of the acid and 
color-developing agent, yields, like strychnine, a series or quick 
succession of colors. Although these objections may be thus 
summarily answered; yet it is only proper that the chemical 
nature of some at least of these fallacious substances be consid- 
ered somewhat in detail. 
Aniline, in its pure state, is a colorless liquid, having a 
rather pleasant odor, and a sharp acrid taste: it is obtained 
from coal-tar, and by the action of potash upon indigo; it may 
also be obtained by various other methods. When treated with COLOR TEST: FALLACIES. 
561 
concentrated sulphuric acid, it undergoes no change of color, 
but it throws down, if present in notable quantity, a white pre- 
cipitate of the sulphate of aniline. The salts of this base are 
colorless, nearly tasteless, and, for the most part, readily crys- 
tallisable. The sulphate has recently been employed as a ther- 
apeutic agent. Pure aniline is readily soluble in chloroform, 
but its salts are almost wholly insoluble in that liquid. 
When the salts of aniline are treated with concentrated sul- 
phuric acid, they, like the salts of strychnine, yield no colora- 
tion ; but, when a crystal of bichromate of potash, or a small 
portion of any of the other oxidising agents, is stirred in the 
acid mixture, the latter slowly acquires a yellowish or greenish 
tint, then presents bluish streaks, and after a little time, assumes 
a beautiful deep blue color, which undergoes but little change 
for half an hour or even much longer, but it finally becomes 
nearly or entirely black. Prom this description, it is obvious 
that the reaction of this substance bears but little similarity to 
that of strychnine, about the only resemblance being in the 
production of a deep blue color. But in the case of strychnine, 
as remarked by Dr. Guy, this color is the first produced, and 
is developed either immediately or at most within a few mo- 
ments, and is quickly followed by other characteristic colors, it 
being itself exceedingly transient j whereas, in the case of ani- 
line, this color is but slowly developed, is preceded by other 
colors, and when once established is exceedingly persistent, and 
ultimately becomes black. In this connection, it may be stated 
that Dr. Letheby reports (Chem. News, vol. v, p. 71) two cases 
of accidental poisoning by nitro-benzole, in which he found that 
it was changed in the animal body into aniline. 
Curarine is the name applied to the active principle, or 
alkaloid, found in Woorara, or Curara, the substance employed 
by the Indians of South America for poisoning their arrows. 
Much doubt exists as to the true nature of woorara. According 
to Waterton, it is prepared from several different plants, two 
species of poisonous ants, and the fangs of certain snakes; 
while Schomburgk states that it consists alone of vegetable mat- 
ter, and chiefly of an extract of the bark of the strychnos tox- 
tfera, a tree found native in Guiana. Various other statements 562 
STRYCHNINE. 
have been made in regard to its composition. That there are 
at least several varieties of this substance current among the 
different tribes of Indians, seems to be fully established by the 
recent investigations of Drs. Hammond and Mitchell (Amer. 
Jour. Med. Sci., July, 1859, pp. 13-61); and it is even proba- 
ble that each tribe has its own method for preparing the poison. 
It was formerly believed that the poisonous properties of woo- 
rara were due to the presence of strychnine, but this alkaloid 
has not been found in any of the specimens yet examined. In 
fact, the physiological effects of this substance are the very 
opposite to those of strychnine, and it has even been advised 
as an antidote in poisoning by that alkaloid. 
Woorara is usually described as a hard, black or nearly 
black, brittle, resin-like solid, of an intensely bitter taste ; in 
the state of powder, it has a dark brown color. It is, for the 
most part, readily soluble in water and in alcohol, but only very 
slightly acted upon by ether and chloroform, even in the pres- 
ence of a free alkali. The statements in regard to the chemical 
properties of this substance have been somewhat conflicting. 
The active principle, or curarine, as obtained by MM. Roulin 
and Boussingault, who were the first to isolate the .alkaloid, was 
in the form of a transparent solid, having a pale-yellow color, 
and an exceedingly bitter taste. It, as well as all its salts, was 
uncrystallisable. According to Bernard, curarine dissolves in 
concentrated sulphuric acid with the production of a beautiful 
carmine color; and Pelikan states that under the combined 
action of this acid and a color-developing agent, as bichromate 
of potash or a current of electricity, it yields a brilliant red 
color. It would appear that quite recently M. Preyer obtained 
curarine, as well as its soluble salts, in the crystalline form. 
(Chem. News, London, July, 1865, p. 10.) According to this 
observer, the pure alkaloid yields with concentrated sulphuric 
acid a magnificent and lasting blue color; while with this acid 
and bichromate of potash, it yields much the same series of 
colors as strychnine. With strong nitric acid, it yields a pur- 
ple coloration. 
A specimen of ordinary woorara, kindly furnished us in lib- 
eral quantity by Dr. S. Wier Mitchell, of Philadelphia, has the COLOR TEST: FALLACIES. 
563 
following properties. Its physical properties are the same as 
those just described. When treated, in its erode state, with 
concentrated sulphuric acid, it slowly yields, without entirely 
dissolving, a reddish-brown solution, which when stirred with a 
small portion of bichromate of potash, or any other oxidising 
agent, gives a series of colors very similar to that produced 
from a very impure mixture of strychnine. Concentrated nitric 
acid dissolves it, with evolution of binoxide of nitrogen, to a 
deep reddish-brown solution. It is for the most part readily 
soluble in water, especially upon the application of heat j the 
insoluble portion consists apparently of vegetable fragments. 
The filtered aqueous solution has a deep brownish color, an 
intensely bitter taste, and a just perceptible acid reaction. It 
is about equally soluble in strong alcohol. The concentrated 
aqueous solution yields with a solution of bichromate of potash 
a yellow amorphous precipitate, which when washed and treated 
with a small quantity of concentrated sulphuric acid, yields a 
series of colors not to be distinguished from that produced 
under similar circumstances from the chromate of strychnia. 
This precipitate, however, differs from the strychnia compound, 
in being uncrystallisable, and readily soluble in water. 
When a strong aqueous solution of several grains of an alco- 
holic extract of the crude poison, is rendered strongly alkaline 
with potash and agitated with chloroform, this liquid remains 
colorless, and leaves upon spontaneous evaporation, a slight, 
yellowish, gum-like residue, having an intensely bitter taste. 
When a minute portion of this residue is touched with a drop 
of sulphuric acid, it acquires a red color and very soon dis- 
solves to a solution of the same hue; if a small crystal of 
bichromate of potash be now stirred in the solution, it produces 
a series of colors the perfect counterpart of that from strych- 
nine, with perhaps the exception that the blue and purple colors 
are somewhat more persistent than those from an equal quantity 
of the latter substance. Under the action of nitric acid, the 
chloroform residue assumes a red color, and dissolves to a red- 
dish solution 5 this color is discharged by heat, and the cooled 
liquid remains unchanged on the addition of protochloride of 
tin. The alkaline solution from which the chloroform extract 564 
STRYCHNINE. 
was obtained, has an intensely bitter taste, and yields with a 
solution of bichromate of potash a rather copious amorphous 
precipitate, having the same properties as the precipitate from 
an aqueous solution of the crude poison. When a small quan- 
tity of the alkaline solution is treated with sulphuric acid, it 
acquires a beautiful purple color, which on the addition of a 
crystal of bichromate of potash is changed to a deep blue, fol- 
lowed by purple and the other peculiar colors. The alkaline 
solution also yields other reactions indicating that but little of 
the active principle had been removed by the chloroform. 
Various efforts were made to obtain this principle, and some 
of its compounds, in the crystalline state, but in all cases with- 
out success. 
It thus appears that this sample of woorara contains a prin- 
ciple having certain chemical properties in common with strych- 
nine. Thus, like strychnine, it has an intensely bitter taste; 
yields under the combined action of sulphuric acid and an oxid- 
ising agent a particular series of colors; and its bichromate of 
potash precipitate yields, with this acid alone, similar results. 
But these are about the only respects in which it resembles that 
alkaloid. Among the differences existing between this principle, 
at least in the sample under consideration, and strychnine, may 
be mentioned the following: it and all its compounds are un- 
crystallisable; it is colored by sulphuric acid alone; its bichro- 
mate of potash precipitate is rather readily soluble in water and 
is amorphous *, it is almost wholly insoluble in chloroform, and 
readily soluble in potash; and its solutions are not precipitated 
by the caustic alkalies. In addition to these facts, the extreme 
rarity of this substance in civilized communities, would deprive 
it of any practical force as a source of fallacy in medico-legal 
investigations for strychnine. 
It may here be added, that three grains of the above woo- 
rara were administered in solution to a young cat without pro- 
ducing any appreciable effect whatever; although the animal 
was closely watched for twelve hours. But, a very small quan- 
tity of the paste introduced under the skin of the inside of 
the thigh of a similar animal, produced almost immediate stu- 
por, and in eight minutes complete prostration ; this condition COLOR TEST: FALLACIES. 
565 
continued, with occasional convulsive movements, for some 
hours, after which the animal completely recovered. 
Cod-liver oil has also been mentioned as a source of fallacy. 
This substance when treated with sulphuric acid alone, yields a 
series of colors which might be confounded with that produced 
from strychnine by the combined action of this acid and an 
oxidising agent. But as strychnine yields no coloration with 
sulphuric acid alone, it is obvious that when the acid is applied 
first and its action observed, all grounds for objection, so far as 
this oil is concerned, are at once removed. Moreover, the 
physical state of cod-liver oil would at once distinguish it from 
strychnine, or any of its salts, in the solid state. 
The objections in regard to the other substances heretofore 
mentioned, have already been answered, namely, that they are 
colored by sulphuric acid alone, and under no circumstance do 
they yield a quick succession of colors. Thus, pyroxanthine, 
which has a bright red color, yields with the acid, a blue solu- 
tion ; papaverine, a purple ; narceine, a reddish-yellow or brown- 
ish color; veratrine, a yellow, slowly becoming crimson; and 
solanine, an orange-brown mixtui’e. It may be remarked, that 
the exact tint of color produced by the acid with at least some 
of these substances, is more or less modified by the quantity of 
material employed. 
In addition to the substances now considered, there are a 
number of alkaloids and other organic proximate principles, 
which when treated either with sulphuric acid alone or with 
this acid and an oxidising agent, give rise to more or less col- 
oration. The action of this test with a number of these sub- 
stances, was first examined by M. Eboli (Chem. Gazette, 1856, 
p. 251) ; then by Dr. T. E. Jenkins, of Louisville, Ky., who 
extended the investigation to about fifty of these principles 
(Semi-Monthly Med. News, April, 1859, p. 214); and still more 
recently, by Dr. Guy, of London (Chemical News, Aug., 1861, 
P- 113), who added some sixteen substances to those examined 
hy Dr. Jenkins. But of all the substances thus examined, ex- 
clusive of some already mentioned, none gave results resembling 
the reactions of strychnine, even to the extent of those already 
considered. 566 
STRYCHNINE. 
Galvanic Test.—This in principle is the same as the pre- 
ceding method, only that the oxygen is rendered nascent by a 
current of voltaic electricity, instead of being evolved from a 
metallic oxide, by means of sulphuric acid. It may be applied, 
according to Dr. Letheby, who, we believe, first advised the 
process (London Lancet, June 28, 1856, p. 708), by placing a 
drop of the strychnine solution in a cup-shaped depression made 
in a piece of platinum-foil, evaporating the liquid at a low tem- 
perature, and moistening the residue with a small drop of con- 
centrated sulphuric acid. The foil is then connected with the 
platinum pole of a single cell of Grove’s or Smee’s battery, and 
the acid liquid touched with the platinum terminal of the nega- 
tive pole. In a moment the violet coloration manifests itself in 
great intensity. 
In regard to the delicacy of this method, it is much the 
same as that of the test as ordinarily applied. Thus, according 
to our own experiments, the 10,000 th part of a grain of strych- 
nine, yields a fine display of colors; and the 100,000 th of a 
grain, a distinct reaction. Since, however, this process is not 
so readily applied as the ordinary method and, according to the 
observations of Dr. J. J. Reese (Amer. Jour. Med. Sci., Oct., 
1861, p. 417), as well as our own, is about equally open to the 
interferences and so-called fallacies that hold against the ordi- 
nary method, it seems to possess no advantage over the latter. 
In fact, as observed by Dr. Reese, it is less satisfactory, than 
the usual method, for the recognition of very minute traces 
of the poison. 
8. Sulphocyanide of Potassium. 
This reagent throws down from solutions of salts of strych- 
nine, when not too dilute, a white crystalline precipitate of the 
sulphocyanide of strychnine, which, according to Nicholson and 
Abel, has the constitution C 42 CyS2. The precipitate is 
insoluble in excess of the precipitant, and but sparingly soluble 
in diluted acetic and hydrochloric acids. 
1. Tto grain of strychnine, in one grain of water, yields an 
immediate crystalline deposit, and in a few moments the BICHROMATE OF POTASH TEST. 
567 
mixture becomes a nearly solid mass of crystals, of tbe 
forms shown in Plate X, fig. 2. 
2. raToo grain; by stirring the mixture, in a very little time it 
throws down crystals, and soon, there is a very satisfac- 
tory deposit. 
6- t,wo grain, yields, especially if the mixture be stirred, after 
some minutes, a satisfactory deposit of crystalline needles. 
Sulphocyanide of potassium also produces white crystalline 
precipitates in solutions of several of the other alkaloids. 
4. lodide of Potassium. 
Somewhat strong solutions of salts of strychnine, yield with 
iodide of potassium, a white crystalline precipitate, which is 
insoluble in excess of the precipitant and in the free alkalies, 
and only slowly soluble in large excess of acetic, nitric, and 
hydrochloric acids. The formation of the precipitate is much 
facilitated by stirring the mixture with a glass rod. 
1. xto grain of strychnine: in a few moments, the mixture be- 
comes a nearly solid mass of crystals, of the same forms as 
those produced by the preceding reagent (Plate X, fig. 2). 
2. ytfo’o grain : after a few minutes, especially if the mixture be 
stirred, a quite good deposit of stellate groups of crystals. 
3. j-jo-jj grain: after several minutes, there is a quite satisfac- 
Tory crystalline deposit. 
The precipitates produced by this and the preceding reagent, 
can not readily be confirmed by the color test. 
5. Bichromate of Potash. 
This reagent produces in solutions of salts of strychnine a 
bright-yellow precipitate of the chromate of strychnia, which 
almost immediately becomes crystalline. The precipitate is 
insoluble in excess of the precipitant, and in acetic acid, and 
only very sparingly soluble in diluted nitric acid, but readily 
soluble in the concentrated acid; its color is changed to pale 
yellow by potash, and, if from dilute solutions, the deposit is 
slowly dissolved. Prom dilute solutions of the alkaloid, the 568 
STRYCHNINE. 
precipitate does not appear until after a little time, and it then 
separates in the crystalline formj under these circumstances, 
its formation is much facilitated by stirring the mixture with a 
glass rod. 
1. yJo grain of strychnine, yields a very copious precipitate, 
which in a very little time becomes a dense mass of bush- 
like crystals. 
2. xiTo grain: an immediate deposit, and very soon, a copi- 
ous, crystalline precipitate. If after the addition of the 
reagent, the mixture be allowed to remain quiet, the pre- 
cipitate, after a little time, forms most beautiful dendroidal 
groups of crystals, Plate X, fig. 3. 
3* r.iroio grain, yields no immediate precipitate, but very soon 
crystals appear, and in a few minutes, there is a quite 
good deposit. If the mixture be stirred, it yields almost 
immediately, a very good crystalline precipitate. 
4. rrswo grain r on stirring the mixture, in a few moments, it 
yields streaks of granules along the path of the glass rod, 
and soon a quite good deposit of octahedral and bush-like 
crystals, Plate X, fig. 4. 
5- tttooTo grain: if the mixture be stirred, it yields, after some 
minutes, a very satisfactory deposit of small octahedral 
crystals and plates. 
6- rovWo grain; when treated with a small quantity of reagent 
and the mixture stirred, it yields, after several minutes, 
small granules; after about twenty minutes, there is a very 
satisfactory microscopic crystalline deposit of long plates, 
granules, and small octahedral crystals. 
decanted, the crystals dried, and then touched with a small 
drop of concentrated sulphuric acid, they immediately assume 
a magnificent blue color, quickly changing to purple or violet, 
and dissolve to a purple or violet solution, which, passing 
through various shades of color, becomes red, then slowly fades. 
In other words, these crystals may be confirmed by the color 
test by the simple addition of sulphuric acid. The precipitate 
obtained from the 10,000 th of a grain of strychnine, in solution 
in one grain of water, will, in this manner, yield a magnificent 
If the supernatant liquid of any of the above deposits be BICHROMATE OF POTASH TEST. 
569 
display of colors; and even the least microscopic crystal of the 
compound, when touched under this instrument with a very 
small drop of the acid, will yield a very distinct coloration. It 
must, however, be borne in mind, that a solution of strychnine 
may be too dilute to yield any precipitate whatever with this 
reagent, and yet it may have a distinctly bitter taste, and leave 
upon spontaneous evaporation, even of a single drop of the solu- 
tion, a residue, which when examined by the color test in the 
ordinary manner, will yield very satisfactory results. State- 
ments have been made in regard to the delicacy of the reac- 
tion of this test, which are well calculated to lead to erroneous 
conclusions. 
For the separation of the precipitate, for the application of 
this confirmatory reaction, from dilute solutions of the alkaloid, 
it is best to stir the mixture, by means of a glass rod, in a 
watch-glass, and then allow it to repose for about half an hour, 
when the crystallised deposit will be found strongly adherent to 
the glass, and thus permit of the ready separation of the super- 
natant liquid by decantation. Or, the mixture may be allowed 
to evaporate spontaneously to dryness, and the residue touched 
with a drop of pure water, which will readily dissolve any ex- 
cess of the reagent present, while the attached crystals of the 
strychnia compound will remain. 
As bichromate of potash also produces yellow crystalline 
precipitates with brucine, narceine, codeine, and some few other 
principles, and amorphous deposits with morphine, narcotine, 
and a number of other substances, it is obvious, that the mere 
production of even a crystalline precipitate by this reagent, is 
not in itself positive evidence of the presence of strychnine. 
However, the crystalline form of the strychnine compound, as 
usually produced, is somewhat peculiar; and when the crystals 
yield a positive reaction with sulphuric acid, the results are 
perfectly unequivocal. Even a positive reaction by this acid 
from an amorphous deposit, would exclude every other known 
substance, except the active principle of certain kinds of the 
woorara poison. By this method, therefore, the two most char- 
acteristic tests yet known for the recognition of strychnine, may 
he applied to the same quantity of the poison. 570 
STRYCHNINE. 
Protochromate of Potash occasions no precipitate in neutral 
solutions of salts of strychnine, unless they be very concen- 
trated. But with acidulated solutions—providing they do not 
contain very large excess of a mineral acid—it produces results 
similar to those by the bichromate, due to the fact that the free 
acid converts the reagent, in part at least, into the latter salt. 
One grain of a 100 th neutral solution of the alkaloid, yields, 
especially after a little time, a quite good crystalline deposit, 
very similar to that produced by sulphocyanide of potassium 
(Plate X, fig. 2). This, however, is very nearly the limit of 
the reaction of the reagent under these conditions. 
6. Chloride of Gold. 
Terchloride of gold produces in solutions of salts of strych- 
nine, even when highly dilute, a yellowish amorphous precipi- 
tate, which after a time becomes more or less crystalline. The 
precipitate is insoluble in acetic acid, and only sparingly soluble 
in diluted nitric acid; when treated with caustic potash, it 
slowly assumes a dark color. 
1. Yihr grain of strychnine, in one grain of water, yields a very 
copious deposit, which at first has an orange-yellow color, 
but soon becomes yellow and more or less crystalline, form- 
ing groups of bush-like crystals, and granules. If the 
precipitate contains even but little foreign matter, it may 
remain amorphous. 
2. y,tT(To grain; a copious, yellow precipitate, which in a little 
time, becomes converted into groups of crystals, Plate 
X, fig. 5. 
3. r<r;Wo grain, yields a very satisfactory, yellowish deposit, 
which soon furnishes small crystalline groups. 
4. yv.vjTT) grain : a very satisfactory turbidity. 
5. YoToTTo grain, yields a very distinct cloudiness. 
When the precipitate from ten grains of a 5,000 th or more 
dilute solution of the alkaloid, is boiled in the mixture, the de- 
posit dissolves to a clear yellow solution, and it is re-deposited 
with little or no change as the liquid cools; the precipitates 
from stronger solutions, when treated in this manner, do not BICHLORIDE OF PLATINUM TEST. 
571 
entirely dissolve, but undergo more or less decomposition, with 
the deposition of metallic gold upon the sides of the tube. 
Caustic potash dissolves the precipitate from a 5,000 th solution 
to a clear liquid; but the deposit from stronger solutions, is not 
readily soluble in this mineral alkali. Upon the application of 
heat, the potash solution acquires a purplish color, and throws 
down a precipitate. 
Chloride of gold also produces yellow precipitates with many 
other substances, but the crystalline form of the strychnine de- 
posit is somewhat peculiar. The formation of these crystals, 
however, as already intimated, is readily interfered with by the 
presence of foreign matter. 
7. Bichloride of Platinum, 
This reagent produces in solutions of salts of strychnine, a 
pale-yellow amorphous precipitate, which soon becomes crys- 
talline. The precipitate, especially when it has assumed the 
crystalline form, is insoluble in acetic and diluted nitric acids; 
it is unchanged in color and only sparingly soluble in caustic 
potash. 
1. yff grain of strychnine, yields a very copious precipitate, 
which soon becomes a mass of crystals. 
2. YoVo grain: a very good deposit, which is soon converted 
3. rroFo grain: by stirring the mixture, it yields, after a few 
moments, a granular deposit, and after a few minutes, a 
quite good crystalline precipitate. 
into beautiful crystals, Plate X, tig. 6. 
4. YoToiro grain, yields after a little time, if the mixture has 
been stirred, a quite satisfactory deposit of stellate groups 
of crystals, and granules. 
This reagent also produces yellow crystalline precipitates 
with nicotine, potash, and ammonia, a granular deposit with 
morphine, and amorphous precipitates with a number of sub- 
stances ; but the strychnine precipitate is usually readily dis- 
tinguished from these by its crystalline form. In mixtures 
containing much foreign organic matter, however, the strych- 
nine compound may not assume the crystalline state. 572 
STRYCHNINE. 
Chloride of Palladium throws down from solutions of salts of 
strychnine a yellow precipitate, which assumes the same crys- 
talline form as that produced by the platinum reagent; the limit 
of the reaction is also the same. 
8. Carhazotic Acid. 
An alcoholic solution of carhazotic acid occasions in solu- 
tions of salts of strychnine a yellow precipitate of the carbazo- 
tate of strychnia, which is only sparingly soluble in large excess 
of acetic acid, and in alcohol. The precipitate is readily solu- 
ble, to a colorless solution, in sulphuric acid, and the mixture, 
when treated with a color-developing agent, yields the peculiar 
strychnine-series of colors", not, however, in the same intensity 
as many of the other salts of the alkaloid. 
1. xwo grain of strychnine, yields a very copious, amorphous 
precipitate, which slowly becomes converted into a mass 
of irregular crystalline tufts. 
2. rrff oi) grain: a very good precipitate, which soon becomes 
changed into crystals, having the very singular forms illus- 
trated in Plate XI, fig. 1. 
3. ro7SUU grain: on stirring the mixture, it yields, after a little 
time, a very satisfactory, granular deposit. 
4. 2T:Voo grain, yields after a little time, if the mixture has 
been stirred, a quite perceptible, granular precipitate. 
Carhazotic acid also produces crystalline precipitates with 
various other substances. The crystalline form, however, of 
the strychnia compound is somewhat peculiar. 
9. Corrosive Sublimate. 
Chloride of mercury throws down from concentrated neutral 
solutions of salts of strychnine a white amorphous precipitate 
of the double chloride of strychnine and mercury, which is 
readily soluble in acids, even acetic acid. After a time, the 
precipitate becomes crystalline. 
1. yro grain of strychnine, yields a very copious precipitate, 
which in a little time becomes somewhat granular, then lODOHYDRARGYRATE OF POTASSIUM TEST. 
changes into groups of radiating crystals, usually attached 
to a granular nucleus, and aggregations of large granules, 
Plate XI, fig. 2. The general form of these crystals, is 
readily modified by slight circumstances. 
2. xihr grain: after some minutes, the mixture yields a quite 
satisfactory precipitate of stellate crystals. 
In solutions but little more dilute than the last-mentioned, 
the reagent fails to produce a precipitate, even after long repose. 
10. lodohydrargyrate of Potassium. 
This reagent may be prepared by dissolving one part of 
pure corrosive sublimate in one hundred parts of water and 
then adding just sufficient iodide of potassium to redissolve the 
scarlet precipitate first produced, which will require very nearly 
four parts of the iodine compound. A small quantity of this 
mixture throws down from solutions of salts of strychnine a dull 
white precipitate of the double iodide of strychnine and mer- 
cury, Avhich is insoluble in excess of the precipitant and in the 
caustic alkalies, as well as in acetic and hydrochloric acids. 
The precipitate is also insoluble in alcohol; concentrated sul- 
phuric acid readily decomposes it with the production of a 
reddish-brown or purplish color. 
1. XFTT grain of strychnine, in one grain of water, yields a very 
copious curdy precipitate, which after a little time becomes 
partly converted into granules and short crystalline nee- 
dles. If the reagent contain an excess of iodide of potas- 
sium, the precipitate assumes the same crystalline form as 
when this salt alone is employed as the precipitant. 
2. YTcftTo grain, yields a rather copious precipitate. 
8* Totsito grain: a quite good precipitate, which in a little time 
becomes converted into opake granules and short irregular 
needles. On the addition of a few drops of acetic or 
hydrochloric acid, the precipitate is soon changed into 
irregular groups of rather long needles. 
4. rorVou grain, yields a quite distinct precipitate, and in a 
little time, a very satisfactory deposit. This deposit is 
very similar in appearance to that produced from dilute 574 
STRYCHNINE. 
solutions of atropine by bromohydric acid, as illustrated 
in Plate XII, fig. fi. 
5. ro-oVcTo grain: no immediate change, but in a very little 
time, the mixture becomes cloudy, and soon yields a very 
satisfactory deposit of opake granules and short irregular 
needles. 
The production of a white precipitate by this reagent is 
common to solutions of most, if not all, of the alkaloids. 
11. Ferricyanide of Potassium. 
Red Prussiate of potash produces in quite strong neutral 
solutions of salts of strychnine a yellowish amorphous precipi- 
tate, which in a little time becomes crystalline. The precipitate 
is only slowly soluble in acetic acid, but readily soluble in the 
stronger acids, and is, therefore, not produced in their presence. 
1. two grain of strychnine, yields a quite copious precipitate, 
which in a few moments becomes converted into a mass of 
2. jxto grain, yields a very good crystalline precipitate. 
3. T:h~o grain, yields little or no indication of the presence of 
beautiful groups of crystals, Plate XI, fig. B. 
the poison, even after the mixture has stood half an hour 
or longer. 
When a small portion of the precipitate, occasioned by this 
reagent, is treated with a drop of concentrated sulphuric acid, 
it, like that produced by the bichromate of potash, dissolves 
with the production of the same series of colors as obtained by 
the color test as ordinarily applied. The least visible crystal 
of the deposit will respond to this reaction. It will be observed, 
however, that as a precipitant for strychnine, ferricyanide of 
potassium in point of delicacy, is far inferior to bichromate 
of potash. 
Nitro-prusside of Sodium throws down from neutral solutions 
of salts of strychnine a white or dirty-white precipitate, which 
assumes the same crystalline form as that produced by ferri- 
cyanide of potassium, and the limit of the reaction is about 
the same. But, notwithstanding the contrary has been as- 
serted, this precipitate, unlike that occasioned by ferricyanide lODINE TEST 
575 
of potassium, dissolves without change of color in concentrated 
sulphuric acid. 
Ferrocyanide of Potassium fails to precipitate solutions of 
salts of strychnine, unless very concentrated and perfectly neu- 
tral. One grain of a 100 th solution of the alkaloid will yield 
a quite good crystalline deposit; but this is very nearly the 
limit of the reaction. 
12. lodine in lodide of Potassium. 
An aqueous solution of iodine in iodide of potassium pro- 
duces in solutions -of salts of strychnine, even when highly 
diluted, a reddish-brown amorphous precipitate, which is read- 
ily soluble in alcohol, but only very sparingly soluble in acetic 
acid. The precipitate is readily soluble in caustic potash, but 
it is soon replaced by a white deposit. Dr. W. B. Herapath 
has shown (Chem. Gaz., 1855, p. 320), that an alcoholic solu- 
tion of strychnine yields with iodine, crystalline compounds, 
having very peculiar optical properties. 
1. grain of strychnine, yields a very copious deposit, which 
2. rrooo grain.: a copious precipitate, which after a time be- 
comes, in part at least, converted into crystals, Plate XI, 
tig. 4. These crystals are most readily obtained when 
large excess of the reagent is avoided. 
after a time becomes more or less crystalline. 
3. xoTtraij grain, yields a very good precipitate, which readily 
dissolves to a colorless solution in caustic potash, but after 
a little time the mixture becomes turbid. The precipitate 
is slowly converted into crystalline nodules. 
4. sotVou grain, yields a very satisfactory deposit. 
5. rooViTo grain, furnishes a very distinct turbidity. 
This reagent also produces precipitates with a variety of 
organic substances, and with certain inorganic compounds, but 
the character of the strychnine crystals is quite peculiar; their 
formation, however, is readily interfered with by the presence 
of foreign matter. 
The strychnine may be recovered from the washed precipi- 
tate, by dissolving the latter in strong alcohol, and treating the 576 
STRYCHNINE. 
solution with slight excess of nitrate of silver, which will pre- 
cipitate the iodine as iodide of silver; this is removed by a 
filter, and the excess of the silver reagent precipitated from the 
filtrate by the cautious addition of diluted hydrochloric acid; 
the chloride of silver thus produced is then separated by a filter, 
and the filtrate evaporated to dryness on a water-bath, when 
the strychnine will be left in its pure state. This method will 
serve for the recovery of even extremely minute quantities of 
the alkaloid. 
13. Bromine in Bromohydric Acid. 
A strong aqueous solution of bromohydric acid saturated 
with bromine, occasions in solutions of salts of strychnine, even 
when very dilute, a yellow amorphous precipitate, which is 
readily soluble in alcohol, and in acetic acid. The precipitate 
remains amorphous. 
1. jwo grain of strychnine, yields a very copious, bright-yellow 
deposit, which after a time disappears, but it is reproduced 
upon further addition of the reagent. 
2. x7crou grain, yields a copious precipitate. 
6* ToToiro grain: a very good deposit. 
4. sir;Vu-o grain, yields a very satisfactory, yellow precipitate. 
5* Too Toon grain, yields a distinct turbidity, which after a time 
disappears, and is not reproduced upon further addition of 
the reagent. 
The reaction of this reagent is common to a large class of 
organic substances. 
14. Physiological Test. 
Dr. Marshall Hall proposed to take advantage of the extreme 
sensibility of frogs to the effects of strychnine, as a means of 
detecting its presence. He advised to immerse the frog to be 
experimented upon, in a solution of the poison; when sooner or 
later, according to the strength of the solution, the animal is 
seized with violent tetanic convulsions, in which the extremi- 
ties become extended to their uttermost and the whole body PHYSIOLOGICAL TEST. 
577 
perfectly rigid. By this method Dr. Hall states that he was 
enabled to detect the 5,000 th part of a grain of strychnine. 
More recently Dr. Harley proposed to inject the strychnine 
solution into the thoracic or abdominal cavity of the animal y 
and he states that the 16,000 th part of a grain of the acetate 
of strychnia introduced into the lungs of a very small frog, will 
render it violently tetanic in about ten minutes. 
In the following examinations of this test, about two grains 
of the strychnine solution were taken up by a pipette, the tilled 
end of which was then introduced into the stomach of the frog, 
and the liquid discharged by blowing through the tube. The 
animals were then placed under an open glass receiver. The 
frogs were fresh, and varied in weight from fifteen to fifty 
grains. The results for each quantity of the poison are based 
upon numerous experiments, and chiefly upon the species of 
animal known as Rana Halecina. 
