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REPORT OF COMMITTEE
Method  of Stating Water-Analyses.
A. C. PEALE, M. D.   1

WM. H. SEAMAN, M. D. }- Committee.

C. H. WHITE, M. D.
[From Bulletin No. 2, Chemical Society of Washington.]
WASHINGTON:

  JAN., 1887.
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REPORT OF  COMMITTEE  ON METHOD OF
         STATING  WATER-ANALYSES.

                 Appointed November 12th, 1885.
 To the President and ^Members of the
                      Chemical Society of Washington :
   Gentlemen :  Chemists are called upon to  make  analyses of
 natural waters,  mainly from three  points of  view,  in  order to
 answer one of three questions, viz :
   1st. Does the water contain any substances that  render it use-
 ful for medicinal purposes?
   id.  Does the water contain anything injurious to health ?
   $d.  Is the water suitable for certain manufacturing purposes or
 technical uses?
   The first question  