1. 100 th solution—equal to about the 50th of a grain of strych- 
nine—usually produces immediate and violent spasms, and 
death in about eight minutes. 
2. I,oooth solution: the symptoms generally manifest them- 
selves in three or four minutes, and death usually takes 
place in from fifteen to thirty minutes. 
3. 10,000 th solution: in some instances the symptoms appeared 
within ten minutes, while in others they were delayed as 
long as half an hour. 
4. 20,000 th solution, generally produces characteristic symp- 
toms in from thirty to forty-five minutes; but in some 
few instances the results were not well marked, even after 
long periods. 
5. 30,000 th solution, or the 15,000 th of a grain of strychnine: 
in most instances, especially when very small animals were 
employed, the symptoms appeared within fifty minutes; 
but in some cases there were no marked effects, even after 
some hours. 
In applying this test, the frogs should always be fresh from 
fhe pond. Occasional agitation of the animal hastens the action 
°f the smaller quantities of the poison ; and frequently a violent 
paroxysm may be induced by a sudden noise, such as clapping 
37 578 
STRYCHNINE. 
of the hands. From experiments made at different times, we 
are strongly inclined to believe that the sensibility of this animal 
to the effects of strychnine, differs somewhat with the seasons 
of the year. The Spring and early part of the Summer seem 
to be the most favorable for the application of the test. It may 
be remarked, that in regard to weight, the 20,000 th of a grain 
of strychnine bears about the same relation to a frog weighing 
twenty-five grains, that two grains do to a man weighing one 
hundred and forty pounds. When, therefore, the foregoing 
experiments are taken in connection with the known effects of 
this poison upon the human subject, it would appear, that, if 
any difference, the frog was relatively somewhat less sensitive 
than man to its action. 
This physiological test certainly affords a very valuable 
means of corroborating the chemical evidence of the presence 
of strychnine, and at the same time, as we have just seen, it is 
extremely delicate; yet it should never be employed to the ex- 
clusion of at least some of the chemical tests. In regard to 
delicacy, for the pure alkaloid, it is much inferior to the color 
test, the latter yielding satisfactory results with a quantity of 
the poison that would produce no appreciable effect upon a frog, 
even of the smallest size. 
Other Reagents.— Chlorine gas passed into somewhat strong 
solutions of salts of strychnine produces a white amorphous pre- 
cipitate. Ten grains of a I,oooth solution of the alkaloid yields 
a quite good deposit, which is unchanged upon the addition of 
ammonia; a similar quantity of a 10,000 th solution yields a 
distinct milkiness, which quickly disappears on the addition of 
ammonia. 
Tannic acid, phosphomolybdic acid, a solution of perchloride 
of antimony in phosphoric acid, and Nessler’s test for ammonia, 
also precipitate strychnine from solutions of its salts, even in 
some instances when highly diluted. But as the reactions of 
these reagents are common to a large class of organic com- 
pounds, the results have little or no positive value. Gallic acid 
fails to produce a precipitate, even in highly concentrated solu- 
tions of salts of the alkaloid. SEPARATION FROM ORGANIC MIXTURES. 
579 
Separation from Organic Mixtures. 
From Nux Vomica. Strychnine may be separated from 
powdered nux vomica, by digesting the powder, for some time, 
at a moderate heat with a small quantity of water slightly acid- 
ulated with acetic acid; when the decoction has cooled, it is 
filtered, and the filtrate concentrated over a water-bath to a 
small volume. The concentrated solution, which will have the 
intensely bitter taste of the alkaloid, is now treated with slight 
excess of caustic potash or soda, and violently agitated with its 
own volume or more of chloroform. After the liquids have 
completely separated, the chloroform is carefully withdrawn, 
and allowed to evaporate spontaneously in a watch-glass, when 
the alkaloid will be left, usually in its amorphous state, together 
with more or less foreign matter. 
The residue thus obtained may either be examined at once 
by the chemical tests or be further purified, by dissolving it in 
a very small quantity of acidulated water, rendering the solu- 
tion alkaline, and again extracting with chloroform. After 
examining a portion of the residue by the color test, any re- 
maining portion may be dissolved in a small quantity of water 
containing a trace of acetic acid, and the solution examined by 
the bichromate of potash, or any of the other liquid tests for 
the alkaloid. A single grain of powdered nux vomica, in its 
free state, when treated after the above method, will yield very 
satisfactory evidence of the presence of strychnine. 
Suspected Solutions and Contents of the Stomach.— 
Any organic solids present in the mixture presented for ex- 
amination, are cut into small pieces and the mass, after the 
addition of water if necessary, treated with about half its vol- 
ume of strong alcohol and sufficient acetic acid to give it a dis- 
tinctly acid reaction. The acidulated mixture is now digested 
at a moderate heat on a water-bath, with frequent stirring, for 
about half an hour or longer. It is then, after cooling, thrown 
Upon a wet linen strainer, and the solid residue well washed 
with diluted alcohol, and strongly pressed. The mixed strained 
fluids are concentrated at a moderate temperature to a small 580 
STRYCHNINE. 
volume, again strained, and if practicable filtered, then evap- 
orated on a water-bath to about dryness. Any strychnine 
present, will now be in the residue, in the form of acetate of 
strychnia, mixed with more or less foreign matter. 
The residue, obtained by this operation, is thoroughly stirred 
with a small quantity of water containing a drop of acetic acid, 
the mixture filtered, the filter washed with a little water, and 
the mixed filtrates, after concentration if necessary, transferred 
to a stout test-tube or small bottle, and treated with slight ex- 
cess of caustic potash or soda, by which the strychnine will be 
set free from its saline combination. Should the mixture con- 
tain a comparatively large quantity of the alkaloid, the latter 
may after a time assume the crystalline form. The alkaline 
mixture is now violently agitated for about a minute with some- 
thing more than its own volume of pure chloroform. When the 
liquids have completely separated, the supernatant aqueous fluid 
is carefully transferred, by moans of a pipette, to another test- 
tube, and the chloroform decanted into a watch-glass, great care 
being taken that no remaining drops of the aqueous liquid pass 
over with the chloroform; the alkaline aqueous mixture is then 
washed with a fresh portion of chloroform, and this collected 
with that first employed. A very good method for separating 
the last drops of the aqueous liquid from the decanted chloro- 
form, is to collect the latter liquid in a dry test-tube and decant 
it from this into the watch-glass : the last traces of the former 
fluid will now usually remain attached to the sides of the tube. 
If, however, the chloroform has still a milky appearance, the 
liquid may be passed through a small paper-filter, previously 
moistened with pure chloroform. 
The decanted chloroform, which contains any strychnine that 
was present in the alkaline mixture, is now allowed to evaporate 
spontaneously to dryness. If the liquid contained a very nota- 
ble quantity of the alkaloid, the latter may remain in its crys- 
talline form: this result, however, is rarely obtained from the 
first chloroform extract, when operating on the contents of a 
stomach containing the poison. A portion of the residue may 
be examined by the color test, as also by the taste; and 
any remaining portion dissolved in an appropriate quantity of SEPARATION FROM ORGANIC MIXTURES. 
581 
distilled water containing a trace of acetic acid, and the solution, 
after filtration if necessary, examined by some of the liquid 
tests for strychnine, beginning with the bichromate of potash. 
If, however, the examination of a small portion of the dry resi- 
due indicate the presence of much foreign matter, the acidu- 
lated aqueous solution is rendered alkaline, again extracted by 
chloroform, and this liquid separated and evaporated as before, 
when the alkaloid, even if present only in very minute quan- 
tity, will usually be left in its crystalline state, or at least 
sufficiently pure for the application of the most important tests. 
When the mixture presented for examination is extremely 
complex, as is frequently the case with the contents of the 
stomach, it sometimes happens that on agitating the prepared 
alkaline solution with chloroform, the whole becomes a white 
frothy emulsion, from which the chloroform will not separate, 
even after several hours. When this occurs, the mixture may 
be moderately agitated with about half its volume of pure water, 
and the whole allowed to repose, if necessary, for some hours, 
when more or less of the water will separate as a highly colored 
fluid; this is decanted, and the operation repeated with fresh 
portions of water as long as the liquid becomes colored. By 
this means, much of the foreign matter will be separated, while 
any strychnine present will remain in solution in the chloroform 
mixture, at most only the merest trace of it being taken up by 
the decanted water. The mixture is now slightly acidulated by 
a drop or two of acetic acid. It may then be transferred to a 
small dish and evaporated to dryness on a water-bath, and the 
residue stirred with a very small quantity of pure water, the 
solution, after filtration if necessary, rendered slightly alkaline, 
and again agitated with fresh chloroform, which will now usually 
readily separate. Instead of treating the acidulated chloroform 
mixture in the manner just described, it may be agitated with 
consecutive portions of pure water as long as this liquid acquires 
a bitter taste, when the alkaloid will be extracted as acetate of 
strychnia, and be left as such on evaporating the solution to 
flryness over a water-bath. 
On applying the general method now described, to the ex- 
amination of the contents of the stomach of several different STRYCHNINE. 
cats, each of which had been killed by half a grain of strych- 
nine, we in no instance failed to recover the poison in quanti- 
ties several times more than sufficient to fully establish its true 
nature in the most satisfactory manner. The only instance 
among these in which a quantitative analysis was performed, 
was in the case of a young cat, to which the poison had been 
administered in solution, upon a very full stomach, and death 
ensued in ten minutes; the third chloroform extract furnished 
yVoths of a grain of the pure crystallised alkaloid. During the 
purification of the alkaloid in this case, there was, of course, a 
very notable quantity of the poison, which would have been 
available for qualitative purposes, lost. 
On following the same method in a recent case, for the 
examination of the contents of the stomach of a man, who had 
died from the effects of strychnine, administered, there is every 
reason for believing, in comparatively small quantity, yyirths of 
a grain of the pure alkaloid, chiefly in its crystalline state, were 
recovered. And in another case, in which an unknown quan- 
tity of the poison had been administered and death took place 
in about an hour, the final residue furnished iVoths of a grain 
of the pure alkaloid. 
Method hy Dialysis.—To apply this process, the details of 
which have heretofore been pointed out {ante, p. 420), the 
organic mixture, acidulated with acetic or hydrochloric acid, is 
prepared in the manner already described for the examination 
of the contents of the stomach, and the concentrated solution 
placed in the dialyser, which is then floated in a dish contain- 
ing four or five times as much pure water as the volume of 
fluid to be dialysed 5 after twenty-four or thirty-six hours, the 
diffusate is transferred to a porcelain dish, evaporated to dry- 
ness on a water-bath, and the residue examined. 
In regard to the relative merits of this method, even with 
mixtures containing comparatively large quantities of strych- 
nine, experiments indicate that the diffusate usually becomes 
contaminated to such an extent with foreign matter, that to 
separate the alkaloid from this, requires just the same opera- 
tions as required to recover it directly, by the ordinary methods, 
from the original mixture 5 moreover, the relative quantity of RECOVERY BY DIALYSIS. 
583 
the alkaloid that passes into the diffusate, even after twenty- 
four or thirty-six hours, never exceeds the proportion existing 
between the volume of liquid in the diffusate and that in the 
dialyser. Of many experiments, in support of the statements 
just made, that might be mentioned, the two following may 
be cited:— 
Ist. Three-quarters of a grain of strychnine, in solution, 
were administered to a cat, which had recently been fed; in 
about four minutes, the animal was seized with violent tetanic 
convulsions and died during the paroxysm. The contents of 
the stomach, together with the cut-up tissue of the organ, were 
.mixed with six ounces of distilled water containing about half 
its volume of alcohol, the whole acidulated with acetic acid, and 
digested on a water-bath for twenty minutes ; then strained and 
the solution concentrated to twelve fluid drachms. This solu- 
tion was then dialysed, with Jive volumes of pure water as the 
diffusate, for forty hours. 
a. The diffusate was now concentrated on a water-bath to 
one fluid drachm, when it formed a highly turbid, reddish-brown 
mixture, having a decidedly acid reaction and intensely bitter 
taste; the liquid was then filtered, rendered alkaline by potash, 
and agitated with little more than its own volume of pure chlo- 
roform. This liquid, after some difficulty, was separated, the 
aqueous fluid washed with a fresh portion of chloroform, and 
the mixed chloroforms allowed to evaporate spontaneously. The 
residue, obtained by this operation, was amorphous, and evi- 
dently contained a large proportion of foreign matter, although 
the least portion of it, when examined by the color test, very 
plainly indicated the presence of strychnine. On stirring the 
deposit with a small quantity of acidulated water, it furnished a 
quite turbid mixture. This was filtered, and the filtrate, after 
the addition of a drop of potash, again extracted by chloroform, 
which upon spontaneous evaporation, left the alkaloid in its pure 
state, and chiefly in the crystalline form. The residue, when 
perfectly dried, weighed yVVths of a grain. 
b. The contents of the dialyser were evaporated to dryness, 
the residue stirred with about a drachm of acidulated water, 
the solution passed repeatedly through a plug of raw cotton, 584 
STRYCHNINE. 
then rendered alkaline, and agitated with about its own volume 
of chloroform. This fluid, which readily separated, was then, 
together with a fresh portion of the liquid used for washing the 
aqueous mixture, exposed to spontaneous evaporation, when it 
left a small residue, which contained some few crystals of pure 
strychnine ; but it was quite evident that the amorphous part of 
the deposit contained a large proportion of foreign matter. On 
now dissolving the residue in acidulated water, and again ex- 
tracting the solution in the ordinary manner by chloroform, this 
liquid, on spontaneous evaporation, left the alkaloid in its pure 
state, and principally in the crystalline form; this residue, when 
dried, weighed yfroths of a grain. 
It will be observed, in the case now detailed, that although 
the conditions, both in regard to the time the dialysation was 
continued and the quantity of fluid employed for the diffusate, 
were most favorable for the diffusion; yet, nearly one half as 
much strychnine was obtained from the mixture dialysed as 
from the diffusate, and with about the very same operations as 
enqployed in the examination of the latter. The labor consumed 
by the two operations was, therefore, apparently fully twice 
that which would have been required to separate the poison at 
once from the original mixture; and, at the same time, there is 
little doubt but more of the alkaloid would have been recovered 
in this manner than by the two separate operations. It is, 
however, but proper to add, that perhaps more difficulty would 
have been experienced in the purification of the original mix- 
ture before subjecting it to the process of dialysis, than there 
was after this operation. 
2d. The finely-divided liver of a cat, which had been killed 
by a blow upon the head, was gently boiled with several ounces 
of water acidulated with hydrochloric acid, until the organic 
matter was well broken up; the mixture was then strained, and 
the solution concentrated to twelve fluid drachms. Half a grain 
of pure strychnine was now added to the concentrated liquid, 
and the mixture dialysed, with five volumes of pure water, for 
thirty-seven hours. 
The diffusate was then evaporated to dryness, the gummy 
residue dissolved in a small quantity of water, the solution RECOVERY BY DIALYSIS. 
585 
filtered, then rendered alkaline, and agitated with chloroform. 
This fluid separated readily, and when evaporated spontane- 
ously, left a comparatively large residue, consisting principally 
of crystals of pure strychnine. The deposit was again dissolved 
in a small quantity of liquid, and the solution extracted a sec- 
ond time by chloroform. On spontaneous evaporation, the chlo- 
roform now left a residue of pure crystallised strychnine, which, 
when thoroughly dried, weighed -jVoths of a grain. 
The mixture in the dialyser was concentrated on a water- 
bath to six fluid drachms, then strained through cotton, and the 
turbid solution evaporated to dryness, when it left a quite large, 
gummy residue. This was stirred with a little water, and many 
attempts made to clear the mixture by filtration, but the liquid 
still remained turbid. It was then rendered alkaline, and agi- 
tated with chloroform, with which it formed a white saponaceous 
mass from which the chloroform would not separate. This was 
now washed several times with pure water, then acidulated with 
acetic acid, and evaporated to dryness, the residue dissolved in 
water, the solution filtered, then rendered alkaline and again 
agitated with chloroform. About three-fourths of this liquid 
readily separated, but the remaining portion did not, even after 
some hours. The clear chloroform was now removed, and the 
frothy mixture again evaporated to dryness, and the residue, 
after solution and filtration, extracted with fresh chloroform, 
which now readily separated. The mixed chloroforms were 
then allowed to evaporate spontaneously, when they left a 
residue of pure strychnine, chiefly in the form of large col- 
orless stellate crystals, which, when dried, weighed yiroths of 
a grain. 
It will be observed that in this instance the purification of 
the dialysed mixture was attended with much more difficulty 
than in the preceding experiment; and that the reverse, to a 
certain extent, was true in regard to the diffusate. It also ap- 
pears, that the alkaloid, in this case, distributed itself between 
the diffusate and fluid in the dialyser, very nearly in the pro- 
portions of the volumes of these liquids; and that only eight 
per cent, of the strychnine was lost in the experiment. The 
two instances now cited represent about the extremes, in 586 
STRYCHNINE. 
regard to results, of several experiments of this kind that might 
be adduced. 
From the Tissues.—The soft organ, such as a portion of 
the liver, is placed in a porcelain evaporating dish, and cut into 
very small pieces, taking care that none of the fluid present is 
lost; the mass is rendered sufficiently liquid by water, some 
strong alcohol added, and the whole well stirred, and acidulated 
with sulphuric acid, in the proportion of about eight drops of 
the concentrated acid for each fluid ounce of the mixture. It 
is then digested at a temperature of about 180° F., with fre- 
quent stirring, for half an hour or longer, and, after cooling, 
strained through a fine linen cloth, the residue washed with 
acidulated water and strongly pressed. 
The strained liquid, including the washings, thus obtained, 
is concentrated on a water-bath, and, when much solid matter 
has separated, again strained, these operations being repeated 
until the fluid is reduced to a small volume. This is nearly 
neutralised with caustic potash, taking care however that the 
mixture still retains a very decided acid reaction; then filtered, 
and the filtrate evaporated, on a water-bath, until only a few 
drops of liquid remain. When this residue has cooled, it is well 
stirred with about half an ounce of concentrated alcohol, which 
will dissolve, in the form of sulphate, any strychnine present, 
while the sulphate of potash, formed from the sulphuric acid 
and potash added, together with more or less of the foreign 
organic matter, will remain undissolved. The alcoholic solution, 
after filtration, is evaporated on a water-bath to almost dryness, 
the residue stirred with a small quantity of pure water, and the 
filtered solution rendered slightly alkaline by caustic potash or 
soda. It is then agitated with pure chloroform in the usual 
manner, and this fluid, after careful separation, allowed to evap- 
orate spontaneously. 
If on stirring the above nearly dry residue with concen- 
trated alcohol, for the separation of the poison from the sulphate 
of potash, it should form a tenacious gummy mass that will not 
mix with the liquid—as is sometimes the case, especially when 
the subject under examination is the liver—the fluid is expelled 
by evaporation, the residue stirred with water, the filtered RECOVERY FROM THE BLOOD. 
587 
solution evaporated to nearly dryness, and the residue again 
treated with alcohol, with which the deposit will now usually 
readily mix. Again, should the final alkaline solution when 
agitated with chloroform, form a white emulsion from which the 
chloroform will not separate, the mixture is treated after one or 
other of the methods before described for mixtures of this kind. 
The sixth of a grain of strychnine, in solution, was given to 
a healthy cat, which had just been fed. Twelve minutes after- 
wards, the animal was seized with violent tetanic symptoms, 
and died three minutes later. The liver, together with the con- 
tained blood, was then treated after the preceding method. The 
first chloroform solution thus obtained, left on spontaneous evap- 
oration, a very small gummy residue, which when examined in 
three separate portions by the color test, gave, in each instance, 
perfectly satisfactory evidence of the presence of strychnine. 
Although the quantity of the poison thus recovered, was even 
more than sufficient to fully establish its presence by this test; 
yet it was, probably, too minute to have permitted the reaction 
of this test being confirmed by any of the other tests, except 
by the taste. Whether the strychnine recovered in this instance 
was simply present in the blood contained in the liver, or whether 
a portion of it had been deposited in the tissue of this organ, is 
difficult to decide. None of the other tissues of this animal were 
examined. An analysis of the gall-bladder and its contents, of 
a similar animal, killed in fifteen minutes by the sixth of a 
grain of strychnine, failed to reveal the presence of a trace of 
the poison. 
The Blood.—This fluid may be examined for absorbed 
strychnine in much the same manner as just described for the 
analysis of the tissues. About four fluid ounces of the sus- 
pected blood, placed in a wide-mouthed bottle, are mixed with 
an equal volume of water and about half a volume of strong 
alcohol, and about eight minims of concentrated sulphuric acid 
added for each ounce of blood, and the whole thoroughly agi- 
tated, until the mixture becomes perfectly homogeneous. It is 
then heated in a dish, on a water-bath, to near the boiling tem- 
perature, with constant stirring, for about fifteen minutes, and 
while still warm, the liquid portion squeezed through a fine 588 
STRYCHNINE. 
linen cloth, and the black viscid residue washed with alcohol 
and pressed. Should the whole of the mixture pass through 
the strainer, as will be the case if too much acid has been 
added, it is returned to the dish, treated with a few drops of 
caustic potash, and again heated for a few minutes, then 
strained. If, on the other hand, the solid matter separated by 
the strainer, when pressed, is dry and pulverisable, it is re- 
turned to the strained liquid, the mixture heated with a few 
drops more of sulphuric acid, and again returned to the strainer. 
The highly colored, turbid liquid, thus obtained, is treated 
with a few drops of caustic potash, so as to somewhat diminish 
its acidity, then concentrated somewhat, and again strained. 
The solution is now nearly neutralised by the cautious addition 
of a caustic alkali, and again heated, when most of the albu- 
minous matter will separate in the form of little brownish flakes. 
These are separated, from the cooled mixture, by means of a 
linen strainer, washed with diluted alcohol, and strongly pressed. 
If the flocculent matter is not entirely separated by the first 
straining, in this operation, the fluid is returned to the cloth 
until it passes through perfectly clear. The liquid will now 
usually have only a light brownish color, while the separated 
solids will be dry and pulverisable. 
The clear liquid, thus obtained, is concentrated on a water- 
bath to a small volume, passed through a small filter, previously 
moistened with water, the filter washed, and the mixed filtrates 
evaporated to about dryness. The residue, thus left, is well 
stirred, by means of a glass rod or the clean finger, with about 
an ounce of nearly absolute alcohol, the solution filtered, the 
filter washed with similar alcohol, and the clear liquids evap- 
orated at a very moderate temperature to almost dryness. This 
residue is thoroughly stirred with about a drachm of pure water, 
and the solution filtered. The filtrate may now be examined 
by the taste. It is then rendered slightly alkaline by caustic 
soda or potash, and agitated in the ordinary manner with chlo- 
roform. This liquid, after separation, is allowed to evaporate 
spontaneously, and the residue examined in the usual manner. 
In the examination of this residue, the operator should bear in 
mind, that at most there is only a very minute quantity of RECOVERY FROM THE BLOOD. 
589 
strychnine present, and unless great care be exercised, it may 
entirely escape detection. 
Absorbed strychnine seems to adhere more tenaciously to 
the solids of the blood than any other poison, with, perhaps, 
the single exception of morphine. For its recovery from this 
fluid, it is essential that the liquid, after the addition of water 
and alcohol, be at first acidulated as strongly as possible com- 
patible with the separation of at least a small portion of the 
solid matter. The exact quantity of acid necessary for this 
purpose will vary somewhat with different samples of blood; it 
also appears, that sulphuric acid is better adapted than any 
other acid for this purpose. If the poisoned blood be acidu- 
lated only moderately, as for the recovery of most of the other 
alkaloids, the whole of the strychnine will usually be separated 
along with the solid albuminous matter. Before resorting to the 
method just described, we had followed various methods advised 
by others, and these variously modified, with the blood of not 
less than fifteen separate animals, killed by strychnine, without 
in any instance obtaining distinct evidence of the presence of 
the poison. In fact, it was only by applying the process under 
consideration to the solids separated by some of these methods, 
and thus clearly recovering the poison, that we were led to 
apply it directly to the blood. 
On following this method for the examination of the blood 
of six different cats, and of two dogs, poisoned by compara- 
tively small doses of strychnine, we in every instance obtained 
perfectly satisfactory and unequivocal evidence of the presence 
of the poison. In two of these cases, in each of which half a 
grain of strychnine had been administered to young cats and 
death took place in three and six minutes respectively, six fluid 
drachms of blood from each—the whole that was obtained— 
furnished residues, about the fifth part of each of which, when 
examined by the color test, gave unquestionable evidence of the 
presence of the alkaloid. These instances show the extreme 
rapidity with which a quite notable quantity of the poison may 
be absorbed. In fact, in these two cases, there was apparently 
as much strychnine recovered as in those in which life was 
prolonged for about half an hour. 590 
STRYCHNINE. 
In none of these cases did the chloroform leave the strych- 
nine in a distinctly crystalline form. But in one of them, after 
the presence of the poison had been shown in a portion of the 
residue by the color test, the remaining portion, when stirred 
with a drop of a very dilute solution of bichromate of potash, 
and the fluid allowed to evaporate spontaneously, furnished a 
number of octahedral crystals of the chromate of strychnia: 
this was the only instance in which the residue was thus treated. 
In every instance, the whole of the blood that could be obtained 
from the animal, was examined at one operation. It does not, 
of course, follow, that a given quantity of blood taken from the 
human subject, poisoned by strychnine, would contain the same 
amount of the poison as would be present, under like conditions, 
in a similar quantity of blood from a cat. Indeed, the differ- 
ence between the smallest fatal dose for the former and that for 
the latter, seems to be very much less than that between the 
absolute quantities of blood found in each. 
On following the method of Dialysis, in three different cases, 
for the examination of the blood of animals poisoned by strych- 
nine, we in no instance detected a trace of the poison in the 
diffusate. Previously to introducing the blood into the dialyser, 
the strongly acidulated fluid was heated for some time with 
diluted alcohol, then strained and concentrated. On examining 
the dialysed blood, in one case, by the method heretofore de- 
scribed, it furnished very distinct evidence of the presence of 
the poison. 
From the Urine.—Strychnine may be separated .from the 
urine, by acidulating the liquid with a few drops of acetic acid, 
and evaporating it on a water-bath to a thick syrup. When 
this has cooled, it is well stirred with about a fluid ounce of 
nearly absolute alcohol, the solution filtered, and the residue on 
the filter washed with similar alcohol, and then strongly pressed. 
The yellowish filtrate thus obtained, is concentrated to a thick 
syrup, and the residue dissolved in a small quantity of pure 
water. This solution, after filtration if necessary, ds rendered 
slightly alkaline, by either of the fixed caustic alkalies, and 
agitated in the ordinary manner with pure chloroform, which, 
after separation, is allowed to evaporate spontaneously, when FAILURE TO DETECT. 
591 
the alkaloid, if present in very notable quantity, will be left in 
its crystalline state. 
By following this method for the examination of a fluid 
ounce of normal urine, to which the 100 th part of a grain of 
strychnine has been purposely added—the dilution being one 
part of the poison in about 50,000 parts of the liquid—the 
alkaloid may be recovered, in the pure crystalline form, with 
scarcely any appreciable loss. 
One-fourth of a grain of strychnine, in solution, was given 
to a very large dog, weighing about eighty-five pounds. Slight 
tetanic symptoms manifested themselves in about fifteen minutes. 
These continued for about a quarter of an hour, when a second 
dose, containing a similar quantity of the poison, was adminis- 
tered. The animal was now soon seized with violent symptoms, 
but survived the effects of the poison, one hour and three- 
quarters after the administration of the first dose. Five ounces 
of urine were recovered from the bladder, and treated after the 
foregoing method; but the examination failed to reveal any 
distinct evidence of the presence of strychnine. A second dog, 
weighing about sixty pounds, was given a quarter of a grain 
of the acetate of strychnia. Symptoms appeared in twenty 
minutes, and after twenty minutes more, the animal was found 
dead. An examination of five and a half ounces of urine 
obtained from this animal, also failed to indicate the presence 
of the poison. In this case, the urine was strongly acidulated 
with sulphuric acid, instead of acetic acid, as in the preceding 
examinations. In another instance, however, in which the above 
method was employed, for the examination of two ounces of 
bloody urine obtained from the bladder of a man, who had died 
in one hour and three-quarters, from the effects of an unknown 
quantity of strychnine, the second chloroform residue, when 
examined by the color test, gave satisfactory evidence of the 
presence of the poison. 
Failure to Detect the Poison.—lt has not unfrequently 
happened, in fatal poisoning by strychnine, that there was a 
failure to detect a trace of the poison, even in the contents of 
the stomach and under circumstances apparently very favorable 
for its recovery. There is little doubt but some of these failures 592 
STRYCHNINE. 
may be justly attributed to the imperfect methods of analyses 
employed; yet they have occurred in the hands of the most 
experienced manipulators. The whole of the poison may be 
rapidly removed from the stomach by the process of absorption 
or the act of vomiting, or by these combined; and, in protracted 
cases, even that which has been absorbed may be entirely elim- 
inated from the body previous to death. 
In the case reported by Dr. J. J. Reese, already cited, in 
which about six grains of the poison had been taken and life 
was prolonged for six hours, separate analyses, made eight 
weeks after death, of the contents of the stomach, of the con- 
tents of the small intestines, and of the tissues of the stomach 
and intestines, failed to reveal the presence of a trace of strych- 
nine, either by the taste of the final extract or by the color 
test. From the quantity of strychnine taken in this instance, 
and the fact that there seems to have been no vomiting, it was 
one apparently favorable for the recovery of the poison. Since 
the tissues were in a good state of preservation at the time of 
the examination, it can not reasonably be supposed that the 
poison had undergone decomposition in the dead body. Dr. 
Reese attributed the failure to the fact, that just before death 
the deceased had taken a quarter of a grain of morphine, 
which, as we have already seen, has the property of disguising 
the ordinary reaction of the color test. But, as the final ex- 
tracts were obtained through the agency of ether, in which 
morphine is almost wholly insoluble, especially in the presence 
of a free alkali, this explanation can hardly be admitted; more- 
over, morphine has not the property of concealing the intensely 
bitter taste of strychnine. 
In regard to the effects of decomposition, experiments indi- 
cate that strychnine may be kept in contact with decomposing 
animal matter, for at least several months, without itself under- 
going any change. It would, however, be an error to suppose 
that the alkaloid could be recovered, under these conditions, 
after as long periods as some of the mineral poisons. In a case 
of fatal poisoning by strychnine reported by Dr. A. A. Hayes, 
of Boston, he recovered over half a grain of the pure crystal- 
lised alkaloid, from the fourth part of the contents of the BRUCINE. 
593 
stomach, two weeks after death. (Boston Med. and Surg. Jour., 
March, 1861, p. 133.) At the trial of Mary Freet, charged 
with the murder of her husband by strychnine, it was alleged, 
that a few weeks prior to the administration of the fatal dose, 
the defendant prepared a bowl of mush and milk for the de- 
ceased, and that he complained of its having a bitter taste and 
threw the contents of the bowl into the yard; and that after- 
wards a cat having eaten the mush very suddenly died. A 
chemical examination of the contents of the stomach of the 
animal two months after death, the body having part of the 
time been exposed in a common alley, clearly revealed the 
presence of strychnine. 
Quantitative Analysis.—The quantity of strychnine pres- 
ent in a pure aqueous solution of any of its salts, may be 
estimated, with sufficient accuracy for ordinary purposes, by 
treating the somewhat concentrated solution with slight excess 
of caustic potash, and allowing the mixture to stand in a cool 
place for from twelve to twenty-four hours, when the deposit 
will have assumed the crystalline form. The precipitate is 
then collected on a small equipoised filter, washed with a small 
quantity of cold water, dried on a water-bath, and weighed. 
Since strychnine is not wholly insoluble in water, even in the 
presence of a free alkali, a minute portion of the alkaloid will 
remain in the alkaline liquid. The quantity, however, that 
may thus escape precipitation, will rarely exceed the 10,000 th 
part by weight of the fluid present. If on extracting the alka- 
loid from its aqueous solution by means of chloroform or ether, 
it is left, on evaporation of the liquid, in its pure state, it may, 
of course, be at once weighed. One hundred parts by weight 
of the alkaloid correspond to about 133 parts of the pure crys- 
tallised sulphate, 118 of the acetate, or about 120 parts of 
crystallised chloride of strychnine. 
111. Brucine. 
History.—Brucine, or brucia, occurs in most if not all the 
Strychnos plants in which strychnine is found. It was first 
38 594 
BRUCINE. 
discovered, in 1819, by Pelletier and Caventou, in what was 
formerly known as false Angustura bark, but which has since 
been shown to be nothing else than the bark of the nux vomica 
tree. It occurs both in the bark and seed of this tree; in the 
bark—which contains less strychnine and more brucine than 
the seed—it is said to be in combination with gallic acid, while 
in the seed it is believed to be combined with strychnic acid. 
The composition of the anhydrous alkaloid, according to Reg- 
nault, is C 46 H26 N2 08. 
Preparation.—Brucine may be obtained from the bark of 
nux vomica, in a manner similar to that by which strychnine 
is obtained from the seed, except that the alcoholic extract 
obtained from the precipitate produced by lime, is treated with 
oxalic acid, and subsequently with a mixture of alcohol and 
ether, which dissolves the coloring matter, while the oxalate 
of brucia remains undissolved. This salt is then decomposed 
by magnesia, and the liberated brucine dissolved in alcohol, 
which on spontaneous evaporation leaves the alkaloid in its 
crystalline state. (U. S. Dispensatory, 1865, p. 563.) 
Physiological Effects.—The effects of brucine on the animal 
economy are precisely the same in kind as those of strychnine; 
but it is less energetic in its action than the latter alkaloid, 
having only about one-twelfth the power of that substance. 
Dr. Christison cites two instances of poisoning by this sub- 
stance; and Professor Casper relates three cases in which death 
resulted from the taking of a mixture of arsenic and brucine 
(Forensic Medicine, vol. ii, p. 102). The ordinary medicinal 
dose of brucine is from half a grain to one grain, repeated two 
or three times a day. 
General Chemical Nature,—Brucine is a white, odorless 
solid, having an intensely bitter taste, very similar to that of 
strychnine. In its pure state, it is readily crystallisable, form- 
ing beautiful groups of very delicate, transparent needles; when 
the crystals are only slowly produced, they usually appear in 
the form of bold, colorless, four-sided prisms: the crystals con- 
tain eight equivalents, or about 15‘45 per cent, of their weight, 
of water of crystallisation. When moderately heated, the crys- 
tals fuse and become anhydrous; and at a higher temperature, SPECIAL CHEMICAL PROPERTIES. 
595 
the residue takes fire and burns with a dense smoky flame. 
Brucine is unacted upon by the fixed caustic alkalies, but it is 
readily decomposed by concentrated nitric acid. 
The salts of brucine are colorless, except when they contain 
a colored acid, and are, for the most part, easily crystallisable. 
They have the bitter taste of the pure alkaloid, and are readily 
decomposed by the caustic alkalies, with the elimination of the 
brucine. In regard to its basic properties, brucine is somewhat 
inferior to strychnine, it being displaced from its saline combi- 
nations by that base. 
Solubility.—When excess of pure powdered brucine is fre- 
quently agitated with 'pure tvater, at the ordinary temperature 
for twenty-four hours, one part of the crystallised alkaloid dis- 
solves in 900 parts of the liquid: this corresponds to one part 
of the anhydrous alkaloid in about 1,050 parts of the menstruum. 
It is much more soluble in hot water, from which, however, the 
greater j>art of the excess separates as the solution cools. Its 
solubility in this liquid is somewhat increased by the presence 
of foreign organic matter. 
Absolute ether, when frequently agitated for several hours 
at the ordinary temperature with excess of the powdered alka- 
loid, dissolves one part of the anhydrous base in 440 parts of 
the liquid. Chloroform readily dissolves the alkaloid in nearly 
every proportion. It is thus obvious that this liquid is better 
adapted than ether for the separation of the alkaloid from alka- 
line aqueous mixtures. The alkaloid is also readily soluble in 
nearly every proportion in absolute alcohol. But it is insoluble 
m the fixed caustic alkalies j and only sparingly soluble in large 
excess of ammonia. Most of the salts of brucine are freely sol- 
uble in water and in alcohol. 
Special Chemical Properties. Concentrated sulphuric 
ueid dissolves brucine and its salts with the production of a 
faint rose-red color. If the acid contains nitric acid—as is fre- 
quently the case—the alkaloid dissolves to a deep red solution. 
If a small crystal of bichromate of potash be stirred in the sul- 
phuric acid solution, the liquid acquires an orange or brownish- 
orange color, which slowly changes to a greenish hue, due to 
the separation of oxide of chromium. This reaction at once 596 
BRUCINE. 
distinguishes brucine from strychnine. Concentrated nitric acid 
dissolves the alkaloid, as well as its salts, to a deep red solu- 
tion, the color of which slowly fades to yellow. The alkaloid 
is readily soluble in concentrated hydrochloric acid, without 
change of color. 
In the following examination of the reactions of solutions of 
brucine, the pure crystallised alkaloid was dissolved, by the aid 
of just sufficient acetic or sulphuric acid, in pure water. The 
fractions employed, indicate the fractional part of a grain of the 
crystallised alkaloid in solution in one grain of water; and the 
results, unless otherwise indicated, refer to the behavior of one 
grain of the solution. One grain of pure crystallised brucine 
corresponds to 0*845 of a grain of the anhydrous alkaloid. 
1. Potash and Ammonia. 
The caustic alkalies produce in concentrated solutions of 
salts of brucine a white amorphous precipitate of the pure an- 
hydrous alkaloid, which after a little time, by the assimilation 
of water, assumes the crystalline form. The precipitate is 
readily soluble in free acids, even in acetic acid; but it is insol- 
uble in large excess of either potash or soda. In its amorphous 
state, the precipitate is rather freely soluble in large excess of 
ammonia; but when it has assumed the crystalline form, it is 
only very sparingly soluble in that liquid. 
1. ytto grain of brucine, in one grain of water, yields with 
either of the fixed alkalies an immediate amorphous pre- 
cipitate, which in a very little time gives rise to very 
beautiful groups of exceedingly delicate crystalline needles, 
Plate XI, fig. 5 ; and soon the mixture becomes converted 
into a nearly solid mass of crystals. Ammonia produces 
a similar precipitate, but it does not usually appear until 
after some little time 5 it then separates in the crystalline 
form. If large excess of ammonia be added, the precipi- 
tate may fail to appear, even after several hours. 
2. 510 grain, yields with a fixed alkali, an immediate cloudi- 
ness, and soon a very good crystalline precipitate. The 
formation of the precipitate is much facilitated by stirring NITRIC ACID AND CHLORIDE OF TIN TEST. 
597 
the mixture. Very similar results may be obtained by 
ammonia, providing it be added in very minute quantity. 
Solutions of salts of brucine but little more dilute than the 
last mentioned, fail to yield a precipitate by either of the fore- 
going reagents. 
The alkaline carbonates behave with solutions of salts of 
brucine, much in the same manner as the free alkalies. The 
true nature of the precipitate produced by either of the rea- 
gents now mentioned, may be confirmed by either of the two 
next-mentioned tests. 
2. Nitric Acid and Chloride of Tin. 
If a few crystals of brucine or of any of its colorless salts, 
in the dry state, be treated with a drop of concentrated nitric 
acid, they immediately assume a deep blood-red color, and 
quickly dissolve to a solution of the same hue 5 on heating this 
solution, its color is changed to orange-yellow or yellow. If, 
when the solution has cooled, a drop of a solution of protochlo- 
ride of tin be then added, the mixture immediately acquires a 
beautiful purple color, which is discharged by large excess of 
either nitric acid or of the tin compound, as also by sulphurous 
acid gas. The red color of nitric acid solutions of brucine con- 
taining a quite notable quantity of the alkaloid, is changed to 
a faint purple on the addition of the tin solution alone, without 
the application of heat: but the intensity of the color, as thus 
obtained, is much inferior to that obtained from the brucine 
solution after it has been heated 5 and if only a minute quantity 
of the alkaloid be present, without the application of heat, the 
purple color entirely fails to appear. 
The following quantities of brucine obtained by evap- 
orating one grain of the corresponding solution of the acetate to 
dryness on a water-bath. 
grain of brucine, dissolves in a drop of the acid to a 
deep red solution, which, when heated and allowed to cool, 
acquires an intense purple color, on the addition of the tin 
compound. 
Troon grain: the drop of acid acquires a very satisfactory 598 
BRUCINE. 
solution has been heated, is changed to a beautiful lilac. 
3. rtrrWo grain: on the addition of a very small drop of the 
red color, which upon the addition of the tin salt, after the 
acid, the deposit assumes a very decided red color, and 
dissolves to a faint red solution; the tin salt produces a 
quite distinct lilac coloration. To obtain the latter color, 
the acid and tin compound must be well apportioned, 
otherwise the reaction may entirely fail to manifest itself. 
This is about the limit of the tin reaction. 
4. s-»r,Wo grain, when moistened with a minute trace of the 
acid, assumes a quite perceptible red color; if this mix- 
ture be evaporated to dryness, on a water-bath, it leaves 
a very satisfactory red deposit. 
5. ro'oVo'o grain, when treated as under 4, leaves a quite dis- 
tinct red residue. 
These reactions of nitric acid and chloride of tin, when 
taken in connection, are quite characteristic of brucine; and at 
the same time, as we have just seen, they are exceedingly 
delicate. In these respects, this test bears much the same 
relation to brucine that the color test does to strychnine. Nitric 
acid also produces a red color with morphine and with several 
other substances, besides brucine; but the subsequent addition 
of chloride of tin, fails to produce, with any of these fallacious 
solutions, a purple coloration. The red color of the acid solu- 
tion of morphine, is but little affected by the tin compound, at 
most being changed to yellow; when the acid solution has been 
heated and allowed to cool, the tin salt produces no visible 
change. 
3. Sulphuric Acid and Nitrate of Potash 
Brucine and its salts, as already pointed out, dissolve in 
concentrated sulphuric acid with the production of a rose-red 
color. If a crystal of nitrate of potash be stirred in a solution 
of this kind, the mixture acquires a deep orange-red color, due 
to the action of the nitric acid of the nitre. This test, there- 
fore, is very similar in its action to the one just considered. 
1. grain of brucine, when treated with a small drop of the 
concentrated acid, dissolves to a solution having a faint SULPHOCYANIDE OF POTASSIUM TEST. 
599 
rose color, which on the addition of a small crystal of 
nitre, is changed to deep orange-red. 
2. 1700 I) grain: on the addition of the acid, the deposit assumes 
a quite perceptible rose-red color, and dissolves to a color- 
less solution, which on the addition of the nitre acquires a 
beautiful orange color. 
3. yo.ooo grain: the acid dissolves the deposit with little or no 
change of color; but the solution, when treated with the 
potash salt, acquires an orange color, which soon changes 
to yellow. 
4. y5-J6iro grain: when the acid solution is treated with the 
nitre, it yields only a faintly yellow coloration. But if a 
small crystal of nitre be moistened with the acid and then 
stirred over the dry brucine deposit, the crystal acquires 
a distinct orange color. 
The production of these colors is quite peculiar to brucine. 
Sulphuric acid solutions of narcotine, opianyl, and morphine, 
when treated with nitrate of potash, yield colors somewhat 
similar to that produced from brucine; but neither of these 
substances dissolves in the acid with the production of a rose- 
red color. 
4. Sulphocyanide of Potassium. 
This reagent throws down from quite concentrated solutions 
of salts of brucine a white precipitate of the sulphocyanide of 
brucine, which is insoluble in acetic acid. As produced from 
very concentrated solutions, the precipitate is in the amorphous 
form, but it soon becomes more or less crystalline. From some- 
what more dilute solutions, the precipitate does not appear until 
after some time, and it then separates in the form of small 
granules. The formation of the precipitate from solutions of 
this kind, is much facilitated by stirring the mixture with a 
glass rod. 
One grain of a 100 th solution of the alkaloid, yields no 
immediate precipitate, but in a few moments, comparatively 
large groups of minute granules appear, and after a few min- 
utes there is a quite good deposit of these groups, with occa- 
sionally, small transparent crystalline plates, Plate XI, fig. 6. 600 
BRUCINE. 
A similar quantity of a 500 th solution, fails to yield a precip- 
itate, even when the mixture is allowed to stand for some hours. 
5. Bichromate of Potash. 
Bichromate of potash throws down from solutions of salts of 
brucine, even when highly diluted, a yellow precipitate of chro- 
mate of brucia, which is insoluble in acetic acid. The precip- 
itate is readily soluble, with the production of a deep red color, 
in concentrated nitric acid, and in sulphuric acid, with the 
production of a reddish-brown color. 
1. yo~o grain of brucine, in one grain of water, yields a quite 
copious amorphous precipitate, which in a few moments 
becomes converted into crystalline groups of the forms 
illustrated in Plate XII, fig. 1. 
2. tttoo grain: if the mixture be stirred, it immediately yields 
streaks of granules and small crystals, along the path of 
the rod, and in a little time, there is a quite copious crys- 
talline deposit. 
3. sToVo grain, yields after a little time, especially if the mix- 
ture has been stirred, a quite satisfactory crystalline pre- 
cipitate. 
4. To'irdi) grain: after several minutes, a quite distinct precip- 
itate, and after about half an hour, a very satisfactory 
deposit of crystalline needles. 
The crystalline form of the precipitate, as produced from 
somewhat strong solutions of the alkaloid, together with the 
subsequent reaction of nitric acid, serve to distinguish the 
chromate of brucia from all other precipitates produced by 
this reagent. 
Protochromate of potash produces in solutions of the alkaloid, 
results very similar to those occasioned by the bichromate, only 
that the reaction is not quite so delicate. 
G. Bichloride of Platinum, 
Solutions of salts of brucine yield with bichloride of plati- 
num, a yellow precipitate of the double chloride of platinum CHLORIDE OF GOLD TEST. 
601 
and brucine, which is unchanged by acetic acid, but readily 
decomposed by the caustic alkalies. 
1. j-jfo grain of brucine, yields a very copious deposit, which 
almost immediately becomes a mass of irregular crystalline 
needles. The precipitate is slowly soluble in nitric acid, 
yielding an orange-red solution. 
2. r.ifoo grain: an immediate, light-yellow, crystalline precipi- 
tate, which in a little time, becomes converted into irregu- 
lar needles, Plate XII, fig. 2. 
0- rrdcro grain: very soon crystals appear, and after a little 
time, there is a quite good crystalline deposit. 
4. hewo grain: if the mixture be stirred, it immediately yields 
crystalline streaks, and very soon a quite fair deposit. 
5. 2T,f0"0 grain: after a few minutes, if the mixture has been 
stirred, crystalline needles appear, and after a little time, 
there is a quite satisfactory deposit. 
This reagent also produces yellow crystalline precipitates 
with various other substances, but the form of the brucine 
deposit is somewhat peculiar. 
7. Terchloride of Gold. 
This reagent produces in solutions of salts of brucine a 
yellow amorphous precipitate, which in a little time acquires 
a flesh color. The precipitate is but sparingly soluble in 
acetic acid; the caustic alkalies cause it to quickly assume 
a dark color. 
1. iTo grain of brucine, in one grain of water, yields a very 
copious deposit. 
2. TToVo grain, yields a greenish-yellow precipitate, which soon 
becomes yellow j the deposit is readily soluble to a clear 
solution in caustic potash. 
3. roroiro grain: a quite good, yellowish deposit. 
4. 2T751T0 grain, yields, in a very little time, a distinct turbidity, 
and after a few minutes, a quite satisfactory precipitate. 
5. 5o.lo6~u grain: after some minutes, a quite distinct deposit. 
All these precipitates remain amorphous. The reactions of 
this reagent are common to a large class of substances. 602 
BRUCINE. 
8. Carhazotic Acid. 
An alcoholic solution of carhazotic acid throws down from 
aqueous solutions of salts of brucine a yellow precipitate, of the 
carbazotate of brucia, which is but sparingly soluble in large 
excess of acetic acid. 
1. xow grain of brucine, yields a very copious precipitate, 
which after a time becomes, in part at least, crystalline. 
The formation of these crystals is readily prevented by 
the presence of foreign organic matter. 
2. r,Wo grain, yields a very good precipitate, which after a 
time is converted into groups of aggregated granules, 
similar to those produced by sulphocyanide of potassium 
(Plate XI, fig. 6). 
3. roTSiro grain, yields, after several minutes, especially if the 
mixture has been stirred, a quite distinct precipitate. 
confirms the reactions of the other tests for brucine. 
The reaction of this reagent is valuable only in so far as it 
9. Ferricyanide of Potassium. 
Concentrated neutral solutions of salts of brucine, when 
treated with this reagent, yield a light-yellow crystalline pre- 
cipitate, which is readily soluble in the mineral acids. The 
formation of the precipitate is readily prevented by the pres- 
ence of a free acid, even of acetic acid, but after the crystals 
have formed they are only very sparingly soluble in large 
excess of acetic acid. 
1. yihr grain of brucine, yields an immediate precipitate, and 
in a few moments, there is a very copious deposit of crys- 
tals, grouped in various and most beautiful forms, Plate 
XII, fig. 3. These crystalline groups are, perhaps, the 
most brilliant polariscope objects yet known. The produc- 
tion of these crystals is quite characteristic of brucine. 
2. xo'Tr grain: after stirring the mixture, it yields, in a very 
little time, a copious granular deposit. 
3. rrcMTo grain: after some time, a slight turbidity. lODINE AND BROMINE TESTS. 
603 
Ferrocyanide of potassium produces no precipitate Avith a 
100 th solution of brucine, even if the mixture be allowed to 
stand for some time. 
10. lodine in lodide of Potassium. 
A solution of iodine in iodide of potassium produces in 
normal solutions of salts of brucine, even when very highly 
diluted, an orange-brown, amorphous precipitate, which is insol- 
uble in acetic acid. 
1. y-jj-Q grain of brucine, yields a very copious deposit, which 
is decomposed by large excess of potash, with the produc- 
tion of a dirty-white precipitate. 
2. itcToo grain: much the same results as 1. 
3* roTToi) grain, yields a quite good, brownish precipitate, which 
is soluble to a clear solution in potash. 
4. riyoiro grain, yields a yellowish deposit. 
5. uroVoo grain: a very distinct, dirty-yellowish turbidity. 
6. 5-?ro7oiro grain, yields a perceptible cloudiness. 
It need hardly be remarked that, this reagent produces 
similar precipitates in solutions of most of the alkaloids and of 
various other organic substances. 
11. Bromine in Bromohydric Acid. 
A strong aqueous solution of bromohydric acid saturated 
with bromine produces in solutions of salts of brucine, when 
not too dilute, a deep-brown amorphous precipitate, which after 
a time dissolves, but is reproduced upon further addition of the 
reagent. The precipitate is soluble in acids, even acetic acid, 
and in potash. 
1. yihr grain of brucine, yields a very copious, deep-brown 
deposit, which soon acquires a yellow color, then a bright 
yellow, and after some minutes dissolves. 
2. yo*oo grain: much the same results as 1. 
3* To7oiro grain, yields a yellowish precipitate, which after a 
time disappears, and is not repi’oduced upon further addi- 
tion of the reagent. 604 
BRUCINE. 
4. grain, yields a greenish-yellow deposit, which soon 
dissolves. 
The brown color of the brucine deposit distinguishes it from 
the precipitates produced by this reagent with other alkaloids. 
Other Reactions.—Corrosive sublimate throws down from a 
100 th solution of salts of brucine a quite good, white, amorph- 
ous precipitate, which soon becomes granular; with solutions 
but little more dilute than this, the reagent fails to produce a 
precipitate. lodide of potassium produces in a 100 th solution 
of the alkaloid no immediate precipitate, but after a time there 
is a quite good deposit of rough needles and crystalline plates. 
Tannic acid throws down from even highly diluted solutions of 
the alkaloid a dirty-white, amorphous precipitate, which is solu- 
ble in acetic acid. 
Chlorine gas passed into concentrated solutions of salts of 
brucine produces at first a yellow, then a red color, which is 
discharged by excess of the gas. Upon the subsequent addition 
of ammonia, the liquid acquires a light brown color. These 
reactions manifest themselves only in very strong solutions of 
salts of the alkaloid. 
Administered to frogs, brucine produces violent tetanic con- 
vulsions, similar to those occasioned by strychnine, but their 
production requires relatively a much larger quantity of the 
former than of the latter alkaloid. 
Separation from Organic Mixtures. 
Brucine may be separated from organic mixtures in the 
same manner as heretofore directed for the recovery of strych- 
nine. When the analysis furnishes only a small residue for the 
application of the chemical tests, a portion of it should first be 
examined by the nitric acid and chloride of tin test. If this 
yields a positive reaction, it fully establishes the presence of 
the alkaloid. When, however, sufficient material is at hand, the 
reaction of this test should be confirmed by some of the other 
tests. Should the nitric acid and tin test fail, it is quite certain 
that, under similar conditions, the other tests would also fail. RECOVERY FROM ORGANIC MIXTURES. 
605 
One grain of brucine in solution was given to a recently 
fed cat; thirty minutes afterwards, the animal was seized with 
violent tetanic convulsions and died during the paroxysm. On 
now applying the method directed for the recovery of strych- 
nine, to the examination of the contents of the stomach of the 
animal, a very notable quantity of pure crystallised brucine was 
recovered. And six fluid drachms of blood, taken from the 
same animal and treated after the strychnine method, gave, 
when the first chloroform residue was examined by the tin test, 
perfectly unequivocal evidence of the presence of brucine. 606 
ACONITINE. 
OHAPTEE IY. 
ACONITINE, ATROPINE, DATURINE. 
Section I.—Aconitine. (Aconite.) 
History.—Aconitine is the name applied to the active prin- 
ciple, or alkaloid, of Aconite, Monkshood, or Wolfsbane, the 
Aconitum napellus of botanists. It exists in all parts of the 
plant, but in the greatest proportion in the root, and is said to 
be combined with a peculiar organic acid, the aconitic. The 
dried root is usually estimated to contain from OT to o’2 per 
cent, of the alkaloid. It is also found in several other species 
of this genus of plants; the Aconitum ferox is generally con- 
sidered to be the most poisonous of the species. Aconitine 
was first obtained, although in an impure state, by Geiger 
and Hesse, in 1832. Its composition, according to Planta, is 
CcoH47N0i4. (Chemical Gazette, 1850, p. 352.) In its pure 
state, this substance is perhaps the most powerful poison yet 
known. According to Hubschmann, aconite contains another 
alkaloidal principle, which he has described under the name 
of napellina. 
Preparation.—Various methods have been proposed for the 
preparation of aconitine. The following process has recently 
been advised by MM. Liegeois and Hottot. The bruised root 
of the plant is digested for eight days with rectified spirit, 
slightly acidulated with sulphuric acid; the alcoholic liquid is 
then pressed out, and the alcohol removed by distillation. The 
residue is allowed to cool, and any solid resinous matter that 
separates removed. The liquid is now concentrated to the con- 
sistency of a syrup, then treated with two or three volumes of 
pure water, and the mixture allowed to repose, as long as any 
green oil collects upon its surface; this is then removed, the PREPARATION. 
607 
last traces being separated by a filter previously moistened with 
water. The liquid is next treated with slight excess of hydrate 
of magnesia, and repeatedly agitated with pure ether, which 
will extract the alkaloid. The united ethereal extracts are 
evaporated to dryness, and the residue dissolved in water by 
the aid of slight excess of sulphuric acid. The alkaloid is then 
precipitated from the filtered solution by slight excess of am- 
monia, and further purified by repeated solution in water acidu- 
lated with sulphuric acid and re-precipitation by ammonia. The 
final precipitate is washed with cold water, as long as any odor 
of ammonia is present, then dried at a low temperature. 
Another method, for the preparation of the alkaloid, has still 
more recently been proposed by Mr. T. B. Groves. Five parts 
of the coarsely-powdered root are macerated for about seven 
days with one part of methylated spirit, strongly acidulated 
with hydrochloric acid. The liquid portion is then expressed 
from the solid matters, treated with a little water, and the spirit 
separated by distillation. When the residue has cooled, any 
oily matters that have separated are removed by a filter. The 
clear filtrate is treated with slight excess of a strong solution of 
iodohydrargyrate of potassium, and the mixture moderately 
heated, with constant stirring, until the precipitate has com- 
pletely separated. This is collected, washed, and dissolved in 
hot methylated spirit, and the iodine precipitated from the warm 
liquid by slight excess of a hot aqueous solution of nitrate of 
silver. The iodide of silver thus produced, is separated by a 
filter, and the filtrate treated with sulphuretted hydrogen gas, 
for the purpose of removing any nitrate of mercury present. 
The liquid is again filtered, then treated with slight excess of 
carbonate of potash, which will precipitate the alkaloid. This 
is extracted by repeatedly agitating the mixture with ether, and 
the united ethereal extracts are evaporated to dryness. The 
residue, which consists of nearly pure aconitine, is dissolved in 
water acidulated with nitric acid, the solution filtered, and set 
aside to crystallise. The author of this method states that by 
it, the alkaloid may readily be obtained in its crystalline state, 
in the form of nitrate. (Amer. Jour. Pharmacy, Nov., 1866, 
p. 518.) 608 
ACONITINE. 
Poisoning by aconitine in its pure state, lias been of very 
rare occurrence 5 but there have been numerous instances of 
poisoning by the root, leaves, and some of the preparations of 
aconite, chiefly, however, as the result of accident. The root 
has not unfrequently been mistaken for horseradish. The prin- 
cipal pharmaceutical preparations of aconite are the tinctures 
of the root and of the leaves, and the alcoholic extract. Each 
of these preparations is subject to considerable variation in 
strength, depending both on the formula followed for its prepa*- 
ration and the quality of the material employed. The medicinal 
dose of the pure alkaloid is said to be about the 1-130 th part of 
a grain; it is rarely prescribed in this form, and requires great 
caution in its administration. 
Symptoms.—The effects of poisonous doses of aconite are 
in some respects quite peculiar. At first there is a sense of 
tingling and numbness in the lips, mouth, and throat, with a 
feeling of warmth or burning in the stomach. These effects 
are succeeded by tingling in various parts of the body, pain in 
the abdomen, headache, vertigo, and nausea, frequently attended 
by vomiting, and sometimes purging ; there is also, diminished 
sensibility of the skin, constriction in the throat, frothing at the 
mouth, partial or entire loss of voice, impaired vision, ringing 
in the ears, a feeling of tightness in various parts of the body, 
cold perspirations, muscular tremors, and great prostration of 
strength. The pulse becomes small and feeble, or altogether 
imperceptible 5 the countenance pale and sunken ; the extremi- 
ties cold and clammy : the pupils are usually dilated, but not 
unfrequently contracted. Death usually takes place by syncope. 
In some instances, death is preceded by delirium and convul- 
sions. In fifty-three cases of aconite poisoning collected by 
Dr. Tucker, of New York, and cited by Wharton and Stille, 
general convulsions occurred only in seven. 
The symptoms usually manifest themselves within a few 
minutes after the poison has been taken; but they have been 
delayed for more than an hour. In a case quoted by Dr. Beck 
(Med. Jur., vol. ii, p. 890), in which a man had eaten some 
salad containing, by mistake, a quantity of aconite, the patient 
immediately experienced a burning heat in the tongue and gums, PHYSIOLOGICAL EFFECTS. 
609 
and irritation in the cheeks. This tingling sensation extended 
over the whole body, and was accompanied by muscular twitch- 
ings. The eyes and teeth became fixed; the extremities cold 
and bathed with perspiration ; the pulse imperceptible, and the 
breathing so short as scarcely to be distinguishable. Under the 
active use of remedies, the patient gradually recovered. 
In a case reported by Dr. Gray, in which a healthy boy 
fourteen years of age, was given by mistake a tablespoonful of 
the tincture of aconite, the following symptoms were observed. 
In about five minutes the patient began to experience the effects 
of the poison, and in twenty minutes the pupils were slightly 
dilated and nearly insensible to light; the countenance was pale, 
and he moved with difficulty; his head felt heavy, and there 
was frequent retching, with the discharge of small quantities of 
mucus. An emetic of sulphate of zinc was immediately admin- 
istered, and quickly produced copious vomiting. The patient 
now experienced a sense of intense burning in the stomach and 
oesophagus, and was greatly prostrated; the pulse became slow, 
the extremities cold, the pupils widely dilated, and he com- 
plained of great numbness of his head, but not of any other 
part of the body, and lost the power of sight. Under the use 
of a laxative enema, and external and internal stimulants, there 
was a slight amelioration of the symptoms for about half an 
hour 5 but the collapse again returned, the respiration became 
slow and difficult, the muscles of the head and trunk rigid, the 
surface cold, deglutition impossible, and death supervened sud- 
denly, under full consciousness, two hours after the poison had 
been taken. (New York Jour, of Med., Nov., 1848, p. 836.) 
In another case, a healthy man ate some greens consisting 
for the most part of the root of aconite. Almost immediately 
afterwards he complained of a feeling as if he could not draw 
m his tongue, and various hallucinations of sight. These symp- 
toms were soon succeeded by vomiting, involuntary stools and 
passage of urine, a peculiar sensation in the extremities, a feei- 
ng of pricking in the whole body, and fainting, followed by 
death. (ReiFs Monograph upon Aconite, p. 46.) 
The following case of recovery occurred in the practice of 
bb'. McCready, of New York. A healthy Irish woman, about 
39 610 
ACONITINE. 
twenty-five years of age, swallowed a tablespoonful of a satu- 
rated tincture of aconite, mistaking it for brandy. When seen 
an hour afterwards her countenance was flushed, the pupils 
dilated, though sensible to light; the pulse frequent, soft and 
weak, the beat being sometimes so feeble as to be almost imper- 
ceptible. She complained of a feeling of fullness about her 
limbs, as if they were about to burst, accompanied by a sensa- 
tion of numbness and pricking over the whole surface; and 
there were numbness and tingling of the tongue, and a strange 
sensation about the throat. There was no sickness at the stom- 
ach, and the head was perfectly clear. An emetic of sulphate 
of zinc and ipecacuanha was administered and produced copious 
vomiting. Half an hour afterwards, the pulse was still frequent 
and feeble, the beats continuing irregular in force. She com- 
plained of feeling weak, but in other respects was about the 
same as when first seen. Three hours later, the dilatation of 
the pupils had passed away, but the numbness and tingling 
remained. The next day she was almost in her usual health. 
(Amer. Jour. Med. Sci., Jan., 1852, p. 268.) 
Period when Fatal.—ln fatal poisoning by aconite or any of 
its preparations, death usually occurs in from two to six hours 
after the poison has been taken j but considerable variation has 
been observed in this respect. A case is reported in which 
one drachm of the tincture, taken by an adult, proved fatal in 
one hour and a half, the patient being strongly convulsed just 
before death. In another instance, a child aged two years and 
seven months, having eaten an unknown quantity of the fresh 
leaves of aconite, was soon seized with violent symptoms, but 
death did not occur until after the lapse of about twenty hours. 
(Lancet, London, June, 1856, p. 715.) In this case, shortly 
after the symptoms manifested themselves there was violent 
vomiting, which brought away pieces of the leaves: no vege- 
table matter was found in the stomach after death. 
Fatal Quantity.—Since the preparations of aconite are sub- 
ject to great variation in strength, similar quantities of the same 
form of preparation have given rise to very different results. 
Thus Dr. Fleming mentions an instance where two grains of 
the alcoholic extract occasioned alarming effects, and another in 611 
FATAL QUANTITY. 
which four grains proved fatal; whilst Dr. Christison relates an 
instance in which he gave six grains of a carefully prepared 
alcoholic extract, to a woman suffering from rheumatism, with- 
out being able to observe any effect whatever. (On Poisons, 
p. 667.) In a case reported by Dr. Easton, tAventy-five minims 
of a tincture of the root of aconite, with twenty minims of tinc- 
ture of belladonna, caused the death of a healthy young man, 
within three hours; and in another instance, twenty-five drops 
of the tincture, prescribed through ignorance, proved fatal to a 
man, in about four hours. (American Medical Monthly, March, 
1854, p. 223.) Several instances are reported in which about 
a drachm of the tincture destroyed life. 
In a case communicated to Dr. Pereira, two doses of six 
drops each of the tincture, taken at an interval of two hours, 
by a young man aged twenty-one years, produced most alarming 
symptoms. (Mat. Med., vol. ii, p. 1091.) We are acquainted 
with an instance in which a very intelligent physician adminis- 
tered to his wife a dose of five drops of Thayer’s fluid extract 
of the root of aconite. In from ten to fifteen minutes after- 
wards she experienced a burning sensation in the throat and 
great numbness in the arms ; these effects were soon folloAAred 
by tingling in the surface of the whole body, difficulty of breath- 
ing, impending suffocation, dimness of \nsion, and alarming pros- 
tration, Avhich continued for about two hours: she then rapidly 
recovered. 
Recovery has not unfrequently taken place after compara- 
tively large quantities of some of the preparations of aconite 
Were taken. In a case recently reported by Mr. Kay, a lady 
took by mistake two teaspoonfuls of the tincture, and entirely 
recovered in eight hours afterwards. In this case the symp- 
toms did not manifest themselves until an hour after the poison 
bad been taken. An emetic was then given, which quickly 
operated. The patient then lost the use of her lower extremi- 
ties ; the face had an anxious expression; the forehead was 
wrinkled and corrugated; the pupils slightly dilated; pulse 
slow, feeble, and intermitting; the extremities cold, but the 
intellect quite unaffected. She complained of a burning sensa- 
tion in the throat, and a constriction at the chest; and lost the 612 
ACONITINE. 
sense of feeling in her legs, arms, and face. (Lancet, Reprint, 
Oct., 1861, p. 278.) In another case, related by M. Devay, a 
porter in a druggist’s shop, swallowed by mistake nearly one 
ounce and a half of an alcoholic solution of aconite, and although 
he immediately experienced a sense of heat and constriction in 
the throat and was soon seized with the most violent symptoms, 
yet he was quite well three days afterwards. (Chemical Ga- 
zette, vol. ii, p. 220.) 
Aconitine in its pure state, as already mentioned, is one of 
the most virulent poisons known. Dr. Headland considers that 
one-tenth of a grain of the pure alkaloid would be sufficient to 
destroy the life of a healthy adult man. And Dr. Pereira 
mentions an instance in which one-fiftieth of a. grain nearly 
proved fatal to an elderly lady. (Mat. Med., ii, p. 1093.) A 
most remarkable instance of recovery, in which a gentleman 
had taken two grains and a half of aconitine, is related by Dr. 
Golding Bird. It seems that almost immediately after taking 
the poison the patient fell, and was seized with violent vomiting, 
by which it is believed that most of the poison was ejected. 
Some time after the occurrence, the patient was in a most fear- 
ful state of collapse; the surface cold and perspiring; the action 
of the heart scarcely perceptible, but the intellect was unim- 
paired. The most prominent symptom, which continued for 
some hours, was repeated and most violent convulsive vomiting. 
On attempting to swallow any fluid the patient was seized with 
violent spasms of the throat, somewhat similar to those observed 
in hydrophobia. This latter symptom continued for several 
hours, and it was not until about thirty hours after the poison 
had been taken that the patient was considered convalescent. 
(New York Journal of Medicine, March, 1848, p. 285.) 
Treatment.—The first indication is to thoroughly evacuate 
the contents of the stomach, either by an emetic or the use of 
the stomach-pump. As an emetic sulphate of zinc is usually 
preferred. Stimulants, such as ammonia and brandy, may often 
be employed with great advantage; and the use of stimulating 
injections have been attended with good results. As an anti- 
dote, the free administration of finely-powdered animal char- 
coal, mixed with water, has been strongly recommended by Dr. PATHOLOGICAL EFFECTS. 
613 
Headland, and others. It is claimed that this substance will 
unite with the poisonous alkaloid, and thus prevent its absorp- 
tion into the system. The charcoal is then removed from the 
stomach by an emetic. Vegetable infusions containing tannic 
acid, and a solution of iodine in iodide of potassium, have also 
been strongly advised, on the grounds that they form insoluble 
compounds with the alkaloid. 
From the apparent antagonism existing between the physio- 
logical effects of aconite and those of mix vomica, these sub- 
stances have been recommended as mutual antidotes. The fol- 
lowing case, in which this remedy was employed, is reported 
by Dr. Hanson. A boy, aged five years, swallowed a mixture 
of tincture of aconite and simple syrup. When first seen by 
Dr. Hanson, the patient was laboring under the usual symptoms 
of aconite poisoning, in an aggravated degree. Emetics and 
tickling the fauces with a feather were resorted to, but without 
producing vomiting, and the patient continued to sink. Half 
an hour after the first dose of tartar emetic had been given, 
three drops of the tincture of mix vomica were administered. 
In a few minutes the action of the heart was increased in force, 
and the respiration much improved. At the end of twenty 
minutes, the dose of mix vomica was repeated. Vigorous vom- 
iting now soon ensued, after which the patient rapidly recovered. 
(Amer. Jour. Med. Sci., Jan., 1862, p. 285.) 
Post-mortem Appearances.—The most common morbid ap- 
pearances, in death from aconite, are an injected condition of 
the blood-vessels of the brain and of its membranes, and con- 
gestion of the lungs and liver, with more or less redness of the 
mucous membrane of the stomach and intestines. The stomach 
and small intestines are frequently found empty. The right 
cavities of the heart usually contain more or less blood; the 
blood throughout the body is generally fluid and of a dark color. 
It need hardly be remarked that none of these appearances are 
peculiar to death from this substance. In two cases of fatal 
poisoning by a tincture of the root of aconite, quoted by Dr. 
Beck, the only morbid appearances observed on dissection were 
great redness of the lining membrane of the stomach and small 
intestines. 614 
ACONITINE. 
In an instance quoted by Orfila (Toxicologic, ii, 443), in 
which five persons swallowed each a glass of brandy in which 
the root of aconite had been macerated, and three of them died, 
death taking place in about two hours, the following appear- 
ances were observed. The oesophagus, stomach, and intestines 
were found much inflamed, and the blood-vessels, especially the 
veins, of the digestive tube much injected. The mesentery was 
also inflamed. The cavity of the peritoneum contained a large 
quantity of yellowish serum. The lungs were dense, of a bluish 
and violet hue, slightly crepitant, and gorged with blood. The 
pericardium contained a large quantity of serum; the heart and 
large vessels presented nothing remarkable. The brain was 
healthy, but its blood-vessels somewhat injected. 
In the case of the child, already cited, in which the leaves 
of aconite had been eaten and life was prolonged for about 
twenty hours, the body presented the following appearances 
sixty hours after death. The abdomen externally was much 
discolored; and patchy discolorations were visible on the thighs 
and legs, but the spots were not so apparent as during life. 
The stomach was highly inflamed throughout its whole extent; 
it contained a little fluid of a lightish-brown color, but no food, 
nor any traces of leaves or other vegetable matter. Various 
parts of the small intestines presented patches of intense inflam- 
mation, in some places approaching to gangrene. The large 
intestines presented nothing particular. The bladder was full 
of urine; the spleen somewhat congested. The pericardium 
contained about half an ounce of bloody serum. The heart was 
full of uncoagulated blood, and the blood throughout the body 
was thin and fluid. The other parts of the body were nearly 
or altogether normal. 
Chemical Properties 
In the Solid State.—Aconitine, in its pure state, is a white, 
transparent, odorless solid, which until recently seems not to 
have been obtained in the crystalline form. It has an acrid 
taste, followed by a sense of tingling and numbness of the 
tongue; applied in the form of solution to the skin, it causes a CHEMICAL PROPERTIES. 
615 
persistent feeling of heat and numbness. These effects are 
produced by even extremely minute quantities of the alkaloid. 
Applied in the form of ointment to the eye, it causes much the 
same effects, with, according to Dr. Pereira, contraction of the 
pupil. Aconitine is unchanged by exposure to the air. When 
moderately heated in a tube, it fuses to a transparent liquid, 
which, as the heat is increased, becomes brown, then black, and 
is finally reduced to a solid carbonaceous mass. Heated in the 
air on a piece of porcelain, it undergoes a similar change, and 
leaves a black cinder, which is but slowly consumed: it can not 
be volatilised unchanged. 
Aconitine, other than that prepared by Mr. Morson, of Lon- 
don, as found in the shops, is usually more or less colored, and 
very variable in strength, many of the samples being almost 
wholly inert. Dr. Pereira states that he met with a French 
preparation of which he took one grain without perceiving the 
least effect either on the tongue or otherwise. And of three 
samples prepared by different German manufacturers that we 
have examined, one of them contained only a mere trace of 
the alkaloid, and the other two appeared to consist entirely 
of foreign matter. The aconitine prepared by Mr. Morson, is 
usually in the form of a dull-white powder, consisting chiefly of 
small granules and thin transparent plates. This manufacturer, 
as well as Mr. Groves, has recently obtained the alkaloid in the 
form of large well-defined crystals. 
Aconitine has strongly basic properties, completely neutral- 
ising acids to form salts, several of which have been obtained 
in the crystalline form. When touched in the dry state with 
concentrated sulphuric acid, pure aconitine acquires a faint yel- 
low color, and dissolves to a colorless solution; a small crystal 
of nitrate of potash stirred in the solution, produces no visible 
change, even on the application of a moderate heat; if a crys- 
tal of bichromate of potash be stirred in the solution, the mix- 
ture slowly acquires a green color. Concentrated nitric acid 
also dissolves the alkaloid to a colorless solution, which is un- 
changed by a moderate heat, and by a solution of protochloride 
of tin. The alkaloid is also dissolved to a colorless solution, by 
hydrochloric acid. 616 
ACONITINE. 
Solubility.—When excess of Morson’s aconitine is kept in 
contact with pure water at a temperature of about 60° F. for 
ten hours, one part dissolves in 1,783 parts of the fluid. On 
evaporating the solution to dryness, the alkaloid is left in the 
form of a hard, transparent, colorless pellicle, which when 
broken up, presents the appearance of crystalline plates. Abso- 
lute ether kept in contact with excess of the alkaloid for several 
hours, at the ordinary temperature, takes up one part hi 777 
parts of the menstruum. On allowing the solution to evaporate 
spontaneously, the alkaloid is left as a transparent glacial mass. 
Chloroform readily dissolves it in nearly every proportion, and 
leaves it on spontaneous evaporation in the form of a vitreous 
mass. It is also freely soluble in alcohol. The salts of aconi- 
tine are, with few exceptions, readily soluble in water. They 
are also soluble in alcohol, but insoluble in ether. 
Of solutions of Aconitine.—ln the following investiga- 
tions in regard to the behavior of solutions of aconitine, pure 
aqueous solutions of the chloride were employed. The frac- 
tions indicate the fractional part of a grain of the pure alka- 
loid present in one grain of liquid; and, unless otherwise stated, 
the results refer to the behavior of one grain of the solution. 
1. Potash and Ammonia. 
The caustic alkalies throw down from somewhat concentrated 
solutions of salts of aconitine a dirty-white flocculent precipitate 
of the hydrate of the alkaloid, which is nearly wholly insoluble 
in excess of the precipitant, but readily soluble in free acids, 
even acetic acid. 
1. yoW grain of aconitine, in one grain of water, yields a rather 
copious precipitate, which is insoluble in large excess of 
the reagent. 
2. yyo grain, yields a quite good precipitate, which dissolves, 
not however without difficulty, in several drops of the 
precipitant. 
3. y,Wo grain: no satisfactory indication. 
The alkaline carbonates fail to produce a precipitate with 
a 100 th solution of the alkaloid. CARBAZOTIC ACID AND lODINE TESTS. 
617 
2. Chloride of Gold. 
Tercliloride of gold produces in solutions of salts of aconitine, 
even when highly diluted, a yellow amorphous precipitate of the 
double chloride of aconitine and gold, which is but very spar- 
ingly soluble in hydrochloric acid. According to Planta, the 
precipitate has the composition, C6OH47N0i4, HCI, AuC13, 2 HO. 
1. ytht grain of aconitine, yields a very copious precipitate. 
2. xtoVo grain, yields a quite good deposit, which is readily sol- 
üble to a clear solution in caustic potash. 
6* 570 0~0 grain: in a very little time, a quite fair precipitate. 
4. rinVoo grain, yields, after a little time, a quite perceptible 
deposit. 
5. yoTToo grain: after some time, a just perceptible turbidity. 
3. Carbazotic Acid. 
An alcoholic solution of carbazotic acid occasions in solutions 
of salts of aconitine a yellow amorphous precipitate, which is 
insoluble in ammonia. 
1. yu~o grain of aconitine, in one grain of water, yields a very 
copious precipitate. 
2. two grain, yields a quite fair, greenish-yellow deposit. 
3. 57oLoo grain: after a little time, a quite perceptible precipitate. 
4. lodine in lodide of Potassium. 
An aqueous solution of iodine in iodide of potassium throws 
down from solutions of aconitine and of its salts, even when 
highly diluted, a reddish-brown or yellowish, amorphous precip- 
itate, which is readily decomposed by the caustic alkalies. 
1- tq-q grain of aconitine, yields a very copious precipitate, 
which on the addition of caustic potash is changed to a 
white deposit. 
2. r,Wo grain: a copious, yellowish precipitate, which is soluble 
in the caustic alkalies, but immediately replaced by a 
white deposit. 618 
ACONITINE. 
8- rsrro'o grain: a quite good precipitate, 
4. granp yields a quite distinct deposit. 
5- nroVoo grain: the mixture becomes distinctly turbid. 
5. Bromine in Bromohydric Acid. 
A strong aqueous solution of bromohydric acid saturated 
with bromine produces in solutions of salts of aconitine, and of 
the free alkaloid, a yellow flocculent precipitate. 
1. yfo grain of aconitine, in one grain of water, yields a copi- 
2. rroVo grain : a quite good deposit. 
3- ro;Wo grain: a quite fair precipitate. 
4- yttWo grain, yields a distinct cloudiness. 
ous precipitate. 
Other Reagents.—Corrosive sublimate produces in one grain 
of a 100 th solution of salts of aconitine a quite good, dirty- 
white, caseous precipitate, which is readily soluble in hydro- 
chloric acid. A similar quantity of a 500 th solution of the alka- 
loid fails to yield a precipitate. Sulpha cyanide of potassium and 
tannic acid produce a perceptible cloudiness in a 100 th solution 
of salts of the alkaloid. With stronger solutions, these reagents 
produce distinct precipitates. 
Bichloride of platinum, the chromates of potash, iodide of 
potassium, and ferro- and ferri-cyanide of potassium fail to 
produce a precipitate with a 100 th solution of the chloride of 
the alkaloid. 
Fallacies.—None of the reactions now described are in them- 
selves characteristic of aconitine, they being common to many 
of the alkaloids and certain-other organic principles; nor is 
there at present any chemical reaction known that in itself is 
peculiar to this substance. By, however, the concurrent reac- 
tion of several of these reagents, taken in connection with the 
peculiar effects of the alkaloid upon the tongue, its nature may 
be fully established, even when present only in very minute 
quantity. In fact, the symptoms produced by this substance 
are usually so peculiar that they alone, when fully known, may 
enable the medical jurist to determine the cause of death, even SEPARATION FROM ORGANIC MIXTURES. 
619 
when the chemical evidence has entirely failed. A case of this 
kind, in which the root of aconite had been criminally admin- 
istered and no trace of the poison was discovered in the body, 
is related by Dr. Gieoghegan. (Dublin Medical Journal, July, 
1841, p. 403.) 
Physiological Test.—Much the most characteristic test yet 
known for the recognition of aconitine, is its pecidiar physiolog- 
ical action when applied to the tongue or in the form of solution 
to the skin. A drop of water holding in solution, in the form 
of a salt, only the I,oooth part of a grain of the alkaloid, when 
placed upon the end of the tongue, causes, as first observed by 
Dr. Headland, a very decided tingling and numbness of that 
organ, which continue for nearly an hour. According to Dr. 
Headland (Action of Medicines, p. 448), the 100 th of a grain 
dissolved in alcohol and rubbed into the skin, produces loss of 
feeling, lasting for some time; and the 50th of a grain will kill 
a small bird almost instantly. 
Separation from Organic Mixtures 
Suspected Solutions and Contents of the Stomach.—ln sus- 
pected poisoning by aconite in its crude state, before proceeding 
to a chemical examination of the mixture presented for examin- 
ation, the analyst should carefully examine it for any solid por- 
tions of the plant, which, if found, may be identified by their 
botanical characters. All parts of the plant have a bitter taste, 
which is soon followed by a persistent sense of numbness and 
tingling in the lips and tongue. 
Aconitine may be separated from the contents of the stom- 
ach, and like mixtures, in the same manner as heretofore de- 
scribed for the recovery of nicotine {ante, p. 438), or by the 
method of Stas. The alkaloid is more readily extracted from 
aqueous mixtures by chloroform than by ether, it being much 
more soluble in the former than in the latter liquid. The resi- 
due obtained on evaporating the chloroform or ether extract, 
should at first be stirred with a few drops of water containing 
a trace of acetic acid, and a small portion of the mixture ap- 
plied to the end of the tongue. If this experiment indicates 620 
ACONITINE. 
the presence of a very notable quantity of the poison, the 
remaining portion of the mixture may be dissolved in an appro- 
priate quantity of acidulated water snd the solution examined 
by some of the chemical tests. Should, however, the portion 
applied to the tongue fail to indicate the presence of the alka- 
loid, another and larger portion should be examined in the same 
manner, even if the whole of the mixture be thus consumed, 
since without the corroboration of this physiological test, the 
chemical tests, at present known, would be of no avail. 
On applying the method heretofore pointed out for the de- 
tection of nicotine, to the examination of the contents of the 
stomach of a dog, killed in fourteen minutes by a drachm of 
ordinary tincture of the root of aconite, the presence of acon- 
itine was very fully established. 
From the Blood.—Absorbed aconitine may be recovered from 
the blood, by slightly acidulating the fluid with sulphuric acid 
and agitating it in a wide-mouthed bottle with something more 
than its own volume of diluted alcohol, until the mixture be- 
comes homogeneous. It is then placed in an evaporating dish 
and exposed for some time, with frequent stirring, to a moder- 
ate heat; the cooled mass is transferred to a moistened linen 
strainer, and the solids retained by the strainer well washed 
with diluted alcohol and strongly pressed. The liquid is now 
concentrated at a moderate heat, again strained, then evapo- 
rated to a small bulk, filtered through paper, and evaporated 
on a water-bath to about dryness. The residue thus obtained 
is well stirred with about half a drachm of pure water, the so- 
lution filtered, then rendered alkaline by caustic potash, and 
thoroughly agitated with about two volumes of chloroform, 
which, after separation and decantation, is allowed to evaporate 
spontaneously, when the alkaloid will usually be left sufficiently 
pure for testing. 
About forty minims of the tincture of aconite root were ad- 
ministered to a small dog. The animal immediately indicated 
an uneasy sensation in the mouth and throat, and soon vomited 
a white frothy mucus, then lost the use of his legs, made re- 
peated attempts to vomit, had spasmodic convulsions with slow 
breathing, and died in sixty-four minutes after the dose had 621 
ATROPINE. 
been given. Twelve fluid drachms of blood, taken immediately 
from the animal, were submitted to the foregoing method of 
analysis, and the chloroform residue stirred with two drops of 
water containing the merest trace of acetic acid. A drop of this 
mixture placed upon the tongue, gave, in a little time, perfectly 
unequivocal evidence of the presence of aconitine. The remain- 
ing drop of the mixture was diluted with two drops of pure 
water, and examined in three separate portions by carbazotic 
acid, chloride of gold, and a solution of bromine, all of which 
produced precipitates very similar in quantity with those pro- 
duced from a 1,500 th solution of the alkaloid. The entire quan- 
tity of the poison recovered, could hardly have exceeded the 
300 th part of a grain, and may have been even much less than 
this, since it is by no means certain that the precipitates pro- 
duced by the reagents were perfectly pure : in fact, the con- 
trary is much the more probable. 
Twenty-five minims of the same tincture of aconite were 
given to a healthy cat. The animal was soon seized with 
violent vomiting, lost the power of walking, frothed at the 
mouth and nose, and died under violent symptoms within thirty 
minutes. The chloroform residue obtained from one ounce of 
blood from this animal, when stirred with a few drops of acid- 
ulated water and examined by chloride of gold and a solution 
of bromine, gave reactions similar to those produced from a 
quite dilute solution of aconitine; yet, about one-half of the 
residue, when applied to the tongue, failed to produce any 
decided effect upon that organ. It can not, of course, under 
these circumstances be claimed that the gold and bromine reac- 
tions were really due to the presence of aconitine. 
Section ll.—Atropine. (Belladonna.) 
History.—Atropine is the active principle, or alkaloid, of 
Atropa Belladonna, or Deadly Nightshade. It exists in the root, 
leaves, and berries of the plant. The existence of this prin- 
ciple was first announced, in 1819, by Brandes; but it was first 
obtained in its pure state by Mein, a German pharmaceutist, 622 
ATROPINE. 
in 1833. Its composition, according to the analyses of Planta, 
is C 34 It is a white crystallisable solid, and a most 
virulent poison. 
Preparation.—Atropine may be obtained, according to M. 
Rabourdin (Comptus Rendus, Oct. 14, 1850), in the following 
manner. The fresh leaves of the plant are well bruised and 
submitted to pressure to extract the juice; this is then heated 
to about 185° F. in order to coagulate the albumen, and filtered, 
after which it is rendered alkaline by caustic potash and thor- 
oughly agitated for a few minutes with chloroform. In about 
half an hour, the latter fluid, holding in solution the atropine 
and having the appearance of a greenish oil, will have subsided 
to the bottom of the mixture. The supernatant liquid is then 
decanted, and the chloroform solution washed with successive 
portions of water, as long as this liquid becomes colored. The 
chloroform solution is then transferred to a tubulated retort, 
and distilled in a water-bath, until all the chloroform has passed 
into the receiver, when the residue is treated with a little water 
acidulated with sulphuric acid, which will dissolve the atropine, 
leaving a green resinous matter. The solution thus obtained is 
filtered, the filtrate treated with slight excess of carbonate of 
potash, and the precipitated atropine collected on a filter, 
washed, and dissolved in rectified alcohol, which upon spon- 
taneous evaporation will leave the alkaloid in beautiful groups 
of acicular crystals. 
In the absence of the fresh plant, M. Rabourdin recom- 
mends to employ the extract of belladonna. Thirty parts of 
the extract are dissolved in one hundred parts of water, and 
the filtered solution agitated, for about a minute, with two parts 
of caustic potash and fifteen parts of chloroform. The subse- 
quent steps of the process are the same as directed above, 
except that the washed chloroform solution, instead of being 
distilled, is allowed to evaporate spontaneously. The product 
obtained by either of these methods, if not perfectly colorless, 
may be further purified, as first advised by Professor Procter, 
of Philadelphia, by redissolving it in water acidulated with 
sulphuric acid, and extracting the foreign organic matter by 
chloroform; the aqueous solution is then rendered alkaline PHYSIOLOGICAL EFFECTS. 
623 
by potash, and the liberated alkaloid extracted with fresh 
chloroform, which on spontaneous evaporation will leave it in 
its pure state. 
Mein, in his experiments, obtained twenty grains of atropine 
from twelve ounces of the fresh root of belladonna; and Luxton, 
between five and six grains from one thousand grains of the 
fresh leaves. (U. S. Dispensatory, 1865, p. 1018.) On an 
average, perhaps, the green root and leaves do not contain 
over about one-third of one per cent, of the alkaloid. The 
ordinary medicinal dose of atropine, and its salts, is about one- 
thirtieth of a grain. The pharmaceutical extracts and tincture 
of belladonna, are each subject to great variation in strength. 
The dose of the former, for an adult, is at first from one-fourth 
to one-half a grain; that of the latter, from fifteen to twenty- 
five minims. 
Poisoning by atropine in its pure state, has been of rather 
rare occurrence; but numerous instances of poisoning by the 
berries and some of the preparations of belladonna, are recorded. 
With few exceptions, however, all these cases have been the 
result of accident, most of them having been occasioned by 
the berries being eaten through ignorance of their properties. 
The berries have considerable resemblance to cherries, and a 
sweet, but mawkish taste. 
Symptoms.—The most constant symptoms occasioned by 
poisonous doses of belladonna are, dryness of the mouth and 
throat, difficulty of deglutition, dilatation of the pupils, impaired 
vision, and delirium, succeeded by drowsiness and stupor. The 
delirium is generally of a pleasing character, but sometimes of 
a furious nature. These effects are usually attended with a 
sense of burning and constriction of the throat, impaired articu- 
lation, great thirst, giddiness, numbness of the limbs, a stagger- 
ing gait, nausea and sometimes vomiting, spectral illusions, 
and great mental excitement. The pulse becomes quick and 
small, and sometimes the face red and turgid, and the eyes 
wholly insensible to light. The secretions are usually increased; 
and irritation of the urinary organs has sometimes occurred; 
and in some instances, a scarlet eruption has appeared on the 
skin. In fatal cases, death is usually preceded by coldness of 624 
ATROPINE. 
the extremities, a rapid and intermittent pulse, deep coma, and 
sometimes, though rarely, convulsions. 
The following symptoms were observed in one hundred and 
fifty French soldiers, who had eaten the berries of the plant; 
Dilatation and immobility of the pupil, with total insensibility 
of the eye to the presence of external objects, or at least con- 
confused vision; bluish injection of the conjunctiva; great prom- 
inence of the eye; dryness of the lips, tongue, and throat; 
difficult, and in some cases impossible deglutition; nausea, but 
no vomiting; great weakness, with difficulty or impossibility of 
standing; continual movement of the hands and fingers; lively 
delirium, accompanied with a silly laugh; aphonia, or confused 
sounds uttered with difficulty; and ineffectual attempts to empty 
the bowels. These effects were followed by very gradual return 
to health and reason, without any recollection of the preceding 
state. (Orfila’s Toxicologic, 1852, ii, 478.) 
The symptoms produced by belladonna, as usually developed, 
could not readily be confounded with those of any other sub- 
stance, except stramonium and hyoscyamus (Pereira). The 
symptoms usually manifest themselves within an hour after the 
poison has been taken; but they have frequently been delayed 
for several hours, especially in poisoning by the berries. Of 
the numerous recorded cases of poisoning by this substance, 
but comparatively few proved fatal, and in these the time of 
death varied from a few hours to some days. The effects in 
non-fatal cases are frequently very slow in disappearing, some- 
times lasting for several days or even weeks. 
A healthy man ate of a pie made with the berries of bella- 
donna and apples. A few minutes after taking his dinner, he 
complained of feeling drowsy; the lethargy soon increased, his 
countenance changed color, the pupils became dilated, and he 
experienced a strange coppery taste in his mouth. On going 
up stairs, he staggered, and upon entering his room, fell, and 
became insensible. He subsequently became delirious and con- 
vulsed, and died the following morning. A child to whom a 
portion of the pie had been given, died on the same day. 
(New York Jour, of Med., vol. viii, p. 284.) In four recent 
cases in which some boys had eaten a quantity of the extract PHYSIOLOGICAL EFFECTS. 
625 
of belladonna, in one instance as much as a draclim, the follow- 
ing symptoms were observed in one of the cases. When first 
seen by a physician the patient was quite delirious, the delirium 
being of a fantastic character; he could neither hear nor speak 
plainly, and labored under hallucinations, but was otherwise 
unconscious. The pupils were widely dilated, and the eyes had 
a staring look. At first he complained of some pain in the 
throat and of his imperfect sight, objects appearing white to 
him. The pulse was very feeble, and almost countless; and 
there was great difficulty of swallowing. Under active treat- 
ment, including the use of an emetic, the delirium having lasted 
eighteen hours gradually passed away; but it was not until the 
lapse of forty hours that he was perfectly rational. Much the 
same symptoms were present in the three other cases. All the 
patients finally recovered. (Lancet, 1860, vol. i, p. 138.) 
The following instance of recovery is related by Dr. H. M. 
Gray (New York Jour, of Med., Sept., 1845, p. 182). A child, 
between two and three years of age, swallowed from eight to 
twelve grains of the extract of belladonna. Something over 
half an hour after taking the poison, the expression of the 
patient was that of terror; the pupils were widely dilated and 
immovable, the conjunctiva highly injected, and the whole eye 
prominent and very brilliant. The face, upper extremities, and 
trunk of the body exhibited a diffuse scarlet efflorescence studded 
with innumerable papillae, very closely resembling the rash of 
scarlatina. The skin was hot and dry; the pulse much increased 
m force and frequency; the respiration anxious, and attended 
with the stridulous sound of croup. There was also a constant 
but unsuccessful effort at deglutition, with spasmodic action of 
the muscles of the throat and pharynx; and paroxysms of 
Violent motion and rapid automatic movements, attended with 
convulsive laughter. Under the action of an emetic, the alarm- 
*ug symptoms passed off in about three hours, and the child 
soon recovered, with the exception of a moderate diarrhoea and 
a slight enlargement of the pupil. 
The external application of belladonna, and its administration 
111 the form of an enema, has in several instances given rise to 
serious and even fatal results. A case is related in which an 626 
ATROPINE. 
injection of a decoction of the root caused the death of an adult 
in five hourg; and another, in which only two grains of the 
extract, administered in the same manner, gave rise to alarming 
symptoms. Dr. Lyman relates an instance in which the appli- 
cation of a small belladonna plaster, to the chest of a nervous 
woman, produced all the usual symptoms of poisoning by that 
substance, from which the patient did not entirely recover until 
after four or five days. Two very recent cases of this kind, 
in which a lotion of belladonna had been applied, are mentioned 
in the “Chemical News” (London, Nov., 186G, p. 216). 
Atropine.—The symptoms produced by atropine in its pure 
state, are the same in kind as those occasioned by belladonna, 
but they are usually much more prompt in appearing. In a 
case related by Dr. Schmid, a stout healthy man swallowed 
from one-sixth to one-fourth of a grain of the alkaloid in solu- 
tion. An hour afterwards, the patient was in a state of fearful 
excitement; the tongue was swollen and projected between the 
teeth, and he incessantly moved it and his lips in a stammering 
manner, but without emitting a single intelligible word. The 
eyes were staring; the head hot, and the countenance livid; 
the pupils dilated to their utmost, and insensible to light; the 
pulse was rapid, full, and strong, and there was a constant 
desire, but without the power, to make water. During the 
following hour the excitement continually increased, when the 
subcutaneous injection of a fifth of a grain of acetate of morphia 
into the right temple was soon succeeded by a state of calm. 
After two hours more, the excitement had again attained almost 
its former hight, but it was again subdued by a repetition of 
the morphine injection. The patient now gradually recovered, 
the only symptoms remaining about twenty-four hours after the 
occurrence being extreme weakness, dryness of the throat, 
slight twitchings of the limbs, and a dilated state of the pupils. 
(Amer. Jour. Med. Sci., July, 1866, p. 269.) 
In a case recorded by Dr. Taylor, two grains of the alkaloid 
caused the death of a young man. The young man took the 
dose on going to bed, and he was found dead the next morning: 
no trace of the poison was detected in the stomach or its con- 
tents. (On Poisons, p. 830.) Dr. Andrew, of Edinburgh, EXTERNAL APPLICATION. 
627 
relates an instance in which two-thirds of a grain, taken in 
mistake by a female, produced most violent symptoms from 
which the patient did not entirely recover for more than a week. 
(Wharton and StillAs Med. Jur., p. 639.) The internal admin- 
istration of even only one-tenth of a grain has been followed 
by alarming symptoms. On the other hand, Dr. Roux has re- 
cently reported an instance in which a lady, in a fit of despair, 
swallowed a solution containing nearly two grains of atropine, 
and entirely recovered, not however without suffering the most 
severe symptoms. The treatment employed in this case, con- 
sisted of emetics, followed by a strong decoction of coffee, and 
M. Bouchardat’s solution of iodine in iodide of potassium. 
The employment of atropine in the form of subcutaneous in- 
jection has in several instances been followed by very serious 
symptoms, even when injected in very minute quantity. Thus, 
Dr. Eulenberg relates an instance in which he employed in this 
manner, in the case of a lady affected with facial neuralgia, 
l-48th of a grain of the alkaloid, and alarming symptoms of 
poisoning soon appeared. The patient threw herself about the 
bed entirely unconscious, and from time to time broke out in 
furious delirium; the limbs, and also the head, were shaken 
with convulsive jerkings. The pupils were moderately dilated, 
the pulse small, and somewhat increased in frequency. An im- 
mediate injection of one-third of a grain of morphine into the 
temporal region, in close proximity to the former place of injec- 
tion, was followed within about three minutes by a cessation of 
the twitchings, and in ten minutes the patient fell into a heavy 
peaceful sleep, from which she awoke in eight hours without 
any symptom of the poison being present. (Amer. Jour. Med. 
Sci., April, 1866, p. 434.) In another case, related by Dr. 
Lorent, less than the 1-100 th of a grain of the alkaloid, em- 
ployed in this manner, produced very alarming results. 
The external application of atropine may speedily produce 
death. In an instance reported by Dr. Floss, of Leipsic, an 
ointment composed of fifteen parts of sulphate of atropia to 
seven hundred parts of lard, applied as a dressing to a blistered 
surface on the neck of a man, caused death, under the most 
violent symptoms of belladonna poisoning, within two hours 628 
ATROPINE. 
after the application had been made. (Ibid., April, 1865, p. 
541.) A few drops of an aqueous solution containing two-thirds 
of a grain of the alkaloid to the ounce of fluid, applied to the 
eye of a man affected with cataract, produced violent constitu- 
tional effects, with constant hallucinations, and inability to pass 
urine 5 the violent delirium continued during the ensuing night, 
and it was some days before the patient entirely recovered. 
Treatment.—This consists, in case the poison has been 
swallowed, in the speedy administration of an emetic or the 
employment of the stomach-pump. Of the various chemical 
antidotes that have been proposed, may be mentioned tannic 
acid, a solution of iodine in iodide of potassium, hydrate of 
magnesia, and animal charcoal. If either of these substances 
be employed, it should only be in connection with emetics or 
the use of the stomach-pump. As a physiological antidote, 
morphine administered either by the mouth or by subcutaneous 
injection, has been strongly advised; and instances are reported, 
as in some of those already mentioned, in which this treatment 
was followed by rapid recovery. (See Treatment of poisoning 
by opium, ante, p. 464.) 
Post-mortem Appearances.—These, as in death from most 
of the vegetable poisons, are subject to considerable variation. 
The more constant appearances are, a dilated state of the pu- 
pils, more or less redness of the raucous membrane of the stom- 
ach and small intestines, fullness of the cerebral vessels, and 
congestion of the lungs. The blood is usually dark colored and 
liquid. Instances are related, however, in which this poison 
produced death without leaving any notable morbid change in 
the body. 
Chemical Properties. 
In the Solid State.—Atropine, in its pure state, is a white, 
odorless solid, which crystallises in the form of transparent 
prisms, usually aggregated into beautiful tufts or stellated 
groups. It has a bitter, acrid taste. When heated in a tube, 
it readily fuses to a colorless, transparent liquid, which ascends 
the sides of the tube; upon cooling, the liquid becomes a clear 
gummy mass, and ultimately concretes to a vitreous solid. When CHEMICAL PROPERTIES. 
629 
gradually heated on porcelain, it fuses and is slowly dissipated, 
giving rise to dense white fumes. According to Planta, the fus- 
ing point of atropine is 194° F., and at 284°, it is volatilised, 
partially unchanged, the greater part undergoing decomposition. 
(Chem. Gazette, 1850, p. 349.) When rapidly heated, it melts, 
puffs up, then evolves dense white fumes, and takes fire, burning 
with a bright flame, and leaving a shining black cinder, which 
may be entirely consumed. Heated in contact with a fixed 
caustic alkali, it readily undergoes decomposition with the evo- 
lution of ammonia. 
Atropine has strongly basic properties, and completely neu- 
tralises even the most powerful acids forming salts, several of 
which are readily crystallisable. Concentrated nitric acid dis- 
solves the pure alkaloid without change of color, even upon the 
application of heat: the subsequent addition of chloride of tin 
produces no visible change. So, also, concentrated sulphuric 
add dissolves it to a colorless solution, which is unchanged by 
a crystal of nitrate of potash; on the addition of a crystal of 
bichromate of potash, the acid solution slowly acquires a green 
color, due to the formation of sesquioxide of chromium. 
Solubility.—A sample of atropine examined by Planta, was 
soluble in 299 parts of water at the ordinary temperature; but 
a single experiment in our own hands, indicated that the alka- 
loid requires 414 parts of that liquid for solution, even after 
several hours digestion. It is readily soluble in nearly every 
proportion in alcohol and in chloroform, and freely soluble in 
absolute ether. Upon spontaneous evaporation, it separates 
from either of these liquids, in the crystalline form. A satu- 
rated aqueous solution of the alkaloid, has a well-marked alka- 
line reaction. Most of the salts of atropine are freely soluble 
m water and in alcohol; but they are almost wholly insoluble 
m ether and chloroform, at least this is the case with the sul- 
phate and chloride. 
Of Solutions of Atropine.—The following results, in re- 
gard to the behavior of solutions of atropine, are based upon 
file examination of two apparently perfectly pure specimens of 
file alkaloid, prepared by different well-known European man- 
ufacturers, one of the samples being employed in the form of 630 
ATROPINE. 
sulphate, and the other as chloride. The fractions employed 
indicate the fractional part of a grain of the pure alkaloid 
present in one grain of water; and the results, unless otherwise 
indicated, refer to the behavior of one grain of the solution. 
1. The Alkalies and Alkaline Carbonates. 
Caustic potash and soda throw down from concentrated 
aqueous solutions of salts of atropine a white, amorphous pre- 
cipitate of the pure alkaloid, which is readily soluble in free 
acids, and also in large excess of the precipitant. After a 
time, especially if the mixture has been stirred, the precipitate 
assumes the crystalline form. The presence of foreign organic 
matter readily prevents the formation of crystals. 
One grain of a 100 th solution of the alkaloid yields a quite 
copious precipitate, which on being stirred with a glass rod, in 
a little time, becomes a mass of crystals, of the forms illustrated 
in Plate XII, fig. 4. Solutions but little more dilute than this, 
fail to yield a precipitate. 
Ammonia produces in solutions of salts of the alkaloid the 
same precipitate as occasioned by the fixed caustic alkalies; 
but the deposit is much more readily soluble in excess of the 
precipitant. 
Carbonate of potash produces in a 100 th solution of the 
alkaloid a distinct turbidity; but the carbonates of soda and 
ammonia fail to produce, in a similar solution, any visible 
reaction. 
2. Bromine in Bromohydric Acid. 
An aqueous solution of bromohydric acid saturated with 
free bromine produces in solutions of salts of atropine and of 
the free alkaloid, even when highly diluted, a yellow amorphous 
precipitate, which in a little time becomes crystalline. The 
precipitate from somewhat strong solutions of the alkaloid, after 
a time disappears; but it is immediately reproduced upon 
further addition of the reagent. The precipitate is insoluble 
in acetic acid, and only very sparingly soluble in large excess 
of hydrochloric, nitric, and sulphuric acids, and in the fixed CARBAZOTIC ACID TEST. 
631 
caustic alkalies: it is even produced from solutions of the alka- 
loid in concentrated sulphuric acid. 
1. Tihr grain of atropine, in one grain of water, yields a very 
copious, bright-yellow, amorphous precipitate, which very 
soon, beginning along the margin, becomes a mass of 
crystals, Plate XII, fig. 5. After several minutes, most 
of the crystals dissolve, but they may be reproduced, 
even several times, by further addition of the reagent. 
2. r,if«ro grain, yields a copious, yellow deposit, which soon 
furnishes crystals, having the forms illustrated above. 
3- rorswo grain: a quite good, yellowish precipitate, which in 
a few moments becomes granular and crystalline, and 
presents the appearance figured in Plate XII, fig. 6. 
I* TstWo grain: in a very little time, a quite satisfactory 
deposit of short crystalline needles, and granules. 
5. 5-irJoiro grain: after some minutes, some few granules appear, 
The production of the above crystals is quite characteristic 
of this alkaloid. Although the reagent produces yellow precip- 
itates with most, if not all, the other alkaloids, and with certain 
other organic substances; yet all these deposits, with the excep- 
tion of that from opianyl, unlike the atropine precipitate, remain 
amorphous. The crystallised atropine deposit is readily distin- 
guished from the opianyl compound, by its form. It may here 
be remarked that the reagent produces a similar crystalline 
precipitate with daturine, but, as will be pointed out hereafter, 
this alkaloid is identical with atropine. We have found the 
precipitate become crystalline in the presence of even compara- 
tively large quantities of foreign organic matter. In the absence 
°f a solution of bromohydric acid, an alcoholic solution of 
bromine may be employed as the reagent. 
but the result is not satisfactory. 
3. Carbazotic Acid. 
An alcoholic solution of carbazotic acid occasions in some- 
what strong solutions of salts of atropine a yellow, amorphous 
precipitate, which is readily soluble in acids, even in acetic acid. 
After a time, the precipitate becomes more or less crystalline. 632 
ATROPINE. 
1. yoo grain of atropine, yields a copious, light yellow deposit. 
If the mixture be stirred with a glass rod, it soon yields 
streaks of granules along the path of the rod, and in a 
little time the deposit becomes entirely crystalline, the 
crystals being principally in the form of transparent plates, 
and these more or less aggregated into very beautiful 
groups, Plate XIII, tig. 1. 
3- r.TTo'o grain: within a few moments, a slight, greenish-yellow 
precipitate appears, and in a little time, there is a quite 
good deposit. If the mixture be stirred, it soon yields a 
tine crystalline deposit. 
3. 5-oVo grain: upon stirring the mixture, it yields, after a little 
time, caseous streaks over the bottom of the watch-glass 
containing the mixture; but the reaction is not very 
satisfactory. 
This reagent also produces crystalline precipitates with vari- 
ous other substances, but the forms illustrated above are quite 
peculiar to atropine 
4. Terchloride of Gold. 
This reagent produces in solutions of salts of atropine, when 
not too dilute, a light yellow, amorphous precipitate of the 
double chloride of atropine and gold, which after a time be- 
comes converted into crystals. The precipitate is insoluble in 
potash, and but sparingly soluble in acetic and hydrochloric 
acids. 
1. yito grain of atropine, yields a copious precipitate, which 
soon becomes a mass of crystals, having the peculiar forms 
shown in Plate XIII, tig. 2. 
2. r,iro“o grain, yields a good deposit, which soon, especially if 
the mixture be stirred, assumes the crystalline form. 
3. s-oVo grain, yields no indication, even after the mixture has 
stood some time. 
The crystalline form of the double atropine salt, as figured 
above, readily distinguishes it from other substances. The 
formation of these crystals, however, is readily prevented by 
the presence of foreign organic matter. PHYSIOLOGICAL TEST. 
633 
5. lodine in lodide of Potassium. 
A solution of iodine in iodide of potassium throws down 
from solutions of salts of atropine, and of the free alkaloid, a 
reddish-brown, amorphous precipitate, which is insoluble in 
acetic acid, and only sparingly soluble in potash. 
1. xinr grain of atropine, yields a very copious precipitate, 
which dissolves, to a clear solution, in about three drops 
of a saturated solution of caustic potash. 
2. ixoVo grain: a quite copious precipitate. 
3- ro.Vffo grain, yields a very good deposit. 
4. rorlro'o grain, yields at first a yellowish turbidity, and after 
a little time, a distinct, reddish-brown precipitate. 
5. rtToVoT) grain, yields a very distinct turbidity 
The reaction of this reagent is common to a large class of 
substances. 
Other Reagents.—Tannic acid produces in solutions of salts 
of atropine, a dirty-white, amorphous precipitate, which is 
readily soluble in the caustic alkalies and in free acids. One 
grain of a 100 th solution of the alkaloid yields a copious 
deposit; and a similar quantity of a I,oooth solution, a quite 
distinct reaction. Bichloride of platinum, and chloride of palla- 
dium, throw down from concentrated solutions of salts of the 
alkaloid, dirty-brown, amorphous precipitates. Strong solutions 
of salts of atropine, when treated with a stream of chlorine gas, 
become slightly turbid, and yield on the subsequent addition of 
ammonia, a white precipitate. 
lodide of potassium, sulphocyanide of potassium, the chro- 
mates of potash, chloride of mercury, nitrate of mercury, ferro- 
and ferri-cyanide of potassium, and gallic acid fail to precipitate 
even concentrated solutions of salts of atropine. 
Physiological Test.—The property possessed by atropine of 
dilating the pupil of the eye, has been proposed as a means of 
detecting its presence. Dr. Headland states (Action of Medi- 
cine, p. 294), that the 3,000 th part of a grain of the alkaloid, 
dropped, in the form of solution, into the eye of an adult, will 634 
ATROPINE. 
answer this purpose; and that one-tenth of a grain taken into 
the stomach, will cause dilatation of both pupils. It must be 
borne in mind, however, that this property is also possessed by 
daturine and hyoscyamine, the former being the active principle 
of stramonium, and the latter of henbane. 
Separation prom Organic Mixtures. 
Suspected Solutions and Contents of the Stomach.—These 
should first be carefully examined for the presence of any solid 
portions of the plant or the seeds, which, if found, may be 
identified by their physical and botanical characters. On ac- 
count of the indigestible nature of the seeds and berries, they 
may remain in the alimentary canal for some days without 
undergoing any change. Dr. Christison cites several instances 
(Ojn Git., p. 644) in which the seeds and fragments of the fruit 
were discharged from the bowels and by vomiting, even several 
days after they had been taken. 
Atropine is separated with considerable difficulty from com- 
plex organic mixtures, especially when it exists in the form of 
portions of the plant. The suspected mixture, after comminu- 
tion of any solids present and dilution if necessary, is treated 
with about an equal volume of strong alcohol, slightly acidulated 
with sulphuric acid, and exposed for about half an hour to a 
gentle heat; when cool, the liquid portion is strained through 
muslin, the residue washed with alcohol, and the strained liquid 
and washings concentrated to a small bulk, at a moderate tem- 
perature on a water-bath. If during the evaporation, much 
insoluble matter separates, it is removed by a strainer. The 
cooled concentrated liquid is passed through a moistened filter, 
then transferred to a test-tube and washed by agitating it with 
about twice its volume of pure ether, which, after repose, is 
carefully decanted and reserved for future examination, if nec- 
essary ; the aqueous solution may again be washed with a fresh 
portion of ether, and this removed as before. The aqueous 
liquid is now rendered slightly alkaline by potash, and thor- 
oughly agitated with about twice its volume of pure chloroform, 
which will dissolve the liberated alkaloid, if present; after the 635 
SEPARATION FROM ORGANIC MIXTURES. 
liquids have completely separated, the chloroform is carefully 
removed to a large watch-glass, and allowed to evaporate spon- 
taneously. 
The residue, thus obtained in the watch-glass, is stirred 
with a few grains of water, containing a trace of sulphuric acid, 
and the solution, after filtration if necessaxy, examined by some 
of the liquid tests for atropine. As the bromine test is much 
the most characteristic yet known for the identification of this 
alkaloid, it should first be applied to a single drop of the solu- 
tion. If it should fail to pi’oduce a crystalline precipitate, it is 
quite certain that neither of the other reagents would produce 
ciystals, without which the results are of little value, since 
otherwise they are common to a large class of organic sub- 
stances. It must not, however, be expected that the bromine 
reagent will always pi’oduce a crystalline deposit containing all 
the forms obtained from a perfectly pure solution of atropine; 
most frequently, under the pi’esent conditions, the pi’ecipitate 
consists of short, opake, irregular needles, and granules, but 
these are characteristic of the alkaloid. 
In case the bromine reagent produces a precipitate which 
will not crystallise, the remaining poi’tion of the solution is 
diluted with a small quantity of water, then rendered alkaline 
by potash, and the alkaloid again extracted by chloroform. 
This fluid may now, upon spontaneous evaporation, leave the 
alkaloid, if present in very notable quantity, in the crystalline 
state. The chloroform x'esidue is dissolved in a few grains of 
acidulated water, and examined as before directed. A small por- 
tion of the solution may be submitted to the physiological test. 
On applying the method now considered, to the examination 
of the contents of the stomachs of inferior animals to which 
comparatively small quantities of a fluid extract of belladonna 
had been purposely added, we, in every instance, obtained per- 
fectly satisfactoiy evidence of the presence of ati’opine. In 
most of these cases, however, the results wei’e quite doubtful, 
until the second chlorofonn exti’act was examined, when the 
bromine pi’ecipitate i-eadily crystallised. 
Atropine may also be recovered from organic mixtures by 
the use of ethex*, the steps of the process being pi’ecisely the 636 
DATURINE. 
same as when chloroform is employed. The alkaloid, however, 
is much less readily extracted from organic liquids by ether 
than by chloroform. 
From the Flood.—Absorbed atropine may be recovered from 
the blood, by acidulating the latter with sulphuric acid, in the 
proportion of about one drop of the acid to each ounce of liquid, 
and agitating it with something more than its own volume of 
alcohol. The mixture is then gently heated for about fifteen 
minutes, and the liquid, after cooling, strained through muslin, 
and the residue washed with alcohol and strongly pressed. The 
strained liquid is concentrated, at a moderate temperature on a 
water-bath, again strained, then evaporated to a small volume, 
filtered, rendered alkaline by potash, and the liberated alkaloid 
extracted by chloroform. If the chloroform residue is not suffi- 
ciently pure for testing, it is extracted, in the usual manner, a 
second time by that liquid. 
Three ounces of blood, taken from a dog that had been 
given five drachms of Tilden’s fluid extract of belladonna and 
killed by a blow on the head one hour and a half afterwards, 
when examined by the foregoing method, furnished very satis- 
factory evidence of the presence of atropine. A similar quan- 
tity of the extract being administered to a cat, a portion passed 
into the lungs of the animal, and caused death in less than three 
minutes. Five drachms of blood taken from this animal, also 
furnished satisfactory and unequivocal evidence of the presence 
of the alkaloid. 
Section lll.—Daturine. (Stramonium.) 
History.—Daturine is the name applied to the active prin- 
ciple, or alkaloid, of Thornapple, Jamestoivn tveed) or Datura 
stramonium. The existence of this principle was announced in 
1819 by Brandes ; but it was first obtained in 1833 by Geiger 
and Hesse. It is found in all parts of the plant, but most 
abundantly, it is said, in the seeds and fruit. Its elementary 
composition, according to the analyses of Planta, is 
it being identical with that of atropine. 637 
PHYSIOLOGICAL EFFECTS. 
Preparation.—Daturine may be obtained from the bruised 
seeds of stramonium, and other parts of the plant, in the same 
manner as atropine is prepared from belladonna and its extract, 
as heretofore described (ante, p. 622.) The proportion of the 
alkaloid present in the plant, is, perhaps, about the same as 
that found in belladonna. 
Numerous instances of poisoning by stramonium more par- 
ticularly by the seeds, have occurred, but, with few exceptions, 
they have been the result of accident. As yet, there seems to 
be no instance in which daturine in its pure state, has been 
taken as a poison. 
Symptoms. The symptoms produced by stramonium are 
very similar, if not identical in kind, with those occasioned by 
belladonna. Thus, they are, dryness of the throat, difficulty of 
deglutition, dilatation and insensibility of the pupil, headache, 
nausea, vomiting, great thirst, obscurity of vision, or total 
blindness, ringing in the ears, great anxiety, hot skin, flushed 
countenance, vertigo, and wild delirium, with spectral illusions, 
and tremors of the extremities, followed by stupor and coma. 
Occasionally convulsions and paralysis have occurred, as also, 
a scarlet eruption over the skin. 
In a case reported by Dr. J. Gi. Johnson, of Brooklyn, 
N. Y., a boy seven years of age, ate a quantity of the green 
seeds of stramonium, picking them from the burs. The first 
symptoms observed, were impaired speech, flushed face, twitch- 
ings of the fingers, and a staggering gait. About two hours and 
a half after taking the poison, the child was in a state of violent 
agitation, and had spasmodic twitchings of the hands, as if 
affected with chorea; the pupils were enormously dilated, and 
insensible to light, and there was total blindness; the face, 
especially around the mouth, was much swollen, the action of 
the heart feeble, and the pulse could not be counted; the lower 
extremities were cold, and perfectly powerless. The action of 
an emetic, now brought away a quantity of the seeds. Two 
hours later, the child was violently maniacal, constantly catching 
at imaginary objects in the air, was also deaf, and unable to 
articulate. These symptoms gradually abated, but it was sev- 
eral days before the patient entirely recovered, the insensibility 638 
DATURINE. 
of the pupils continuing until the fourth day. (American Med. 
Times, 1860, vol. i, p. 22.) 
Dr. H. Y. Evans, of Philadelphia, has very recently re- 
ported an instance in which seven children, aged from six to 
nine years, had each swallowed, it is said, only ten of the seeds. 
Four hours afterwards, the pupils in all seven cases were dilated 
to their utmost. In three of the children, who had swallowed 
the seeds without chewing them, dilatation of the pupils, and 
slight perversion of vision, were the only effects observed. But 
in the four remaining cases, in which the seeds had been 
chewed, in addition to the dilated state of the pupils and per- 
verted vision, there was confusion of intellect, deafness, intoxi- 
cation, full pulse, slow respiration, and entire loss of power to 
direct the motions of the limbs; these symptoms were succeeded 
in a few hours by stupor, and in one case by violent delirium, 
resembling delirium tremens. Emetics having failed to act, 
except in the three slight cases, the stomach was emptied by 
means of the stomach-pump, and on the third day every vestige 
of the poisoning had disappeared, the pupils being the last to 
yield. (Amer. Jour. Med. Sci., July, 1866, p. 278.) 
A somewhat similar instance, to that just cited, has been 
reported by Dr. A. P. Turner (Ibid., April, 1864, p. 552). Of 
seven children who had eaten a quantity of the seeds, in five 
of them vomiting was early produced, and they were but 
slightly affected. In the other two, the most violent symptoms 
with wild delirium manifested themselves; but under the use of 
emetics, and laudanum, the patients were quite well on the 
third day. In a case related by Dr. Calkins, a child four years 
of age, entirely recovered after having swallowed over a table- 
spoonful of the seeds, although they remained undisturbed in 
the body for upwards of seven hours, when they were partly 
ejected by vomiting, and afterwards partly by purging. (Ameri- 
can Medical Monthly, Sept., 1856, p. 220.) 
Dr. C. C. Lee has related an instance (Amer. Jour. Med. 
Sci., Jan., 1862, p. 54) in which three adults were poisoned by 
an alcoholic decoction of the seeds of stramonium. Soon after 
taking the poison, two of the patients were speechless, unable 
to walk, and in a comatose condition; their faces flushed to an PHYSIOLOGICAL EFFECTS. 
639 
almost violet hue, the conjunctive injected, the pupils enor- 
mously dilated and insensible, the face and upper extremities 
burning hot, the tongue and throat dry, the respiration slow 
and labored, and the pulse rapid, very tense and full. In the 
other case, in which a smaller quantity of the decoction had 
been taken, the skin was of a scarlet hue and hot, the pupils 
dilated, the tongue parched, the respiration hurried, the pulse 
very rapid, and fluttering, and there was intense thirst, with 
violent delirium, the patient constantly pursuing, with her hands, 
imaginary objects in the air, or picking at the bedclothes. 
About an hour and a half after the poison had been taken, 
active treatment, including the use of the stomach-pump, was 
resorted to, under which all the patients rapidly recovered. 
In a fatal case, quoted by Dr. Christison (On Poisons, p. 
646), in which a child, aged two years, had swallowed, without 
chewing, about one hundred of the seeds, the following symp- 
toms were observed. The child soon became fretful and like a 
person intoxicated; in the course of an hour efforts to vomit 
ensued, together with flushed face, dilated pupils, incoherent 
talking, and afterwards wild spectral illusions and furious delir- 
ium. In two hours and a half, there was loss of voice and the 
power of swallowing; then croupy breathing and complete coma 
set in, with violent spasmodic agitation of the limbs, occasional 
tetanic convulsions, warm perspiration, and an imperceptible 
pulse. Subsequently the pulse became extremely rapid, the 
abdomen tympanitic, and the bladder paralysed, but there were 
frequent involuntary stools; and death took place twenty-four 
hours after the poison had been taken. At an early period in 
the case, twenty of the seeds were discharged by an emetic; 
and afterwards eighty by purging: none were found in the 
alimentary canal after death. In another case, a decoction of 
about one hundred and twenty-five of the seeds, pi’oved fatal 
to an elderly woman, in seven hours. In a case related by 
b>r. Allan, an unknown quantity of the seeds caused the death 
of a healthy man, in about seven hours and a half. (Lancet, 
London, Sept. 18, 1847, p, 298.) 
The external application of stramonium to a blistered sur- 
face, has, in several instances, given rise to alarming symptoms. 640 
DATURINE. 
In one instance, the extract employed as a suppository, induced 
many of the symptoms of delirium tremens. Even bruising the 
leaves in a mortar has caused dilated pupil and irritation of the 
skin. (Beck’s Med. Jur., vol. ii, p. 877.) 
Treatment.—This is the same as in poisoning by bella- 
donna {ante, p. 628). In a case of stramonium poisoning quoted 
by Dr. A. Stille (Mat. Med., vol. i, p. 754), one grain of chloride 
of morphine was administered every hour, and eight grains were 
taken before any result was perceived. After the eighth dose, 
slight signs of awakening consciousness were visible, but the 
pupil still remained widely dilated. Subsequently, as the symp- 
toms abated, the intervals between the doses were lengthened, 
but in the course of eighteen hours, fifteen grains of the mor- 
phine salt were taken. 
Post-mortem Appearances.—ln the case of the child, here- 
tofore cited, in which death occurred in twenty-four hours, the 
brain was found natural, the stomach and intestines healthy, 
the bladder distended, the larynx and oesophagus slightly red- 
dened, the rima-glottidis thickened and very turgid, and the 
blood throughout the body semi-fluid. In Dr. Allan’s case, 
nineteen hours after death, there was found great turgescence 
of the membranes of the brain; the brain itself was firm and 
highly injected, the choroid plexus turgid, and the ventricles 
contained a little bloody serum. The lungs were very vascular, 
and the heart flaccid. The stomach contained about four ounces 
of ingesta, in which were found eighty-nine entire seeds of 
stramonium, together with many fragments. The mucous mem- 
brane of the stomach throughout was slightly congested, and 
presented two patches of extravasation, the one being in the 
greater curvature of the organ, and the other near the pyloric 
orifice. Many of the poisonous seeds, as well as fragments, 
were also found throughout the entire length of the small 
intestines. The liver, spleen, pancreas, bladder, and kidneys 
were normal. 
Chemical Properties 
Daturine is not only identical with atropine in regard to its 
elementary composition, but is also possessed, as first announced CHEMICAL PROPERTIES. 
641 
by Planta (See Chem. Gaz., 1850, p. 350), of the same physical 
and chemical properties. The chemical reactions of atropine 
and the methods of separating it from organic mixtures, as 
already described, are, therefore, equally applicable for the 
detection of daturine. 
On comparing the various reactions of two samples of datu- 
rine—one prepared by Merck, and the other from a fluid ex- 
tract of stramonium—with those of different samples of atropine, 
we in no instance discovered any difference whatever. Thus, 
solutions of daturine yielded with bromine, carbazotic acid, 
chloride of gold, and with potash, precipitates, which assumed 
the same crystalline, forms as those obtained from solutions of 
atropine ; and the limits of the reactions, as also of the other 
reagents for atropine heretofore described, were precisely the 
same for both alkaloids. Moreover, the two bases appeared to 
have the same degree of solubility in water, as also in chloro- 
form, and in ether. 
Taking these facts in connection with the similarity of the 
physiological effects of atropine and daturine, there seems to be 
no longer any doubt whatever of the entire identity of these 
alkaloidsj or, in other words, that belladonna and stramonium 
owe their activity to the presence of the same alkaloidal prin- 
ciple. It is therefore obvious, that—unless some compound is 
discovered to exist in the one that is not present in the other— 
there can be no chemical means of distinguishing between pois- 
oning by these plants; and that this can only be done when 
portions of the plant are found and identified by their physical 
and botanical characters, or by a knowledge of the attending 
circumstances. 
When one grain of daturine was dissolved, by the aid of a 
gentle heat, in four hundred grains of pure water, and the solu- 
tion agitated with four volumes of chloroform, this liquid left 
upon spontaneous evaporation 088 of a grain of the pure alka- 
loid. When a similar aqueous solution was agitated with four 
volumes of absolute ether, this fluid extracted o*Bo of a grain 
°f the alkaloid. On extracting alkaline complex organic mix- 
tures containing small quantities of a fluid extract of stramo- 
nium, by chloroform, we obtained about the same results as 
41 642 
DATURINE. 
already described from similar mixtures containing the extract 
of belladonna. 
One ounce of blood, taken from a cat killed by half an 
ounce of Tilden’s fluid extract of stramonium, when subjected 
to the same treatment as described for the recovery of atropine 
under similar circumstances, and the chloroform residue dis- 
solved in two grains of water, gave, with the bromine test, per- 
fectly unequivocal evidence of the presence of the alkaloid. 643 
VE KATRINE. 
CHAPTER Y. 
VERATRINE, SOLANINE 
Section I.—Veratrine. (White Hellebore.) 
History.—Veratrine is a powerfully poisonous alkaloid, found 
in Veratrum album, or White hellebore, Veratrum viride, or 
American hellebore, Veratrum sabadilla, and in Sabadilla, the 
seeds and fruit of Asagrcea officinalis. It was obtained from 
sabadilla by Meissner, of Germany, in 1819, and about the 
same time, from the same source, by Pelletier and Caventou, of 
France; in 1820, the latter chemists obtained it from the rhi- 
zoma of white hellebore, and in 1838, Mr. Worthington, of 
Philadelphia, announced its existence in the root of Veratrum 
viride. The identity of the alkaloidal principle of the latter 
plant with that of white hellebore, has been doubted; but the 
recent investigations of Mr. J. G. Richardson, and of Prof. S. 
Ik Percy, as well as of Mr. G. J. Scattergood, seem to leave no 
doubt of the identity of these principles. The composition of 
veratrine, in its pure crystalline state, according to G. Merck, 
is C 64016. 
Preparation.—For commercial purposes, veratrine is usually 
obtained from the seeds of sabadilla, or cevadilla, as it is fre- 
quently called. The bruised seeds, deprived of their capsules, 
are exhausted by repeated portions of hot alcohol, the mixed 
alcoholic solutions concentrated to a small volume, then treated 
Wlth slight excess of ammonia, and the impure precipitated 
alkaloid washed with cold water ;it is then boiled for some little 
time with water acidulated with hydrochloric acid and contain- 
lng animal charcoal, the cooled solution filtered, the concen- 
trated filtrate rendered slightly alkaline by ammonia, the pre- 
cipitate thus produced washed with water, and then dried on a 644 
VERATRINE. 
water-bath. The product thus obtained may be further purified 
by dissolving it in water acidulated with hydrochloric acid, and 
extracting the foreign organic matter by ether 5 after decanting 
this liquid, the aqueous solution is treated with slight excess of 
ammonia, and the liberated alkaloid extracted by fresh ether, 
which is allowed to evaporate spontaneously, when the veratrine 
will be left in its very nearly pure, but amorphous or, at most, 
granular state. 
Instead of the use of alcohol for the extraction of the alka- 
loid from the bruised seeds, Dr. Thomson, of Edinburgh, has 
proposed to treat them with boiling water acidulated with hydro- 
chloric acid, and allow the whole to stand twenty-four hours. 
The liquid is then expressed, filtered, concentrated to a small 
volume, and treated with slight excess of ammonia. The pre- 
cipitate thus produced is collected on a filter, washed, and dried, 
then pulverised and extracted with hot alcohol. The alcoholic 
solution is distilled, until the spirit is entirely expelled, the res- 
idue heated with acidulated water and animal charcoal, and the 
filtered solution rendered slightly alkaline by ammonia, when 
the veratrine will be precipitated in the form of a nearly pure- 
white powder. (Chemical News, June 1, 1861, p. 334.) By 
this method, Dr, Thomson obtained at the rate of twenty grains 
of the alkaloid from one avoirdupois pound of the seeds. From 
one pound, avoirdupois, of the dried root of Yeratrum viride, 
Mr. Gr. J. Scattergood, of Philadelphia, states that he obtained 
about thirty grains of the nearly pure alkaloid. 
Gi. Merck obtained veratrine in the crystalline state by mak- 
ing a dilute solution of the commercial alkaloid in alcohol con- 
taining as much water as possible, without precipitating the 
alkaloid, and evaporating the solution on a water-bath at a 
gentle heat, during which a portion of the veratrine separated 
in the form of a white crystalline powder mixed with brown 
resinous matter. The latter was separated by washing the mix- 
ture with cold alcohol. On dissolving the crystalline residue in 
highly-rectified alcohol, and allowing the liquid to evaporate 
spontaneously, the alkaloid was left in the form of rhombic 
prisms, of about half an inch in length. (Chemical Gazette, 
1855, p. 426.) PHYSIOLOGICAL EFFECTS. 
645 
Poisoning by veratrine, in its pure state, has been of ex- 
tremely rare occurrence, and as yet in no instance, so far as 
we know, has it been taken in fatal quantity by the human 
subject. But poisoning by portions of some of the different 
plants which owe their activity to the presence of this alkaloid, 
has not unfrequently happened, as the result of accident. There 
seems to be no instance on record of criminal poisoning by this 
substance. The ordinary medicinal dose of the commercial 
alkaloid is about one-tenth of a grain. 
Symptoms.— White hellebore root has long been known as a 
poison. When taken in poisonous quantity, the more usual 
effects are, a sense of burning heat in the stomach, with a feel- 
ing of constriction and heat in the mouth and throat, great 
anxiety, nausea, violent vomiting, purging, tenesmus, pain in 
the bowels, trembling of the limbs, great prostration, cold sweats, 
small and feeble pulse, vertigo, dilated pupils, loss of sight, im- 
paired speech, coldness of the extremities, convulsions, and 
insensibility. These symptoms are never, perhaps, all present 
in the same case. Thus instances are recorded in which purg- 
ing was absent, and others in which there was no vomiting. 
This substance has not unfrequently occasioned death. In 
non-fatal cases, the symptoms are sometimes very slow in dis- 
appearing. 
In an instance cited by Dr. Christison, in which three per- 
sons had taken a quantity of the root, and finally recovered, 
the following were observed. In the course of an 
hour all the patients experienced a sense of burning in the 
throat, gullet, and stomach, followed by nausea, dysuria, and 
vomiting; weakness and stiffness of the limbs; giddiness, blind- 
ness, and dilated pupil; great faintness, convulsive breathing, 
nnd small pulse. One of them, an elderly woman, who had 
taken the largest quantity, had an imperceptible pulse, stertor- 
ous breathing, and total insensibility; on the following day, an 
eruption appeared over the body. (On Poisons, p. 673.) Two 
children, aged three and a half and one and a half years 
respectively, drank of a decoction of white hellebore. The 
principal symptoms were violent vomiting, insensibility, a pale 
aud sunken countenance, small sharp pulse, heat of head and 646 
VERATRINE. 
coolness elsewhere, slight spasmodic movements of the face and 
limbs, neck somewhat swollen, deglutition impossible, pupils di- 
lated, and the eyes staring. Both children recovered. (StilD’s 
Mat. Med., vol. ii, p. 314.) 
In a fatal case, in which a man had taken only a small 
quantity of the powdered root, the patient was soon seized with 
violent and incessant vomiting, and died within twelve hours. 
In an instance quoted by Dr. Taylor (On Poisons, p. 575), 
twenty grains of the powder caused convulsions, and death in 
three hours. The external application of hellebore to the epi- 
gastrium has caused violent vomiting. So, also, its employment 
in the form of enema, has given rise to violent symptoms. 
American hellebore, familiarly known as Indian poke, has 
not unfrequently produced alarming, and even, at least in one 
instance, fatal results. All parts of the plant have a nauseous, 
bitter taste, followed by a persistent acrid sensation in the mouth 
and throat. The symptoms occasioned by an overdose of this 
substance are very similar to those produced by white hellebore. 
In a case reported by Dr. J. C. Harris, of West Cambridge, 
a feeble child one and a half years old, was ignorantly given 
four drops of the tincture of veratrum viride mixed with water, 
every half hour, until four or five doses had been taken, when 
by mistake a dose containing about sixteen drops was adminis- 
tered. Repeated efforts to vomit ensued after the administration 
of the second dose, but without success, except once, when a 
small quantity of matter was ejected from the mouth. Seven 
hours after taking the first dose, the child was apparently un- 
conscious, very pale, and breathing stertorously j the pulse was 
very slow, the extremities cold, and a profuse perspiration cov- 
ered the whole body. Treatment was now resorted to, but 
without any attempt to remove the contents of the stomach. 
The symptoms increased in violence, and death ensued in about 
thirteen hours after the first dose had been given. (Amer. 
Jour. Med. Sci., July, 1865, p. 284.) 
Dr. T. M. Johnson, of Buffalo, has very recently related an 
instance in which he made a post-mortem examination of the 
body of a woman whose death was claimed to have been pro- 
duced by two doses of Tilden’s fluid extract of veratrum viride. 647 
PHYSIOLOGICAL EFFECTS. 
It seems that the woman, who was fifty years old and quite 
infirm, had taken at first a dose of about thirty drops of the 
extract, and in about two hours was seized with considerable 
pain in the stomach, nausea, and vomiting. From four to six 
hours after taking the first dose she took another, and larger 
one, probably about forty-five drops. This was followed within 
two hours by severe pain in the epigastrium, retching, vomit- 
ing, weak and rapid pulse, and marked prostration; and within 
twelve hours, she had two or three bloody stools with consider- 
able tenesmus. Diarrhoea continued a few hours after the sub- 
sidence of the dysenteric discharges; but the retching and 
vomiting continued at intervals for about four weeks, when she 
died. No abnormal appearance was detected in the body, ex- 
cepting that the stomach was much less in size than usual. 
(Buffalo Med. and Surg. Jour., Nov., 1866, p. 183.) 
In an instance related by Dr. J. B. Buckingham, two gen- 
tlemen, through mistake, swallowed each about a teaspoonful of 
a fluid extract of the American hellebore. In about half an 
hour one of the patients was found almost speechless, retching 
and vomiting incessantly, bathed in profuse cold perspiration, 
and with a scarcely perceptible pulse. On the administration 
of a teaspoonful of laudanum, the vomiting ceased, and the 
patient rapidly recovered. In the other case, in which the 
laudanum was not administered, the vomiting continued for 
some hours, with total loss of speech and of locomotion for 
some time. (Amer. Jour. Med. Sci., Oct., 1865, p. 563.) A 
case is reported in which an ointment of veratrum viride applied 
to an ulcer on the leg, produced vomiting. 
Veratrine, as found in the shops, is subject to great variation 
in strength. In a case communicated to Dr. Taylor, one six- 
teenth of a grain of the alkaloid nearly proved fatal to a lady. 
Hot long after the dose had been taken, the patient was found 
insensible, the surface cold, the pulse failing, and there was 
every symptom of approaching dissolution. (On Poisons, p. 
took, by mistake, thirty grains of the crude alkaloid prepared 
from veratrum viride. It caused copious vomiting, followed by 
prostration and loss of pulse at the wrist; but under the free 648 
YE KATRINE. 
use of stimulating remedies, the patient entirely recovered on 
the third day. (Prize Essay, 1864, p. 76.) 
Two grains of nearly colorless commercial veratrine being 
administered in solution to a healthy cat, the animal was imme- 
diately rendered prostrate, frothed at the mouth, and died in 
less than one minute after taking the dose. A similar quantity 
given to a second cat, produced similar symptoms, and death 
in one minute and three-quarters. Three grains of the same 
preparation given to a young dog, caused immediate vomiting, 
which was frequently repeated, with purging, involuntary urina- 
tion, and great prostration, followed by death in two hours after 
the administration of the dose. Of another sample of the com- 
mercial alkaloid, two grains each were given to two small dogs, 
without producing any appreciable symptom other than slight 
prostration, from which the animals soon recovered. 
Treatment.—This consists in the speedy removal of the 
poison from the stomach, and the subsequent exhibition of 
stimulants. Opium has in several instances been found highly 
beneficial. No chemical antidote is as yet known. Vegetable 
infusions containing tannic acid have been strongly advised. 
Although this vegetable acid forms with veratrine a compound 
that is only very sparingly soluble in water, yet it is very 
readily soluble in the presence of a free acid. In some instances 
purgatives may be found highly useful. 
Post-mortem Appearances.—ln the few cases that have 
been examined, in death from this substance, the alimentary 
canal was more or less inflamed; but nothing has been observed 
characteristic of the action of the poison. In animals killed by 
commercial veratrine, Esche found the throat and (esophagus 
pale; the stomach and bowels more or less contracted, and the 
latter somewhat reddened; and the lungs, liver, and heart gorged 
with blood. The brain presented nothing abnormal. (Stifle’s 
Mat. Med., vol. ii, p. 312.) 
Chemical Properties, 
In the Solid State.—Veratrine, when perfectly pure, is a 
colorless, odorless solid, which may be obtained, not however CHEMICAL PROPERTIES. 
649 
Avithout considerable difficulty, in the form of transparent crys- 
talline prisms. It has an exceedingly acrid, but not bitter 
taste, followed by a persistent sense of dryness and acridity 
in the fauces. When snuffed into the nostrils, even in only 
very minute quantity, it occasions most violent and prolonged 
sneezing. As found in the shops, veratrine is usually in the 
form of a dull-white or yellowish-white amorphous powder, 
having an intensely acrid, with a more or less bitter taste. 
The impure alkaloid is much more apt, on handling, to become 
diffused in the air and excite sneezing than the pure base. 
When applied, in the form of an alcoholic solution, to the 
sound skin, veratrine .occasions a sense of heat, redness, and 
pricking in the part. Heated on porcelain or in a glass tube, 
the pure alkaloid fuses to a brownish transparent liquid, swells 
up, and is slowly dissipated, under decomposition, without any 
residue; heated in a direct flame, it takes fire and burns with 
dense smoke. Its fusing point, according to Couerbe, is 239° F. 
If a small quantity of pure veratrine be touched with a 
drop or two of cold concentrated sulphuric acid, it assumes a 
yellow color, then a reddish tint, and slowly dissolves to a 
pinkish solution, which after several minutes acquires a deep 
crimson-red color. These changes are brought about almost 
immediately by the application of heat. This is one of the 
most characteristic reactions of veratrine yet known (see post). 
Concentrated hydrochloric acid dissolves the pure alkaloid 
without change of color; but if the solution be heated to the 
boiling temperature, as first observed by Merck and recently 
more minutely by Trapp of St. Petersburg, it quickly acquires 
a red color, which ultimately becomes very intense and resem- 
bles that of a solution of permanganate of potash. Under this 
reaction, if only a drop of the acid be employed, almost the 
least visible quantity of the alkaloid will manifest itself. With 
minute quantities, the coloration is best observed by performing 
the experiment in a white porcelain dish. 
The pure alkaloid is also soluble without change of color in 
concentrated nitric acid. But, under the action of this acid, 
the alkaloid as found in the shops, usually acquires a yelloAv or 
reddish color and dissolves to a more or less yellowish solution. 650 
VE KATRINE. 
Yeratrine has strong basic properties completely neutralising 
even the most powerful acids to form salts, but few of which 
have as yet been obtained in the crystalline state. The sul- 
phate, chloride, tartrate, and oxalate are said to have been 
thus obtained. Merck, however, failed to obtain the sulphate 
and chloride in the crystalline form; but he obtained the crys- 
tallised double salts of the alkaloid and perchloride of mercury, 
and of terchloride of gold. We, also, have obtained these 
double salts, as well as the simple bromide, in this state. The 
uncrystallisable salts form colorless gum-like masses. All the 
salts of veratrine have the intensely acrid taste of the pure 
alkaloid. 
Solubility.—When large excess of pure veratrine was di- 
gested for several hours, with frequent agitation, in pure water 
at the ordinary temperature, one part of the alkaloid dissolved 
in about 7,860 parts of the liquid. Absolute ether, under the 
foregoing conditions, dissolved the pure alkaloid in the propor- 
tion of one part in 108 parts of the fluid. It is very freely 
soluble in chloroform, and also in alcohol. The solubility of 
commercial veratrine in these different liquids, is subject to 
great variation. The alkaloid is readily soluble in water con- 
taining a free acid; but it is only very sparingly soluble in the 
caustic alkalies. 
One grain of pure veratrine was dissolved by the aid of 
just sufficient hydrochloric acid, in one hundred grains of water, 
the solution rendered slightly alkaline by potash, and the gelat- 
inous mixture violently agitated with an equal volume of pure 
ether; this liquid was then separated and allowed to evaporate 
spontaneously, when it left a transparent vitreous residue of 
089 of a grain of the pure alkaloid. Chloroform, under sim- 
ilar conditions extracted 098 of a grain of the alkaloid, which 
it left on spontaneous evaporation, in the form of a transparent 
glacial mass, easily pulverisable to a highly electrical powder. 
The salts of veratrine are, for the most part, freely soluble 
in water, but insoluble, or very nearly so, in ether; they are 
somewhat soluble in chloroform. When one grain of the alka- 
loid in the form of chloride, is dissolved in one hundred grains 
of water, and the solution agitated with an equal volume of 651 
POTASH AND AMMONIA TESTS. 
pure ether, this fluid extracts 0-03 of a grain of the salt. 
Under similar conditions, chloroform extracts o‘3l of a grain of 
the salt, which it leaves, on spontaneous evaporation, in the 
form of a colorless, vitreous mass. 
Op Solutions of Ye ratline.—In the following examina- 
tion of the behavior of solutions of veratrine, as well as in the 
preceding investigations, a perfectly colorless and partly crys- 
talline sample of the alkaloid was employed. It was obtained 
by dissolving colorless amorphous veratrine in water by the aid 
of hydrochloric acid, treating the solution with slight excess 
of caustic potash, extracting the precipitated alkaloid with chlo- 
roform, allowing this. liquid to evaporate spontaneously, dis- 
solving the residue in alcohol, and exposing the solution to slow 
evaporation. The solutions, employed in the following experi- 
ments, were prepared by dissolving the purified alkaloid in pure 
water, by the aid of the least possible quantity of hydrochloric 
acid. The fractions employed, indicate the fractional part of a 
grain of the anhydrous alkaloid present in one grain of the 
liquid; the results, unless otherwise indicated, refer to the 
behavior of one grain of the solution. 
1. Potash and Ammonia. 
The caustic alkalies, as well as their protocarbonates, throw 
down from solutions of salts of veratrine, when not too dilute, 
a white amorphous precipitate of the free alkaloid, which is 
only sparingly soluble in excess of the precipitant, but readily 
soluble in diluted acetic acid. After a time, especially if the 
mixture be stirred, the precipitate becomes more or less granular. 
1. uro grain of veratrine, in one grain of water, yields a very 
copious precipitate, which, after a little time, becomes 
converted into small granules. 
2. ytoVo grain, yields a very good precipitate, which is readily 
soluble, to a clear solution, in excess of the precipitant. 
3- 570V0 grain: if only a mere trace of the reagent be added, 
the mixture becomes distinctly turbid; if a larger quan- 
tity of the precipitant be employed, the alkaloidal solution 
remains clear. 652 
VE KATRINE. 
The true nature of the precipitate produced by these re- 
agents may be established by the following test. 
2. Sulphuric Acid. 
The colorless salts of veratrine, as well as the free alkaloid, 
when treated in the dry state with concentrated sulphuric acid, 
slowly dissolve to a reddish-yellow or pinkish solution, which 
after some minutes acquires a deep crimson-red color. If the 
mixture be gently heated, this color manifests itself within a 
few moments, and remains unchanged for some hours. The 
color is slowly destroyed by the prolonged action of heat, and, 
also, by stirring in the mixture a small crystal of bichromate 
of potash. 
The following quantities of the alkaloid were obtained by 
evaporating one grain of a corresponding solution of the chloride 
to dryness on a water-bath. 
1. y-gro grain of veratrine, when gently warmed with a drop of the 
acid, quickly dissolves to a magnificent crimson solution. 
2. r.TTo-0 grain, yields much the same results as 1. 
3. roXiTo grain : if the veratrine deposit be first gently warmed, 
and then a small drop of the acid be allowed to flow over 
it, the heat being continued, it almost immediately assumes 
a deep red color, and quickly dissolves to a solution hav- 
I- VotWo grain: when treated as under 3, the deposit assumes 
ing a quite distinct red hue. 
a faint reddish tint, and dissolves to a colorless solution. 
Even a much less quantity of the alkaloid than the last- 
mentioned, if collected at one point and touched with a minute 
drop of the warmed acid, will yield a very distinct coloration. 
Fallacies.—lt has been objected to this test, that several 
other organic substances also strike a red color with sulphuric 
acid. But, unless the mixture be heated immediately after the 
application of the acid, these objections have no force, since all 
these substances, unlike veratrine, are immediately colored by 
the cold acid. Moreover, the colors thus produced differ in tint 
from that occasioned, even after some minutes, by veratrine. 
And, furthermore, under the continued action of the acid and 653 
CHLORIDE OF GOLD TEST. 
heat, they differ greatly from the alkaloid under consideration. 
The exact behavior of the more prominent of these fallacious 
substances may be briefly mentioned. 
Narceine, when touched with the cold acid, immediately as- 
sumes a brown color, which quickly changes to brownish-yellow, 
then slowly to greenish-yellow; if the mixture be gently heated, 
the narceine quickly dissolves to a bright, brownish-red solution, 
which, upon continuation of the heat, darkens in color and finally 
becomes dark purple red. Solanine, under the action of the 
cold acid, immediately assumes an orange-brown color, and very 
slowly dissolves to an orange solution, which, after some hours, 
acquires a purplish-brown color and yields a brownish precipi- 
tate ; if the orange colored solution be heated, it soon darkens, 
becoming almost black. Piperine acquires with the acid an 
immediate orange-red color, which soon becomes brown; if the 
mixture be heated, it immediately assumes a very dark brown 
color. Salacine imparts to the acid an immediate crimson-pink 
hue, which, on the application of a gentle heat, is increased 
in intensity, then darkens, and finally becomes almost black. 
Papaverine dissolves in the acid to an immediate purple solu- 
tion, the color of which soon fades; on heating the mixture, 
the color is quickly discharged. 
It must be remembered that the intensity of the color pro- 
duced by veratrine and sulphuric acid, may be more or less 
modified by the presence of foreign matter; and that this is, 
perhaps, never wholly absent when the alkaloid is extracted in 
the ordinary manner from complex organic mixtures. 
3. Chloride of Gold. 
Terchloride of gold produces in solutions of salts of veratrine 
a canary-yellow amorphous precipitate, which is very sparingly 
soluble, without darkening, in caustic potash; it is also only 
sparingly soluble in acetic and hydrochloric acids. Upon 
boiling the mixture containing the precipitate, the latter dis- 
solves, but is redeposited unchanged, as the liquid cools. The 
precipitate is readily soluble in alcohol, from which on slow 
evaporation, it separates in the form of beautiful groups of 654 
VERATRINE. 
yellow, silky crystals, having, according to Gr. Merck, the for- 
mula C 64 HCI, AuC13. 
1. ytto grain of veratrine, in one grain of water, yields a very 
copious precipitate. If the precipitate from a few grains 
of the alkaloidal solution be dissolved in a few drops of 
alcohol, and the alcoholic solution be allowed to slowly 
evaporate, it soon deposits very delicate crystalline tufts, 
and granules, Plate XIII, fig. 3. The formation of these 
crystals, however, is readily prevented by the presence of 
foreign matter. 
2. r:wo grain, yields a quite good deposit, which is readily solu- 
ble, to a colorless solution, in a few drops of caustic potash, 
but only slowly soluble in large excess of hydrochloric acid. 
3. yo.'o'oo grain, yields a very distinct precipitate, which is 
readily soluble by heat, but reproduced as the mixture 
cools. 
4. yotWo grain: the mixture becomes distinctly turbid 
4. Bromine in Bromohydric Acid. 
An aqueous solution of bromohydric acid saturated with 
bromine, occasions in solutions of salts of veratrine, and aqueous 
solutions of the free alkaloid, even when highly diluted, a per- 
manent, yellow, amorphous precipitate, which is only sparingly 
soluble in diluted acetic and hydrochloric acids. The precip- 
itate is readily decomposed by caustic potash. Alcohol dissolves 
it readily, and on spontaneous evaporation leaves it in the form 
of groups of bold prismatic crystals. 
1. grain of veratrine, in one grain of water, yields a very 
copious, bright-yellow precipitate, the color of which, on 
the addition of potash, becomes white. The precipitate, 
when dissolved in alcohol and the liquid allowed to evap- 
orate spontaneously, yields a very good crystalline deposit, 
Plate XIII, fig. 4. 
2. yttol) grain, yields a dirty-yellow precipitate, which is readily 
soluble, to a clear solution, in potash. If the precipitate 
be dissolved in alcohol and the liquid evaporated sponta- 
neously, the deposit is left in the crystalline form. lODINE IN lODIDE OF POTASSIUM TEST. 
655 
3. rovWo grain, yields a greenish-yellow precipitate. 
4. :r075W0 grain: a quite distinct deposit. 
5. yooVo-o grain, yields a very perceptible turbidity. 
5. lodine in lodide of Potassium. 
An aqueous solution of iodide of potassium containing free 
iodine, throws down from solutions of veratrine, and of its salts, 
a permanent, amorphous precipitate, which is soluble in alcohol, 
but only sparingly soluble in acetic and hydrochloric acids. 
The exact color of the precipitate is determined by the quan- 
tity of the alkaloid present. 
1. yiEo grain of veratrine, yields a very copious, reddish-brown 
precipitate, which, upon the addition of potash, assumes a 
white color. 
2. iToVo grain: a copious deposit, which is readily soluble, to a 
clear solution, in caustic potash. 
ro,ooo grain, yields a good, reddish-yellow precipitate. 
4. VFiVoo grain: a distinct, greenish-yellow deposit. 
5. ro'oVo‘o grain, yields a quite perceptible cloudiness. 
6. Carbazotic Acid. 
An alcoholic solution of carbazotic acid produces in solutions 
of salts of veratrine, when not too dilute, a yellow amorphous 
precipitate, which is soluble in alcohol and in free acids, even 
acetic acid. 
1. Tihr grain of veratrine, in one grain of water, yields a very 
copious deposit. 
2- r,iroi) grain: a quite good, greenish-yellow precipitate 
3. sTcToij grain, yields a quite distinct turbidity. 
7. Bichromate of Potash. 
This reagent throws down from concentrated solutions of salts 
of veratrine a yellow amorphous precipitate, which is insoluble 
in excess of the precipitant, and only sparingly soluble in di- 
luted acids. The precipitate is readily soluble in strong alcohol. 656 
VERATRINE. 
1. yg-o grain of veratrine, yields a quite good precipitate, which 
after a time becomes more or less granular. 
2. iio grain, yields a very distinct reaction. 
6* rroVo grain: no indication. 
Chromate of potash produces a precipitate similar to that 
occasioned by the bichromate, but the reaction is somewhat less 
delicate. 
Other Reagents.—Sulphocyanide of potassium, and iodide of 
potassium throw down from concentrate solutions of salts of the 
alkaloid white amorphous precipitates, which are readily soluble 
in acetic acid. Bichloride of platinum, and ferricyanide of po- 
tassium occasion in similar solutions, dirty-yellow precipitates. 
Ferrocyanide of potassium fails to produce a precipitate. Cor- 
rosive sublimate throws down from very concentrated solutions, 
a white amorphous deposit, which is readily soluble in water, 
and left, on slow evaporation of the liquid, in the crystalline 
state. Tannic acid occasions a white flocculent precipitate, even 
in highly diluted solutions of the alkaloid. 
Separation from Organic Mixtures. 
Veratrine may be separated from complex organic mixtures, 
as the contents of the stomach, and from the blood, in pre- 
cisely the same manner as already pointed out for the recovery 
of atropine from similar mixtures (see ante, p. 634). A portion 
of the residue thus obtained from the chloroform extract, is 
examined by the sulphuric acid test, in the manner already 
indicated. Another portion may be heated with concentrated 
hydrochloric acid. Any remaining portion may then be dis- 
solved in a small quantity of water, containing a trace of acetic 
acid, and the solution, after filtration if necessary, examined by 
some of the liquid tests. Should the chloroform residue contain 
much foreign matter, it may be purified by dissolving it in acid- 
ulated water, rendering the filtered solution alkaline with potash, 
and again extracting the liberated alkaloid by chloroform. 
On examining, after the method just recommended, the 
contents of the stomach of the first cat, heretofore mentioned, SOLANINE. 
657 
which had been killed in less than one minute by two grains 
of veratrine, and, also, of the young dog, killed in two hours 
by three grains of the alkaloid, we, in both instances, recovered 
very notable quantities of the poison. 
One fluid ounce of hlood, taken from the cat just alluded to, 
gave, when the chloroform residue was treated with sulphuric 
acid, very satisfactory evidence of the presence of the alkaloid. 
This case shows the great rapidity with which the poison may 
enter the circulation. No part of the second cat, before re- 
ferred to, was chemically examined. The residue from six fluid 
drachms of blood from the young dog, when examined by sul- 
phuric acid, gave perfectly unequivocal evidence of the presence 
of the poison, the coloration being about as well-marked as 
from any quantity of the pure alkaloid. 
Section ll.—Solanine. (Nightshade.) 
History.—Solanine, or solania, is the name given to a poi- 
sonous alkaloid found in Solanum dulcamara, or Woody-night- 
shade, Solatium nigrum, or Garden-nightshade, and in several 
other species of the solanum genus of plants. It was first 
discovered, in 1821, by M. Desfosses, in the solanum nigrum. 
Blanchet assigned to it the formula CB4H68N02S; but according 
to the more recent analysis of M. Moitessier, it consists of 
C 42 Still more recently, Otto Gmelin has stated that 
the alkaloid is destitute of nitrogen, its composition being, 
perhaps, CBBH720;j0. (Chemical Gazette, vol. xvii, p. 385.) 
Preparation.—Solanine is most readily obtained, according 
to M. Wackenroder, from the apples of the common potato, 
Solunum tuberosum. The slightly crushed apples are covered 
in a suitable vessel for about fifteen hours with water containing 
sufficient sulphuric acid to give the mixture a strongly acid 
reaction. They are then expressed and removed, and the 
turbid acid liquid, with fresh portions of sulphuric acid, added 
to two successive quantities of fresh apples, and these macerated 
and removed as before. The liquid is now allowed to stand 
some days, then strained through linen, and treated with slight 
42 ' 658 
SOLANINE. 
excess of powdered hydrate of lime. After about twenty-four 
hours, the lime precipitate, containing the solanine, is collected 
on a linen strainer, dried in warm air, and boiled several times 
with successive portions of strong alcohol, which will extract 
the alkaloid. The united alcoholic extracts are then heated 
and, while hot, filtered; on cooling, the liquid will deposit most 
of the alkaloid, partly in the form of crystalline laminae and 
scales. (Ibid., vol. i, p. 325.) 
By dissolving ordinary solanine in water by the aid of 
hydrochloric acid, precipitating by ammonia, and frequent re- 
crystallisation from nearly absolute alcohol, Otto Gmelin ob- 
tained the alkaloid in the form of beautiful, colorless, silky 
needles of considerable length. 
Some of the plants which owe their activity, principally, if 
not entirely, to the presence of this alkaloid, have in several 
instances occasioned death; but we are not aware of any 
instance of poisoning, in the human subject, by the prepared 
alkaloid. 
Symptoms.—Solatium dulcamara, or Bittersweet, when taken 
in an overdose, may give rise to dryness of the mouth and 
throat, thirst, nausea, headache, vertigo, vomiting, purging, and 
convulsions, followed in some instances by death. A little boy, 
aged four years, who had eaten at least two of the berries of 
this plant, was seized about fifteen hours afterwards, with purg- 
ing and vomiting, and subsequently with convulsions, which 
continued during the day, leaving the child comatose and insen- 
sible during the intervals. Vomiting of bilious matters, having 
a dark-greenish color, continued, and during the evening the 
convulsions became permanent, and death ensued in about thirty- 
two hours after the poison had been taken. A sister of the 
deceased, aged six years, who had eaten only a single berry, 
was seized with sickness and purging, from which, however, 
she recovered without more serious effects. Another sister, 
still two years older, who had eaten two of the berries, escaped 
without any marked symptom. (Lancet, London, June 28, 
1856, p. 715.) In two other cases, an unknown number of the 
berries proved fatal to two children. In an instance cited by 
Dr. Beck (Med. Jur., vol. ii, p. 825), several children who had 659 
PHYSIOLOGICAL EFFECTS. 
eaten some of the berries, were seized with violent pain in the 
intestines, vomiting and purging, and in one instance, a profuse 
secretion of saliva. Under active treatment they all recovered. 
So, also, the Solatium nigrum has in several instances de- 
stroyed life. Two little girls, between three and four years of 
age, ate a quantity of the leaves of this plant. Between two 
and three hours afterwards they were both seized with pain in 
the bowels, vomiting, great uneasiness, picking at the bed- 
clothes, and delirium. On the succeeding day, one of the chil- 
dren, which had suffered for several days from relaxed bowels, 
presented the following symptoms: the abdomen was much 
swollen, the pulse very frequent and scarcely perceptible; the 
respiration was quiet, the face pale, the pupils strongly dilated, 
and there was great uneasiness of the body, picking at the 
bedclothes, and entire loss of consciousness. Notwithstanding 
active treatment, the child died, under extreme exhaustion, 
during the evening of the same day. The other child entirely 
recovered on the second day. (Med.-Chir. Rev., Am. ed., Oct., 
1860, p. 380.) 
In an instance quoted by Orfila (Toxicologie, 1852, i, 313), 
three children who had eaten the berries of the Garden-night- 
shade, were seized with severe headache, nausea, vertigo, colic, 
tenesmus, and copious vomiting. In one of the children, these 
symptoms were succeeded by extreme dilatation of the pupils, 
impaired vision, flushed face, profuse sweating, intense thirst, 
loss of voice, stertorous breathing, and tetanic convulsions, 
followed by death in about twelve hours after the berries had 
been eaten. The two other children, after suffering much the 
same symptoms, almost entirely recovered; but they had a 
relapse, under which they finally sunk. 
Mr. Morris, of Merford, has related an instance in which a 
young lady, aged fourteen years, died from the effects of eating 
the berries of the Solanum tuberosum, or common potato plant. 
The symptoms described were, great jactitation, lividity of the 
skin, cold and clammy perspiration, hurried respiration, and 
exceedingly quick and feeble pulse; the teeth for the most part 
were closed, and the patient was constantly spitting through 
the closed teeth a viscid frothy phlegm. There was also loss 660 
SOLANINE. 
of speech; the tongue was covered with a dark brown moist 
fur; the expression was anxious, and the patient was extremely 
restless. Death took place on the second day. (Med.-Chir. 
Rev., Oct., 1859, p. 389.) Dr. Christison quotes an instance 
in which four persons were seized with vomiting, insensibility 
and convulsions after eating potatoes which had begun to germ- 
inate and shrivel. 
Solanine, in its pure state, seems to be much less potent in 
its effects than most of the alkaloids heretofore considered. In 
a series of experiments instituted by M. Schroff, and cited by 
Dr. Stille (Mat. Med., i, 763), with this substance, administered 
to healthy individuals in doses varying from one-thirtieth of 
a grain to three grains, he observed increased cutaneous sensi- 
bility, itching of the skin, gaping, general numbness, sleepiness, 
slight tonic cramps in the legs, and increased frequency of the 
pulse, which at the same time grew feeble and thready; there 
was also some dyspnoea and oppression in breathing, with nausea 
and unsuccessful efforts to vomit; the head was hot, heavy, and 
dizzy, with drowsiness, yet with inability to sleep; the extrem- 
ities were cold, the skin dry and itching, and there was marked 
general debility: the pupil remained unchanged. 
Treatment.—The treatment in poisoning by solanine or any 
of the plants that owe their activity to its presence, would con- 
sist in the speedy removal of the poison from the stomach by 
an emetic or the use of the stomach-pump. Vegetable infusions 
containing tannic acid, and stimulants, might be found useful. 
Post-mortem Appearances. —ln regard to the morbid 
changes produced by this substance, we are not acquainted 
with any instance in which they have been observed, in the 
human subject. 
Chemical Properties. 
In the Solid State.—Solanine, when perfectly pure, may 
be obtained in the form of beautiful tufts of colorless, delicate, 
crystalline needles. As usually met with in the shops, it has 
a more or less yellow color, and is either in the form of an 
amorphous powder or as crystalline scales and granules. The 
pure alkaloid is destitute of odor, and has a bitter taste, followed 661 
CHEMICAL PROPERTIES. 
by an acrid sensation in the throat. When gradually heated 
on porcelain, it fuses, then turns black, gives off dense white 
fumes, and leaves a solid carbonaceous residue; when heated in 
a direct flame, it readily takes fire, and is quickly consumed. 
Although having only a feeble alkaline reaction, solanine 
readily combines with acids forming salts, several of which have 
been obtained in the crystalline state. The uncrystallisable 
salts usually appear in the form of transparent, colorless, gum- 
like masses. The salts of solanine are odorless, and have the 
bitter, acrid taste of the pure alkaloid. 
Cold concentrated sulphuric acid, when brought in contact 
with pure solanine, immediately causes it to assume an orange- 
brown color, and slowly dissolves it to an orange-yellow solution; 
if the solution be heated, its color is quickly changed to deep 
dark-brown. Concentrated nitric acid readily dissolves the alka- 
loid to a colorless solution, which after a time acquires a rose-red 
tint. This color is developed in considerable intensity, if only a 
drop of the acid be employed, from the 100 th part of a grain of 
the alkaloid; but with the 500 th of a grain, the color is only just 
perceptible. If the nitric acid solution be heated, it acquires a 
faint yellow color. So, also, hydrochloric acid dissolves it with- 
out change of color; under the action of heat, the solution 
throws down a white flocculent precipitate. 
If solanine be heated for some time with diluted sulphuric 
or hydrochloric acid, as first observed by MM. Zwenger and 
Kind, it is resolved into grape-sugar and a new, strongly basic 
alkaloid, which these observers named solanidine, and which, 
especially as the mixture cools, is deposited in combination with 
the acid employed, in the crystalline form. (Chem. Gazette, 
1859, p. 308.) According to O. Gmelin, this decomposition 
takes place with diluted sulphuric acid at a temperature of 
122° F. He assigned to solanidine the formula C 52 
Solubility.—When excess of finely-powdered solanine is di- 
gested in pure water, at the ordinary temperature, with frequent 
agitation, for several hours, one part dissolves in 1,750 parts of 
the menstruum. The alkaloid is freely soluble in alcohol, which 
on slow evaporation leaves it principally in the form of delicate, 
silky, crystalline needles, Plate XIII, fig. 5. It is only very 662 
SOLANINE. 
sparingly soluble in absolute ether, and almost wholly insoluble 
in chloroform, requiring about 9,000 parts of the former, and 
not less than 50,000 parts of the latter liquid for solution. 
Amylic-alcohol, when frequently agitated with excess of the 
powdered alkaloid, for several hours, dissolves one part in 1,060 
parts of the liquid. 
From the facts just stated, it is obvious that solanine can 
not be extracted in very notable quantity from aqueous mix- 
tures, either by ether or chloroform. From mixtures of this 
kind, however, the alkaloid may be separated by hot amylic- 
alcohol, or, better still, by a mixture of ether and alcohol, in 
which mixture it is rather freely soluble. Thus, when ten- 
hundredths of a grain of the alkaloid, in the form of sulphate, 
was dissolved in thirty grains of water, and the solution, after 
the addition of slight excess of caustic potash, agitated with 
five volumes of a mixture of two parts of absolute ether and 
one part of pure alcohol, this mixture extracted nine-hundredths 
of a grain of the pure alkaloid, which on spontaneous evapora- 
tion it left in the crystalline form. 
The salts of solanine are, for the most part, readily soluble 
in water; but they are insoluble in chloroform and in ether. 
Either of the latter liquids, therefore, may be employed to sep- 
arate foreign organic matter from aqueous solutions of salts of 
the alkaloid. 
Of solutions of Solanine.—In the following investigations, 
in regard to the behavior of solutions of solanine, a sample of 
colorless crystallised solanine prepared by E. Merck of Darm- 
stadt, and a purified specimen of the commercial alkaloid were 
employed, the former being dissolved in the form of sulphate, 
and the latter as chloride. Merck’s preparation was in the 
form of delicate crystalline needles and thin transparent laminae. 
The fractions employed indicate the fractional part of a grain 
of the anhydrous alkaloid present in one grain of water; and 
the results, unless otherwise indicated, refer to the behavior of 
one grain of the solution. One grain of a 100 th aqueous solu- 
tion of solanine in the form of sulphate, when allowed to evap- 
orate spontaneously, deposits the alkaloidal salt chiefly in the 
form of groups of delicate acicular crystals, Plate XIII, fig. 6. 663 
SULPHURIC ACID TEST. 
1. The Alkalies and Alkaline Carbonates. 
The caustic alkalies and their protocarbonates throw down 
from concentrated solutions of salts of solanine a colorless, trans- 
parent, gelatinous precipitate of the free alkaloid, which is read- 
ily soluble in excess of the fixed caustic alkalies, but only 
sparingly soluble in ammonia, and nearly wholly insoluble in 
the alkaline carbonates. The precipitate is readily soluble in 
free diluted acids. 
1. yiro grain of solanine, in one grain of water, when treated 
with a small quantity of either of the above reagents, the 
mixture becomes converted into a nearly solid gelatinous 
mass. 
2. -ygy- grain, when treated with a small quantity of ammonia, 
yields a very good flocculent precipitate. On account of 
the ready solubility of solanine in caustic potash and soda, 
it is difficult to obtain a precipitate by either of these 
reagents from a single drop of a 500 th solution of the 
alkaloid. 
3* ttoVo grain, under the action of a trace of ammonia, the 
mixture becomes very distinctly turbid, and after a time 
yields a distinct precipitate. 
The true nature of the precipitate produced by either of 
these reagents, may be established by the following reaction. 
2. Sulphuric Acid. 
If a small quantity of solanine or of any of its colorless salts, 
in the dry state, be treated with a few drops of cold concen- 
trated sulphuric acid, the deposit immediately assumes an orange- 
brown color, and slowly dissolves to a yellow or orange-yellow 
solution, which after about an hour acquires a purplish-brown 
color and throws down a brownish precipitate; after several 
hours, the solution becomes colorless and the precipitate assumes 
a yellowish or dirty-white color. The intensity of the colors 
thus produced and the time of their development, depend some- 
what upon the quantity of the alkaloid present. Results similar 664 
SOLANINE. 
to those just stated, are obtained when a drop of a somewhat 
concentrated solution of a salt of the alkaloid is treated with 
several drops of the acid. 
These results are principally due, according to Zwenger and 
Kind, to the solanidine produced from the solanine by the action 
of the acid. On treating different samples of solanine with 
concentrated sulphuric acid, we have frequently observed the 
peculiar nauseous odor, first noticed by Wackenroder. When 
a solution of the sulphate of solanine is evaporated to dry- 
ness on a water-bath, the salt is left in the form of a hard, 
transparent, vitreous mass, destitute of any distinct crystalline 
structure. 
1. grain of solanine, in the form of a salt, in the dry state, 
when treated with a few drops of the concentrated acid, 
soon dissolves, with an orange color, to a yellow solution, 
from which a precipitate soon begins to separate; this 
increases in quantity, and after a time the liquid acquires 
a deep-orange, then a bright-red, and finally a violet-pink 
color, which slowly fades and after about ten hours en- 
tirely disappears. 
When one drop of a solution containing the 100 th part 
of a grain of the alkaloid is treated with several drops of 
the acid, the mixture immediately assumes a yellow color, 
and then passes through the changes just described. 
2. Yrro'o grain, both in the solid state and when in solution, 
yields much the same results as the preceding quantity of 
the alkaloid, only that the colors are less intense and per- 
sistent. 
3. roTOiTo grain: when the dry deposit is touched with a small 
drop of the acid, it assumes a brownish color and dissolves 
to a solution having a decided yellow tint, which after a 
time changes to a very faint reddish hue. 
4. ytmmTo grain, under the conditions just stated, dissolves with 
a just perceptible brownish tint, to a colorless solution. 
The production of this series of colors, in connection with 
the formation of the precipitate, is quite characteristic of sola- 
nine. Even the I,oooth part of a grain of the alkaloid, as just 
pointed out, will yield very satisfactory results. CHROMATE OF POTASH TEST. 
665 
3. lodine in lodide of Potassium. 
I 
An aqueous solution of free iodine in iodide of potassium 
causes somewhat concentrated solutions of salts of solanine to 
assume a deep orange-red color, and throws down an orange- 
brown precipitate, which is unaffected by diluted acids. 
1. yo"o grain of solanine, in solution in one grain of wrater, 
yields the results just stated. The precipitate is readily 
soluble in caustic potash to a colorless solution, from which, 
2. ytoVo grain: an orange-brown solution, and a slight precipitate. 
3. iToVo grain: the mixture assumes a yellowish-brown color, 
after a time, a dirty-white precipitate separates. 
The reactions of the first-two mentioned solutions are pecul- 
iar to solanine; but with more dilute solutions the results are 
uncertain, since the reagent itself imparts a more or less yel- 
lowish-brown color, even to pure water. It must also be borne 
in mind that the reagent produces reddish-brown precipitates 
with most of the other alkaloids and with certain other organic 
substances. 
but fails to yield a precipitate. 
4. Chromate of Potash. 
Protochromate of potash produces in solutions of salts of 
solanine, when not too dilute, a yellow amorphous precipitate, 
which is insoluble in excess of the precipitant, but readily solu- 
ble in acetic acid. If the mixture, containing the deposit, be 
treated with several drops of concentrated sulphuric acid, the 
precipitate quickly dissolves, and the solution slowly acquires a 
bluish or bluish-green color, which remains unchanged for sev- 
eral hours. The production of this color is peculiar to the pre- 
cipitate produced from solutions of solanine. 
1 • xwo grain of solanine, in one grain of water, yields a very 
copious precipitate, which, when treated with sulphuric 
acid, undergoes the changes just described. 
2. xtfo'o grain: the mixture immediately becomes turbid, and 
after a little time yields a quite fair, yellow, flocculent 
precipitate. If the precipitate be dissolved in a few drops 
43 666 
SOLANINE. 
of sulphuric acid, the solution soon acquires a quite dis- 
tinct bluish-green color. 
3. 57ct00 grain: after a time, a slight deposit of yellowish flakes. 
Bichromate of potash produces much the same reactions as 
the protochromate, but the precipitate does not appear in quite 
as dilute solutions, since it is somewhat soluble in the chromic 
acid eliminated by the reaction, when this reagent is employed. 
5. Bromine in Bromohydric Acid. 
An aqueous solution of bromohydric acid saturated with free 
bromine throws down from solutions of salts of the alkaloid an 
orange-yellow or yellow amorphous precipitate, which is spar- 
ingly soluble in diluted acetic acid. After a time, the precip- 
itate acquires a dirty-white color, and slowly disappears. 
1. YoW grain of solanine, in one grain of water, yields a very 
copious orange-yellow precipitate. 
4. rroVo grain: a quite good, yellow deposit. 
3- y,wo grain, yields only a just perceptible turbidity. 
The reaction of this reagent is common to solutions of vari- 
ous other organic substances, besides solanine. 
Other Reagents.—Carbasotie acid produces in concentrated 
solutions of salts of solanine, a copious, yellow, gelatinous pre- 
cipitate, which is readily soluble in excess of the precipitant. 
Tannic acid occasions a white, flocculent precipitate. Oxalate 
of ammonia, and phosphate of soda produce, in similar solutions, 
white, gelatinous precipitates. 
Neither of the following reagents produce a precipitate, even 
in concentrated solutions of salts of the alkaloid: sulphocyanide 
of potassium, ferro- nor ferri-cyanide of potassium, the chlorides 
of gold, platinum, and palladium, iodide of potassium, sesqui- 
chloride of iron, nor free chromic acid. 
Separation from Organic Mixtures. 
Although there is no difficulty in identifying even a minute 
trace of solanine when in its pure state, yet when present only 667 
SEPARATION FROM ORGANIC MIXTURES. 
in minute quantity in complex organic mixtures, its separation 
in a state sufficiently pure for testing is attended with consid- 
erable difficulty, and is sometimes impossible, at least by any 
method with which we are acquainted. As the alkaloid is nearly 
wholly insoluble both in ether and chloroform, it is obvious, as 
heretofore stated, that neither of these liquids will serve to sep- 
arate it from organic mixtures. 
The suspected mixture, as the contents of the stomach, 
after being carefully examined for the presence of any solid 
portions of the poisonous plant, is very slightly acidulated with 
a drop or two of sulphuric acid, and gently heated with half 
its volume of alcohol, for about half an hour. The mass is 
then allowed to cool, transferred to a linen strainer, and the 
strained liquid concentrated on a water-bath to a small volume, 
after which it is filtered. The filtrate is evaporated, at a tem- 
perature not exceeding 120° F., to almost dryness, the residue 
well stirred with a small quantity of pure water, and the solu- 
tion filtered. Any solanine present will now exist in the filtrate 
in the form of sulphate, and may, if not in too minute quantity, 
be separated by either of the following methods, the first of 
which is based upon the principles first applied by Wackenroder 
for the preparation of the alkaloid, and the second upon those 
first announced by Uslar and Erdmann. 
According to the first of these methods, the clear filtrate is 
treated with slight excess of powdered hydrate of lime, and 
the mixture allowed to repose in a cool place for from twelve 
to twenty-four hours, in order that the eliminated solanine may 
completely subside. The precipitate is then collected on a 
filter, and allowed to drain, then washed with a small quantity 
of cold water containing a trace of carbonate of ammonia, and, 
while still moist, gently warmed with about half an ounce of 
strong alcohol, which will dissolve the alkaloid, whilst the sul- 
phate of lime and any excess of caustic lime employed will 
remain, being insoluble in this liquid. The alcoholic solution, 
after filtration, is gently evaporated to dryness, the residue 
treated with a small quantity of water very slightly acidulated 
with acetic acid, and the solution filtered. A drop of the filtrate 
may now be treated with several drops of cold concentrated 668 
SOLANINE. 
sulphuric acid, and if, after a time, it yields satisfactory evi- 
dence of the presence of solanine, other portions of the solution 
may be examined by some of the other tests for the alkaloid. 
Should, however, the sulphuric acid test fail, the filtrate is 
concentrated and another drop examined in the same manner, 
before applying any of the other tests. 
Or, secondly, the filtrate, supposed to contain the sulphate 
of solanine, may he agitated with an equal volume of warm 
amylic-alcohol, which, after the liquids have completely sepa- 
rated, is decanted, and the operation repeated with a fresh 
portion of the alcohol. By this treatment, much of the coloring 
matter will be removed, while the alkaloidal salt will remain in 
the aqueous solution. This solution is then treated with slight 
excess of carbonate of ammonia, and agitated with hot amylic- 
alcohol, which will now dissolve the liberated alkaloid. The 
alcoholic solution is decanted, the aqueous liquid washed with a 
fresh portion of the hot alcohol, and the mixed alcohols evap- 
orated to dryness on a water-bath. The residue is stirred with 
strong, ordinary alcohol, the solution filtered and evaporated to 
dryness. The residue thus obtained is treated with a small 
quantity of water containing a trace of acetic acid, and the 
filtered solution examined in the manner described in the pre- 
ceding paragraph. 
On following the methods now considered, for the examina- 
tion of complex organic mixtures containing two drachms of 
Thayer’s Fluid extract of Dulcamara—the medicinal dose of 
which is from half a drachm to one drachm—we recovered by 
each a very notable quantity of solanine, in its very nearly 
pure state, especially when precipitated from the final aqueous 
solution by an alkali. The first-mentioned method furnished 
somewhat the best results,; however, the quantity of the alka- 
loid recovered by either process was several times more than 
sufficient to fully establish the presence of the poison. PLATE I Fig. 1. 
grain Potash, in the form of nitrate or chloride, + Bichloride of 
Platinum, X 225 diameters. 
“ 2. xio grain Potash, as nitrate, + Tartaric Acid, X 100 diameters. 
“ 3. six grain Potash, as chloride, + Tartrate of Soda, X 80 diameters 
l< 4. 'grain Potash, as nitrate, + Carbazotic Acid, X4O diameters. 
“ 5. grain Ammonia, as chloride, + Carbazotic Acid, X 40 diameters. 
“ 6. grain Soda, + Carbazotic Acid, X 40 diameters. Plate! 
Mrs. T.G.Wormipy. ad net. dei.el s<nup. PLATE 11. Fig. 1. —xiu grain Soda, + Antimoniate of Potash, X 100 diameters. 
“ 2. grain Soda, + Tartaric Acid, X4O diameters. 
“ 3. xrhro grain Soda, as chloride, + Bichloride of Platinum, X4O diameters. 
“ 4. grain Sulphuric Acid, + Chloride of Barium, X 100 diameters. 
“ 5. Hydrofluosilicic Acid, + Chloride of Barium, X 100 diameters. 
“ 6. y-J-y grain Sulphuric Acid, + Nitrate of Strontia, X 75 diameters. Plate' If 
Mrs. T.G.Wonnley. ad na±. del.et sculp. PLATE 111. Fig. 1. grain Hydrochloric Acid, + Acetate of Leaf X 40 diameters. 
“ 2. grain Oxalic Acid, on spontaneous evaporation, XBO diameters. 
“ 3. xxVo grain Oxalic Acid, + Chloride of Calcium, X 225 diameters. 
“ 4. xxr'o grain Oxalic Acid, + Chloride of Barium, XBO diameters. 
“ 5. xxo grain Oxalic Acid, + Nitrate of Strontia, X 125 diameters. 
“ 6. xxx grain Oxalic Acid, + Acetate of Lead, XBO diameters. Plate 111 
Mra.T.Ur.Wormley. ad net.del.et sculp. PLATE IT. Fig. 1. grain Hydrocyanic Acid vapor, + Nitrate of Silver, X 225 
diameters. 
“ 2. xoTOo'o grain Hydrocyanic Acid vapor, + Nitrate of Silver, X 125 
diameters. 
“ 3- xoVo grain Phosphoric Acid, -f- Ammonia-Sulphate of Magnesia, 
X 80 diameters. 
“ 4. Tartar Emetic, from hot supersaturated solution, X4O diameters. 
“ 5. Arsenious Acid, sublimed, X 125 diameters. 
“ xAo grain Arsenious Acid, + Ammonia-Nitrate of Silver, X 15 di- 
ameters. Plate I\ 
Mrs. T.G.Wormley ad unt. del.et. acvulj' ■ PLATE Y. Fio. I. xJo grain Arsenic Acid, + Ammonio-Sulphate of Magnesia, X 75 
diameters. 
“ 2. Corrosive Sublimate, sublimed, X4O diameters. 
“ 3- j-g-Q grain Lead, -j- diluted Sulphuric Acid, XBO diameters. 
“ 4. xihr grain Lead, -f diluted Hydrochloric Acid, XBO diameters. 
“ 5. xaoo grain Lead, + lodide of Potassium, XBO diameters. 
“ tijVo grain Zinc, + Oxalic Acid, X 80 diameters. Plate V. 
Mrs.T.G.'Wbrmlcy. ad nat.del.et sculp. PLATE YL Fig. 1. Xxny grain Nicotine, + Bichloride of Platinum, X4O diameters. 
“ 2. Tffo grain Nicotine, + Corrosive Sublimate, X4O diameters. 
“ 3. xoVn grain Nicotine, + Ccurbazotic Acid, X4O diameters. 
“ 4. Conine, pure, + vapor of Hydrochloric Acid, X4O diameters. 
“ 5. x£o grain Conine, + Carbazotic Acid, X4O diameters. 
“ 6. xto grain Morphine, + Potash or Ammonia, X4O diameters. Plate VI 
Mrs. T.G.Wontiley. ad nat. del.et sculp. PLATE YIL Pig. 1. xlq grain Morphine, -f lodide of Potassium, X4O diameters. 
“ 2, grain Morphine, + Chromate of Potash, XBO diameters. 
11 3. grain Morphine, + Bichloride of Platinum, XBO diameters. 
“ 4. grain Meconic Acid, + Chloride of Barium, X 80 diameters. 
“ 5. XXo- grain Meconic Acid, + Hydrochloric Acid, X 75 diameters. 
“ 6. TXo grain Meconic Acid, + Ferricyanide of Potassium, X4O diameters. HaloVll. 
Mrs.T.G.Wbrmley. ad nat. del.el sculp. PLATE VIII. Fig. 1, Tls grain Meconic Acid, + Chloride of Calcium, X 75 diameters. 
“ 2. XqV(T grain Narcotine, -f- Potash or Ammonia, X4O diameters. 
“ 3. tist) grain Narcotine, + Acetate of Potash, XBO diameters. 
“ 4. T|-6- grain Codeine, + lodine in lodide of Potassium, X4O diameters. 
“ 5. xihi grain lodide of Codeine, from alcoholic solution, X 75 diameters. 
“ 6- Hjh grain Codeine, + Sulphocyanide of Potassium, X4O diameters. ] lateVm 
Mrs. T.G.Worjnley. ad nat. del.et sculp. PLATE IX. Fig. 1. grain Codeine, + Bichromate of Potash, X 40 diameters. 
“ 2. grain Codeine, -)- lodide of Potassium, X4O diameters. 
“ 3. xfjVo grain Narceine, + lodine in lodide of Potassium, X4O diameters 
“ 4. grain Narceine, + Bichromate of Potash, X 40 diameters. 
“ 5. grain Opianyl, + lodine in lodide of Potassium, X4O diameters. 
“ 6. grain Opianyl, + Bromine in Bromohydric Acid, X 40 diameters. Plate IX 
Mes. T.G.Wovmley. Ed mt. del.et 3>:ulp. PLATE X. Fig. 1. T-£-(T grain Strychnine, + Potash or Ammonia, X4O diameters. 
“ 2. X 5-- grain Strychnine, + Sulphocyanide of Potassium, X4O diameters. 
“ 3. xiu grain Strychnine, + Bichromate of Potash, X4O diameters. 
“ 4. -j-Vg- grain Strychnine, + Bichromate of Potash, XBO diameters. 
“ 5. x-gVir grain Strychnine, -f- Chloride of Gold, X4O diameters. 
14 6. Xg(7(T grain Strychnine, + Bichloride of Platinum, X4O diameters. I late X 
Mrs.T.G.Wormley. a«l nat.del.et sculp PLATE XI. Fig. 1. xxrVo’ grain Strychnine, -f- Oarhazotic Acid, X 80 diameters. 
“ 2. grain Strychnine, -j- Corrosive Sublimate, X4O diameters. 
<£ 3. Tjjo grain Strychnine, + Ferricyanide of Potassium, X4O diameters. 
“ 4. xoVo grain Strychnine, -f- lodine in lodide of Potassium, X 80 di- 
ameters. 
“ 5. xio grain Brucine, + Potash or Ammonia, X4O diameters. 
“ 6- rao grain Brucine, -f- Sulphocyanide of Potassium, X4O diameters. PlateXl 
Mrs. T.G-.Wormley. ad nat. del.et sculp. PLATE XII. Fig. 1. xxu grain Brucine, -f- Bichromate of Potash, XBO diameters. 
“ 2. xoVo grain Brucine, + Bichloride of Platinum, X4O diameters. 
“ 3. xwo grain Brucine, + Ferricyanide of Potassium, X4O diameters. 
“ 4. xtio grain Atropine, -f- Potash or Ammonia, X 75 diameters. 
“ 5. xu(i grain Atropine, + Bromine in Bromohydric Acid, X 75 di- 
ameters. 
“ 6. xuihro grain Atropine, + Bromine in Bromohydric Acid, X 125 di- 
ameters. Plate XII 
Mrs. T.G.Wormley. ad nat.del.el sculp. PLATE XIII. Fig. 1. xji grain Atropine, -f- Carhazotic Acid, X 80 diameters. 
“ 2. jlq grain Atropine, + Chloride of Gold, X 80 diameters. 
11 3. xtro grain Yeratrine, + Chloride of Gold, X 40 diameters. 
“ 4. xno grain Yeratrine, + Bromine in Bromohydric Acid, XBO diameters. 
“ 5. Solanine, from alcoholic solution, X 80 diameters. 
“ 6. Tio grain Solanine, as sulphate, on spontaneous evaporation, X 80 
diameters. Plate XIII. 
Mrs.T.G.Wormley. ad nat.del.et sculp. TABULAR;VIEW OF THE BEHAVIOR OF ALKALOIDS WITH REAGENTS 
- - 
IN THE SOLID STATE. 
IN THE STATE OF AQUEOUS SOLUTION.* 
I 
A LKA L OIDS. 
1. Sulphuric Acid. 
2. Nitric Acid. 
3. Sulphuric Acid 
AND 
Bichromate of Potash. 
4. Sulphuric Acid 
AND 
Nitrate of Potash. 
5. Nitric Acid 
AND 
Chloride of Tin. 
1. Potash 
AND 
Ammonia. 
2. Iodide of Potassium. 
3. Sulphocyaiiide of 
Potassium. 
4. Chromate of Potash. 
5. Bichromate of Potash, 
(>. Carba/otic Acid. 
7. Chloride of Gold. 
8. Bichloride of 
Platinum. 
9. Corrosive Sublimate. 
10. Ferrocyanide of 
Potassium. 
11. Pcrricyauide of 
Potassium. 
12. Iodine 
IN 
Iodide of Potassium. 
13, Bromine 
IN 
Bromohydrie Acid. 
14. Acetate of Lead. 
15. ftesquichlorlde of 
iron. 
13. Chloride of Barium. 
SOLUBILITY. 
1. NICOTINE, 
02oH14N2. 
(See page 423.) 
No change of color. 
Reddish mixture. 
Slowly, green oxide 
of chromium. 
N 0 ppt. 
No ppt. 
No ppt. 
No ppt. 
Yellow cryst. ppt. 
Limit yyl-yy g^m. 
Plate vi, fig. 3. 
Yellow amorp. ppt. 
Limit yyUj-y grain. 
Yellow cryst. ppt. 
Limit yyy grain. 
Plate vi,- fig. 1. 
White cryst. ppt. 
Limit yyyy grain. 
Plate vi, fig. 2. 
No ppt. 
No ppt. 
Reddish-hrown 
amorp. ppt. 
Limit yyyVo 0 grain. 
Yellow amorp. ppt. 
Limit yyAyy gT^Tl. 
White amorp. ppt. 
Limit yyy grain. 
Water, in all proportions. 
Ether, freely soluble. 
Chloroform, freely soluble. 
2, CONINE, 
c16h15n. 
(See page 443.) 
Pale reddish solution. 
Little or no immedi- 
ate change. 
Slowly, green oxide 
of chromium. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
Yellow cryst. ppt. 
Limit yyEy grain. 
Plate vi, fig. 5. 
Yellow amorp. ppt. 
Limit yyiyy grain. 
No ppt. 
White amorp. ppt. 
Limit yyyy grain. 
. 
No ppt. 
No ppt. 
Reddish-hrown 
amorp. ppt. 
Limit yyjyyy grain. 
Yellow amorp. ppt. 
Limit yyfyy grain. 
White amorp. ppt. 
Limit rJ-y grain. 
Water, in 100 parts. 
Ether, freely soluble. 
Chloroform, freely soluble. 
8. MORPHINE, 
C34H19N Os, 2 Aq. 
(See page 4B6.) 
Dissolves slowly 
without change of 
color. 
Orange-red solution. 
Limit gr- 
I msol.-^Vogr. 
Green mixture. 
Dingy-brown mix- 
ture. 
Much as by nitric 
acid alone. 
White cryst. ppt. 
Limit j-Lj grain. 
Plate vi, fig. 6. 
White cryst. ppt. 
Limit two -Tem- 
plate vii, fig. I. 
No ppt. 
Yellow cryst. ppt. 
Limit yAyo grain. 
Plate vii, fig. 2. 
Yellow amorp. ppt. 
Limit grain. 
Yellow amorp. ppt. 
Limit y jy grain. 
Yellow amorp. ppt., 
which immed. 
darkens. 
Limit yylyy grain. 
Yellow granul. ppt. 
Limit Tyy grain. 
Plate vii, fig. 3. 
No ppt. 
No ppt. 
No ppt. 
Reddish-hrown 
amorp. ppt. 
Limit yylyy grain. 
Yellow amorp. ppt. 
Limit yyVy grain. 
No ppt. 
Blue mixture. 
Limit yfy grain. 
No ppt. 
Water, in 4,166 parts. 
Ether, in 7,725 parts. 
Chloroform, in 6,550 parts. 
Amtlic-Alcohol, in 133 parts. 
4. NAKCOTINE, 
C44H23N O14. 
(See page 504.) 
Yellow solution: 
when moderately 
heated, purple. 
Yellow solution. 
Green or blue mix- 
ture. 
Blood-red solution. 
Limit grain. 
As by nitric acid 
alone. 
White cryst. ppt. 
Limit .I;61,li0 grain. 
Plate viii, fig. 2. 
Similar to potash. 
White cryst. ppt. 
Limit ,-jAyo grain. 
Yellow ppt. becomes 
cryst. 
Limit grain. 
Plate viii, fig. 2. 
Yellow granul, ppt. 
Limit grain. 
Yellow amorp. ppt. 
Limit yyAyy grain. 
Yellow amorp. ppt. 
Limit yy jyy grain. 
Yellow amorp. ppt. 
Limit f gVo grain. 
White amorp. ppt. 
Limit yyy grain. 
Dirty-white ppt. 
Limit yy-J-yy grain. 
Yellow amorp. ppt. 
Limit grain. 
Reddish-hrown 
amorp. ppt. 
Limit yyyVtn, grain. 
Yellow amorp. ppt. 
Limit yyyVo-o grain- 
White cryst. ppt. 
Limit Tptnr grain. 
Plate viii, fig. 3. 
No change. 
No ppt. 
Water, in 25,000 parts. 
Ether, in 209 parts. 
Chloroform, in nearly all proportions. 
5. CODEINE, 
C3gH2iN Oe, 2 Aq. 
(See page 513.) 
Dissolves slowly 
without change of 
color. 
Orange-yellow color, 
and dissolves to a 
yellow solution. 
The mixture slowly 
becomes green. 
Greenish, then red- 
dish solution. 
Much as by nitric 
acid alone. 
White amorp. ppt. 
Limit y Ly grain. 
White cryst. ppt. 
Limit too grain. 
Plate ix, fig. 2. 
White cryst. ppt. 
Limit ttW grain. 
Plate viii! fig. 6. 
Yellow cryst. ppt. 
Limit yLg- grain. 
Yellow cryst. ppt. 
Limit yi¥ grain. 
Plate ix, fig. l. 
Yellow amorp. ppt. 
Limit yJyy grain. 
Reddish-yellow 
amorp. ppt. 
Limit yyVtr grain. 
Yellow ppt. 
Limit yAy grain. 
No ppt. 
No ppt. 
No ppt. 
Reddish-brown ppt. 
Limit yyytyyy gf 11)11. 
Plate viii, figs. 4, 5. 
Yellow amorp. ppt. 
Limit yy jyy grain. 
No ppt. 
No change. 
No ppt. 
Water, in 128 parts. 
Ether, in 54-8 parts. 
Chloroform, in 21-5 parts. 
6, NARCEINE, 
c4bh29no18. 
(See page 520.) 
Reddish-hrown, and 
reddish-yellow 
solution. 
Orange-yellow, then 
yellow. 
Dirty-red mixture. 
Reddish-hrown mix- 
ture. 
As by nitric acid 
alone. 
No ppt. 
White cryst. ppt. 
Limit y-Jy grain. 
Yellow cryst. ppt. 
Limit y-ity grain. 
Yellow cryst. ppt. 
Limit y-J-y grain. 
Plate ix, fig. 4. 
Yellow amorp. ppt. 
Limit -grain. 
Yellow amorp. ppt. 
Limit yyjyy grain. 
Yellow ppt. 
Limit yiy grain. 
Reddish-hrown ppt. 
Limit yyVy grain. 
Plate ix, fig. 3. 
Yellow amorp. ppt. 
Limit yyAyy grain. 
No change. 
Water, in 1,660 parts. 
Ether, in 4,066 parts. 
Chloroform, in 7,950 parts. 
7. OPIANTL, 
C2oH1008. 
(See page 524.) 
Colorless solution: 
when heated, deep 
blue or purple 
color. 
Colorless solution. 
Yellowish, and 
slowly, green mix- 
ture. 
Scarlet-orange solu- 
tion. 
Colorless solution. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
N 0 ppt. 
No ppt. 
Dark-brown ppt. 
Limit y-Ayy grain. 
Plate ix, fig. 5. 
Yellow cryst. ppt. 
Limit y-Ayy grain. 
Plate ix, fig. 6. 
No ppt. 
No change. 
No ppt. 
Water, in 515 parts. 
Ether, in 136 parts. 
Chloroform, in nearly all proportions. 
8. MECON1C ACID, 
3 H 0 5 O14H On, 6 Aq. 
(See page 483.) 
Dissolves without 
change of color. 
Dissolves without 
change of color. 
Slowly, green oxide 
of chromium. 
No change of color. 
No change of color. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
Cryst. ppt 
Limit yiy grain. 
Plate vii, fig. 6. 
No ppt. 
No ppt. 
Yellowish-white 
amorp- ppt. 
Limit yjoy-y grain. 
Red Solution. 
Limit gr- 
bn SOI. yylyy “ 
White cryst. ppt. 
Limit Xy!yy grain. 
Plate vii, fig. 4. 
Water, in 125 parts. 
Ether, in 2,200 parts. 
Chloroform, insoluble. 
9. STRYCHNINE, 
C44IM 2e4. 
(See page 534.) 
Dissolves without 
change of color. 
Dissolves without 
change of color. 
Beautiful series of 
colors: blue, violet, 
red. 
Limit xroVfro grain. 
No change of color. 
No change of color. 
White cryst. ppt. 
Limit yyW grain. 
Plate x, fig. 1. 
White cryst. ppt. 
Limit -ygVo grain. 
Plate x, fig. 2. 
White cryst. ppt. 
Limit -joVo grain. 
Plate x, fig. 2. 
Yellow cryst. ppt. 
Limit y-J-y grain. 
Yellow cryst. ppt. 
Limit yyiyy grain. 
Plate x, figs. 3, 4. 
Yellow cryst. ppt. 
Limit- 0 —y'o 0 grain. 
Plate xi, fig. 1. 
Yellow ppt. 
■Limit ooko grain. 
Plate x, fig. 5. 
Yellow cryst. ppt. 
Limit yyiyy grain. 
Plate x, fig. 6. 
White ppt. 
Limit yby grain. 
Plate xi, fig. 2. 
Cryst. ppt. 
Limit yiy grain. 
Yellow cryst. ppt. 
Limit yAy grain. 
Plate xi, fig. 3. 
Reddish-brown ppt. 
Limit yygyo o grain. 
Plate xi, fig. 4. 
Yellow amorp. ppt. 
Limit yyyVoo grain. 
No ppt. 
No change. 
No ppt. 
Water, in 8,333 parts. 
Ether, in 1,400 parts. 
Chloroform, in 8 parts. 
Amylic-Alcohol, in 122 parts. 
10. BRUCINE, 
C46H2gN208| 8 Aq. 
(See page 593.) 
Faint rose tint, and 
solution of same 
hue. 
Deep blood-red, and 
solution of same 
hue. 
Limit grain. 
Orange or brownish- 
orange mixture. 
Orange-red solution. 
Limit 273 ij(5"5 grain. 
The cooled NO5 sol. -f- 
Sn Cl = intense 
purple color. 
Limit Xyiyy grain. 
White cryst. ppt. 
Limit y£y grain. 
Plate xi, fig. 5. 
White cryst- ppt. 
Limit X-Jy grain. 
White cryst. ppt. 
Limit t-L- grain. 
Plate xl fig. 6. 
Yellow cryst. ppt. 
Limit grain. 
Plate xii, fig. 1. 
Yellow cryst. ppt. 
Limit yFJ-yy grain. 
Plate xii, fig. 1. 
Yellow ppt. 
Limit yyiyy grain. 
Yellow amorp. ppt. 
Limit yyiyy g^U. 
Yellow cryst. ppt. 
Limit yyiyy grain. 
Plate xii, fig. 2. 
White granul. ppt. 
Limit yiy grain. 
No ppt. 
Yellow cryst. ppt. 
Limit yiy grain. 
Plate xii, fig. 3. 
Orange-brown 
amorp. ppt. 
Limit yyyVyy grain. 
Brown or yellow 
amorp. ppt. 
Limit yyAyy grain. 
No ppt. 
No change. 
No ppt. 
Water, in 900 parts. 
Ether, in 440 parts. 
Chloroform, very freely soluble. 
11. ACONITINE, 
C60H47N Oi4. 
(See page 000.) 
Dissolves with a 
slightly yellow 
color. 
A faintly yellow col- 
oration. 
The mixture slowly 
becomes green. 
As by sulphuric acid 
alone. 
As by nitric acid 
alone. 
Dirty-white am. ppt. 
Limit yiy grain. 
No ppt- 
Slight turbidity. 
Limit -rJ-0- grain. 
No ppt. 
No ppt. 
Greenish-yellow 
amorp. ppt. 
Limit yyh-y grain. 
Yellow amorp. ppt. 
Limit yyyyy gram. 
No ppt. 
Dirty-white ppt. 
Limit y|y grain. 
No ppt. 
No ppt. 
Reddish-hrown 
amorp. ppt. 
Limit xyJyyy grain. 
Yellow amorp. ppt. 
Limit yy lyy grain. 
No chaige. 
No ppt. 
Water, in 1,783 parts. 
Ether, in 777 parts. 
Chloroform, in nearly all proportions. 
12. ATROPINE and 
DATURINE, 
C34H23IstOg. 
(See pages 021 and 030.) 
Dissolves without 
change of color. 
Dissolves without 
change of color. 
The mixture slowly 
becomes green. 
No change of color. 
No change of color. 
White cryst. ppt. 
Limit jL grain. 
Plate xif, fig. 4. 
No Ppt. 
No ppt. 
No ppt. 
No ppt. 
Yellow cryst. ppt. 
Limit yyVo grain. 
Plate xiii, fig. 1. 
Yellow cryst. ppt. 
■Limit ttVo grain. 
Plate xiii, fig. 2. 
Yellowish amorp. 
ppt. 
Limit T-J-y grain. 
No ppt. 
No ppt. 
No ppt. 
Brownish amorp. 
ppt. 
Limit xisgswh grain. 
Yellow cryst. ppt. 
Limit yy-k<r grain- 
Plate xii, figs. 5, 6. 
No ppt. 
No change. 
No ppt. 
Water, in 414 parts. 
Ether, freely soluble. 
Chloroform, in nearly all proportions. 
13. VERATRINE, 
C64H52N20lf,. 
(Bee page 043.) 
The solution, slowly a 
crimson-red color. 
Limit yyyyy grain. 
Dissolves without 
change of color. 
Much as by sulphuric 
acid alone, but ulti- 
mately, green mix- 
ture. 
White amorp. ppt. 
Limit -jyLy grain. 
White amofp. ppt. 
Limit grain. 
White amorp. ppt. 
Limit toVo grain. 
Yellow amorp. ppt. 
Limit wW grain- 
Yellow amorp. ppt. 
Limit T|y grain. 
Yellow amorp. ppt. 
Limit yy!yy grain. 
Yellow amorp. ppt. 
Limit yyyyy grain. 
Plate xiii, fig. 3. 
Yellowish amorp. 
ppt. 
Limit yyy gram. 
White amorp. ppt. 
Limit yy grain. 
No ppt. 
Yellowish amorp. 
ppt. 
Limit .yiy grain. 
Reddish-hrown 
amorp. ppt. 
Limit X5(JW(J grain. 
Yellow amorp. ppt. 
Limit Ty-Ayyy grain. 
Plate xiii, tig. 4. 
Water, in 7,860? parts. 
Ether, in 108? parts. 
Chloroform, freely soluble. 
14. SOU A NINE, 
O42H35N Gy? 
(See page 657.) 
Orange-brown color- 
ation. 
Limit OTfony grail1- 
Dissolves to a color- 
less solution, be- 
coming faint rose- 
red. 
The mixture slowly 
becomes green. 
Much as by sulphuric 
acid alone. 
No change of color. 
White gelat. ppt. 
Limit for N H„ 
grain. 
No Ppt. 
. 
No ppt. 
Yellow amorp. ppt. 
Limit yyVo grain- 
Much as K O, Cr03. 
Yellow amorp. ppt. 
Limit t<to o' grain- 
No ppt. 
No ppt. 
No ppt. 
No ppt. 
Orange-brown 
amorp. ppt. 
Limit yyVff grain. 
Yellow or orange- 
yellow amorp. ppt. 
Limit yAyy grain. 
No change. 
Water, in 1,750 parts. 
Ether, in 9,000 parts. 
Chloroform, in 50,000 parts. 
A-Mylic-Alcohol, in 1,060 parts. 
— 
— 
— 
* The reactions i 
n all instances, unless otherwise indicated, refer to 
the behavior of a single grain of the solution. The results of the reaction, as expressed, generally 
refer to the behavior of 
somewhat strong solutions of the substance. The limits indicate about the 
least quantity of the substance that will yield a visible reaction. 
... - 
i 11ST D E X 
PAGE. 
Absorption, effects of, 57 
Acetate of lead, fatal quantity, . . 357 
General chemical nature, . . . 858 
Period when fatal, 356 
Poisoning by, 355 
Post-mortem appearances, . . . 357 
Quantitative analysis, .... 372 
Recovery from organic mixtures, 369 
Solubility, 358 
Special chemical properties, 359-369 
Symptoms produced by, . . . 355 
Treatment of poisoning by, . . 357 
Acid, arsenic, 310 
Arsenious, 240 
Comenic, 485 
Hydrochloric, poisoning by, . .138 
Hydrocyanic, poisoning by, . . 167 
Igasuric, 529 
Meconic, 483 
Nitric, poisoning by, 120 
Oxalic, poisoning by, .... 150 
Phosphoric, 206 
Pyromeconic, 485 
Strychnic, 529 
Sulphuric, poisoning by, ... 98 
Acids, mineral, nature and effects of, 97 
Aconite, fatal quantity, . . . .610 
Period when fatal, 610 
Poisoning by, 608 
Post-mortem appearances, . . .613 
Symptoms produced by, ... 608 
Treatment of poisoning by, . . 612 
Aconitine, chemical properties of, . 614 
Fallacies of tests for, . . . .618 
History, 606 
Physiological test for, . . . . 619 
Poisoning by, 612 
Preparation, 606 
PAGE. 
Aconitine, recovery from the blood, 620 
Solubility, 616 
Separation from organic mixtures, 619 
Aconitum napellus, 606 
Alkalies, distinguishing properties, 71 
Fatal quantity, 68 
General chemical nature of, . . 65 
Pathological effects of, . . . . 69 
Period when fatal, 67 
Symptoms produced by, .... 66 
Treatment of poisoning by, . . 69 
Vegetable, 409 
Alkaloids, fixed, general nature of, . 409 
Graham and Hofmann’s method 
for recovering, 419 
Liquid, 409 
Recovery by Dialysis, .... 420 
By method of Stas, . . . .411 
Alkaloids, Rodgers and Girdwood’s 
method, 416 
Uslar and Erdmann’s method, . 417 
Ammonia, carbonate of, .... 67 
Density of solutions of, . ... 88 
Effects of vapor, 67 
General chemical nature, ... 88 
Period when fatal, 68 
Quantitative analysis, .... 96 
Separation from organic mixtures, 95 
Special chemical properties, . 89-95 
Symptoms produced by, ... 66 
Analyses, precautions in regard to, 50 
Analysis, substances requiring, . 49 
Analyst, qualifications requisite, . 60 
Aniline, source of fallacy, .... 560 
Antimonuretted hydrogen, . . .227 
Antimony, history of, 216 
Recovery from the tissues, . . . 236 
Separation from complex mixtures, 233 696 
ANT—BRU 
PAGE. 
Antimony, quantitative analysis, . 237 
Apparatus, chemical, 60 
Appearances, post-mortem, ... 46 
Aqua ammonia, chemical proper- 
ties of, 88 
Poisoning by, 66 
Aqua fortis, 120 
Arsenic acid, general chemical na- 
ture, 310 
Physiological effects of, . . . .311 
Quantitative analysis, .... 317 
Reinsch’s test for, 315 
Special chemical properties, 311-317 
Sulphuretted hydrogen test, . . 312 
Arsenic, compounds of, 240 
Eating of, 36 
Metallic, history, 238 
Physiological effects, .... 239 
Special chemical properties, . 239 
White, 240 
Arsenious acid, 240 
Antidotes for, 246 
Antiseptic properties of, ... 248 
Chromate of potash test, . . . 295 
Danger and Flandin’s method, . 305 
Detection after long periods, . . 308 
Detection in the stomach, . . . 297 
In vomited matters, . . . .297 
Distinguished from arsenic acid, 295 
Duflos and Hirsch’s method, . . 306 
External application of, ... 243 
Failure to detect, 307 
Fallacies of Reinsch’s test, . .273 
Of sulphur test, 267 
Fatal quantity, f. 244 
Fresenius and Babo’s method, . 300 
General chemical nature, . . . 250 
lodide of potassium test, . . . 295 
Lime-water test, 294 
Marsh’s test, 278 
Bloxam’s modification, . . . 292 
Delicacy of, . . . 282, 286, 290 
Fallacies of, . . . 284, 287, 291 
Nitrate of silver test, .... 259 
Of solutions of, 258 
Period when fatal, 244 
Post-mortem appearances, . . . 248 
Quantitative analysis, .... 309 
Recovery from the urine, . . . 307 
PAGE. 
Arsenious acid, reduction test, . . 255 
Reinsch’s test, 269 
Interferences of, 276 
Separation from organic mixtures, 296 
From the tissues, 299 
Solubility in water, 250 
In alcohol, 253 
In chloroform, 253 
Sublimation test for, 254 
Sulphate of copper test, . . .261 
Sulphuretted hydrogen test, . . 263 
Symptoms produced by, . . .241 
Taste of, 241 
Time of symptoms, 242 
Treatment for, v 245 
Vaporisation of, 253 
Varieties of, 241 
Asagrsea officinalis, 643 
Atropa belladonna, 621 
Atropia, 621 
Atropine, chemical properties of, . 628 
External application of, ... 627 
History, 621 
Physiological test, 633 
Poisoning by, 626 
Post-mortem appearances, . . . 628 
Preparation, 622 
Recovery from the blood, . . . 636 
Separation from complex mix- 
tures, 634 
Solubility, 629 
Subcutaneous injection of, . . . 627 
Treatment for poisoning by, . . 628 
Belladonna, poisoning by, . . . 623 
Post-mortem appearances, . . . 628 
Symptoms produced by, .... 623 
Treatment of poisoning by, . . 628 
Binoxalate of potash, poisoning by, 71 
Bittersweet, 658 
Blue vitriol, 374 
Bloxam’s method for detecting ar- 
senic, 292 
Brucia, 593 
Brucine, general chemical nature, . 594 
History, 593 
Nitric acid and tin test, .... 597 
Physiological effects, 594 
Preparation, 594 BRU—DUF 
697 
PAGE. 
Brucine, recovery from the blood, . 605 
From the stomach, 605 
Separation from organic mixtures, 604 
Solubility, 595 
Special chemical properties, . . 595 
Sulphuric acid and nitre test, . 598 
Test for nitric acid, 181 
Burnett’s disinfecting fluid, . . . 394 
CiESIA, 65 
Causes modifying effects of poisons, 85 
Chemical analysis, importance of, . 48 
Failure of, 66 
Decomposition of poisons, ... 58 
Reagents, 59 
Tests, value of, 52 
Chloride of zinc, poisoning by, . . 395 
Classification of poisons, .... 37 
Codeia, 513 
Codeine, general, chemical nature, . 514 
History, 513 
Preparation, 514 
Physiological effects, 514 
Salts of, 616 
Solubility, 515 
Tests for, 516-520 
Comenic acid, 485 
Compound poisoning, 40 
Conia, 443 
Conicine, . . 443 
Conine, distinguished from nicotine, 455 
Fallacies of tests for, .... 454 
General chemical nature, . . . 447 
History, 443 
Physiological effects of, . . . . 445 
Preparation, 444 
Solubility, 448 
Special chemical properties, 448-454 
Recovery from the blood, . . . 456 
Salts of, 450 
Separation from organic mixtures, 455 
Conium maculatum, 443 
Copper, chemical properties of 
salts of, 378 
Combinations, 374 
Fatal quantity, 377 
History and chemical nature, . . 373 
Of solutions of, 379 
Period when fatal, 376 
PAGE. 
Copper, physiological effects, . . . 375 
Post-mortem appearances, . . . 378 
Quantitative analysis, . . . .891 
Recovery from organic mixtures, 388 
From the tissues, 390 
From the urine, 391 
Sulphate, 374 
Special chemical properties, 379-388 
Subacetate, 374 
Symptoms produced by, . . . 375 
Treatment of poisoning by, . . 377 
Corrosive sublimate, chemical prop- 
erties, 328 
Chloride of tin test for, . . 829, 336 
' Chronic poisoning by, .... 322 
Composition, 320 
Copper test for, 337 
External application, .... 323 
Failure to detect, 351 
Fatal quantity, 324 
General chemical nature, . . . 327 
Period when fatal, 323 
Poisoning by, 320 
Post-mortem appearances, . . . 325 
Quantitative analysis, .... 352 
Recovery from organic mixtures, 344 
From the urine, 351 
Reduction test, 330 
Solubility, 327 
Sulphuretted hydrogen test, . . 334 
Symptoms produced by, . . . 320 
Treatment of poisoning by, . . 324 
Curara, properties of, 561 
Curarine, 661 
Danger and Flandin’s method for 
detecting arsenic, 305 
Datura stramonium, 636 
Daturia, 636 
Daturine, chemical properties, . . 640 
History, 636 
Preparation, 637 
Recovery from the blood, . . . 642 
Separation from organic mixtures, 641 
Dialysis, method of application, . 420 
Disease, modifying influence of, . . 87 
Diseases simulating poisoning, . . 43 
Duflos and Hirsch’s method for de- 
tecting arsenic, 806 698 
ELI—MER 
PAGE, 
Elimination of poisons, .... 58 
Evidences of poisoning, .... 39 
Evidence from chemical analysis, . 48 
From post-mortem appearances, . 44 
Failure to detect poison, .... 56 
Fresenius and Babo’s method of 
analysis, 800 
Galvanised iron, poisoning by, . . 396 
Graham and Hofmann’s method for 
recovering strychnine, .... 419 
Habit, modifying influence of, . . 36 
Hellebore, American, poisoning by, 646 
White, poisoning by, 645 
Post-mortem appearances, . . . 648 
Symptoms, 645 
Treatment, 648 
Hemlock, detection in organic mix- 
tures, 455 
Poisoning by, 444 
Post-mortem appearances, . . . 446 
Symptoms produced by, . . . 444 
Treatment of poisoning by, . . 446 
Hydrochloric acid, density of solu- 
tions of, 142 
Fatal quantity, 140 
General chemical nature, . . . 141 
Period when fatal, 139 
Poisoning by, 138 
Post-mortem appearances, . . . 141 
Quantitative analysis, .... 149 
Recovery from organic mixtures, 146 
From organic fabrics, .... 148 
Special chemical properties, 143-146 
Symptoms produced by, . . .139 
Test for meconic acid, .... 490 
Treatment of poisoning by, . . 141 
Hydrocyanic acid, failure to detect, 191 
Fatal quantity, 172 
General chemical nature, . . . 175 
History and composition, . . .167 
Period when fatal, 171 
Poisoning by, 167 
Post-mortem appearances, . . . 174 
Quantitative analysis, .... 192 
Recovery from the blood, . . . 190 
Separation from organic mixtures, 187 
PAGE. 
Hydrocyanic acid, special chemical 
properties, 176-187 
Symptoms produced by, ... 169 
Treatment of poisoning by, . .173 
Hydrofluosilicic acid, as a reagent, 80 
Idiosyncrasy, effects of, .... 35 
Igasuric acid, 529 
Indian poke, 646 
Intestines, perforation of, .... 47 
Irritant poisons, effects of, . . 87, 45 
Irritant poisoning, morbid appear- 
ances in, 45 
Jamestown weed, poisoning by, . 637 
Laudanum, 457 
Lead, acetate, fatal quantity, . . 357 
Acetate, general chemical nature, 358 
Period when fatal, 356 
Post-mortem appearances, . . 357 
Solubility, 358 
Special chemical properties, 359-369 
Symptoms produced by, . . . 355 
Treatment of poisoning by, . . 357 
Detection in the urine, .... 372 
External application of, ... 356 
History and chemical nature, . . 354 
Physiological effects of, . . . . 355 
Quantitative analysis, . . . .372 
Separation from organic mixtures, 369 
From the tissues, 371 
Sulphuretted hydrogen test for, . 861 
Lithia, chemical properties of, . . 65 
Marsh’s test for arsenic, .... 278 
Meconic acid, failure to detect, . . 503 
General chemical nature, . . . 484 
History, 483 
Iron test for, 486 
Physiological effects of, ... . 484 
Preparation, 483 
Recovery from the blood, . . . 500 
From the tissues, 500 
Separation from organic mixtures, 492 
Solubility, 484 
Special chemical properties, 485-492 
Meconine, 524 
Mercury, compounds of, .... 319 MER—OPI 
699 
PAGE. 
Mercury, detection in the urine, . 351 
Metallic, properties of, . . . .319 
Physiological effects, 319 
Protochloride of, 320 
Micro-chemistry of poisons, definition, 33 
Microscope, application of, ... 34 
Mineral acids, nature and effects of, 97 
Monkshood, 606 
Morphia, 466 
Morphine, external application of, 469 
Failure to detect, 503 
Fatal quantity, 468 
General chemical nature, . . . 470 
History and preparation, . . . 466 
Nitric acid test for, 475 
Period when fatal, 468 
Post-mortem appearances, . . . 470 
Quantitative analysis, .... 504 
Recovery from the blood, . . . 500 
From organic mixtures, . . . 499 
From the tissues, 500 
From the urine, 503 
Separation from organic mixtures, 492 
Solubility, 471 
Special chemical properties, 473-483 
Symptoms produced by, . . .467 
Treatment of poisoning by, . .470 
Muriatic acid, 138 
Napellina, 606 
Narceine, chemical tests for, . 522-524 
General chemical nature, . . . 521 
History, 620 
Physiological effects, 521 
Preparation, 520 
Solubility, 522 
Narcotic poisons, symptoms of, . . 38 
Narcotic poisoning, morbid effects of, 45 
Narcotico-irritant poisoning, . . 38, 45 
Narcotine, general chemical nature, 505 
History, 504 
Physiological effects of, . . . . 505 
Preparation, 505 
Solubility, 506 
Special chemical properties, 506-513 
Test for nitric acid, 132 
Nesler’s test for ammonia, .... 92 
Nicotia, 423 
Nicotiana tabacum, 423 
PAGE. 
Nicotine, general chemical nature, . 428 
History, 428 
Period when fatal, 426 
Post-mortem appearances, . . .427 
Preparation, 423 
Recovery from the blood, . . . 440 
From organic mixtures, . . . 437 
From the tissues, 440 
Salts of, 430 
Solubility, 428 
Special chemical properties, 429-437 
Symptoms produced by, . . . 424 
Treatment of poisoning by, . . 427 
Nightshade, deadly, 621 
Garden, symptoms of, .... 659 
AVoody, 657 
Nitrate of potash, poisoning by, . . 70 
Nitric acid, anhydrous, .... 124 
Antidotes for, 122 
Density of solutions of, . . . .125 
Fatal quantity, 122 
Fumes of fatal, 121 
General chemical nature, . . . 124 
Pathological effects, 122 
Period when fatal, 122 
Poisoning by, . 120 
Quantitative analysis, . . . .137 
Recovery from organic mixtures, 134 
From organic fabrics, . . . 137 
Special chemical properties, 125-134 
Symptoms produced by, . . . 120 
Nux vomica, chemical properties, . 533 
Fatal quantity, 532 
History and composition, . . . 529 
Period when fatal, 531 
Physical properties, . . . 529, 533 
Post-mortem appearances, . . . 532 
Symptoms produced by, .... 529 
Treatment of poisoning by, . . 582 
CEsophagus, perforation of, . . . 47 
Oil of vitriol, poisoning by, ... 98 
Opianyl, chemical tests for, . 525-528 
General chemical nature, . . . 625 
History, 524 
Physiological effects of, ... . 525 
Preparation, 524 
Solubility, 525 
Opium, effects of enema of, . . . 460 700 
OPI—SOL 
PAGE. 
Opium, external application, . . . 459 
Failure to detect, 503 
Fatal quantity, 461 
History and chemical nature, . . 457 
Period when fatal, 460 
Physical and chemical properties, 465 
Post-mortem appearances, . . . 465 
Recovery after large doses of, . 462 
From organic mixtures, . . . 492 
Symptoms produced by, . . . 458 
Time of symptoms, 459 
Treatment of poisoning by, . . 463 
Orpiment, 240, 263 
Oxalic acid, fatal quantity, . . . 152 
General chemical nature, . . . 155 
History, 150 
Period when fatal, 152 
Poisoning by, 150 
Post-mortem appearances, . . . 154 
Quantitative analysis, .... 167 
Recovery from organic mixtures, 163 
From the urine, 166 
Solubility, 155 
Special chemical properties, 156-163 
Symptoms produced by, . . . 150 
Treatment of poisoning by, . . 153 
Papayee, somniferum, 457 
Phosphoric acid, general chemical 
nature, 206 
Special chemical properties, 206-210 
Phosphorus, failure to detect, . . 214 
Fatal quantity, 194 
General chemical nature, . . . 197 
History, 192 
Hydrogen test, 203, 213 
Lipowitz test, 205, 212 
Mitscherlich’s test, . . . 200, 211 
Period when fatal, 193 
Poisoning by, 192 
Post-mortem appearances, . . . 196 
Quantitative analysis, .... 214 
Recovery as oxide, 213 
From organic mixtures, . . . 210 
Solubility, 197 
Special chemical properties, 198-206 
Symptoms produced by, . . . 192 
Treatment of poisoning by, . .195 
Varieties of, 198 
PAGE. 
Poison, definition of, 34 
Failure to detect, 49 
Poisons, classification of, .... 37 
Polarised light, test for soda, ... 85 
Porphyroxin, 498 
Post-mortem appearances, as evi- 
dence of poisoning, 44 
Post-mortem examinations, ... 47 
Potash, binoxalate, poisoning by, . 71 
Carbazotic acid test for, ... 79 
Density of solutions of, . . . . 73 
Fatal quantity, 68 
General chemical nature, ... 72 
Nitrate of, 70 
Period when fatal, 67 
Platinum test for, 74 
Post-mortem appearances, ... 69 
Quantitative analysis, .... 82 
Recovery from organic mixtures, 81 
Special chemical properties, . 73-81 
Sulphate, poisoning by, .... 71 
Symptoms produced by, .... 66 
Tartaric acid test for, .... 76 
Tartrate, poisoning by, .... 71 
Treatment of poisoning by, . . 69 
Prussic acid, 167 
Pyromeconic acid, 485 
Rats-bane, 240 
Reagents, chemical, 59 
Realgar, 240 
Reinsch’s test for arsenic, .... 269 
Rodgers and Girdwood’s method for 
recovering alkaloids, 416 
Rubidia, 65 
Sabadilla, 643 
Soda, density of solutions of, . . 83 
General chemical nature, ... 83 
Poisoning by, 66 
Recovery from organic mixtures, 88 
Special chemical properties, . 84-88 
Solania, 657 
Solanine, chemical properties of, . 660 
History, 657 
Preparation, 657 
Post-mortem appearances, . . . 660 
Recovery from organic mixtures, 667 
Solubility, 661 701 
PAGE. 
Solanine, symptoms produced by, . 660 
Treatment of poisoning by, . - 660 
Solanum dulcamara, symptoms of, 658 
Nigrum, syniptoms of, ... • 659 
Tuberosum, poisoning by, . . . 659 
Sonnenschein’s test for ammonia, . 94 
Sources of evidence of poisoning, . 39 
Spectrum analysis, 80 
Spirit of salt, 138 
Stas’ method for recovering alka- 
loids, 411 
Stramonium, external application, 639 
Poisoning by, 637 
Post-mortem appearances, . . . 640 
Symptoms produced by, . . . 637 
Treatment for poisoning by, . . 640 
St. Ignatius’ bean, 534 
Stomach, redness of, 46 
Softening of, 46 
Ulceration and perforation, . . 47 
Strychnia, 534 
Stx-ychnic acid, 629 
Strychnine, accumulative effects of, 540 
Color test for, 553 
Delicacy of, 655 
Fallacies of, 560 
Interferences with, .... 558 
External application of, ... 539 
Failure to detect, 691 
Fatal quantity, 542 
Frog test for, 676 
Galvanic test, 566 
General chemical nature, . . . 548 
History, 534 
Period when fatal, 541 
Physiological test for, .... 576 
Poisoning, diagnosis of, . . . . 540 
Post-mortem appearances, . . . 646 
Preparation, 535 
Quantitative analysis, .... 593 
Recovery from the blood, . . . 587 
From nux vomica, 579 
From organic mixtures, . . . 679 
From the tissues, 586 
From the urine, 690 
- By Dialysis, 582 
Salts of, 550 
Solubility, 549 
Special chemical properties, . . 550 
SOL—TOB 
PAGE. 
Strychnine, symptoms produced by, 536 
Taste of, 551 
Time of symptoms, 537 
Treatment of poisoning by, . . 543 
Strychnos Ignatii, 534 
Sugar of lead, poisoning by, . . . 355 
Sulphate of potash, 71 
Sulphuric acid, density of solutions of, 105 
Fatal quantity, 101 
General chemical nature, . . . 104 
Period when fatal, 99 
Poisoning by, 98 
Post-mortem appearances, . . . 102 
Quantitative analysis, .... 119 
Recovery from organic mixtures, 113 
Separation from organic fabrics, 119 
Special chemical properties, 106-113 
Symptoms produced by, .... 98 
Treatment of poisoning by, . . 101 
Suspected poisoning, 41 
Symptoms, as evidence of poisoning, 39 
Tartar emetic, composition, . . . 216 
Fatal quantity, 219 
General chemical nature, . . . 221 
Period when fatal, 218 
Post-mortem appearances, . . . 220 
Quantitative analysis, . . . .287 
Recovery from organic mixtures, 233 
From the tissues, 236 
Solubility, 221 
Special chemical properties, 222-233 
Symptoms produced by, . . • 216 
Treatment, 220 
Tartrate of potash, poisoning by, . 71 
Tetanus, distinguished from poison- 
ing, 540 
Thornapple, 686 
Tincture of opium, poisoning by, . 458 
Tobacco, chemical properties of, . 428 
Detection in organic mixtures, . 437 
External application of, ... 425 
Fatal quantity, 427 
Period when fatal, 426 
Poisoning by, 423 
Post-mortem appearances, . . . 427 
Smoking of, 425 
Symptoms produced by, . . . 424 
Treatment of poisoning by, . . 427 USL—ZIN 
PAGE. 
Uslar and Erdmann’s method for 
recovering alkaloids, 417 
Valser’s method for the recovery of 
morphine, 498 
Vegetable alkaloids,-. ..... 409 
Poisons, general considerations, 409 
Veratria, 643 
Veratrine, chemical properties, . . 648 
History, 643 
Poisoning by, 645 
Preparation, 643 
Recovery from organic mixtures, 656 
From the blood, 657 
Salts of, 650 
Solubility, 650 
Test for sulphuric acid, . . . .112 
Vcratrum album, 643 
Post-mortem appearances, . . . 646 
Sabadilla, 643 
Treatment, 648 
Viride, poisoning by, .... 646 
PAGE, 
Verdigris, 374 
Vomiting, effects of, 57 
White hellebore, poisoning by, . . 645 
White vitriol, 393 
Wolfsbane, 606 
Woorara, properties of, 561 
Zinc, chloride of, 394 
History and chemical nature, . . 392 
Of solutions of, 398 
Post-mortem appearances, . . . 396 
Properties of salts of, .... 397 
Quantitative analysis, .... 405 
Recovery from organic mixtures, 404 
Salts of, 393 
Special chemical properties, 398-403 
Sulphate of, 393 
Symptoms produced by, . . . 394 
Treatment of poisoning by, . . 396 
Use of for culinary purposes, . 396 
THE END.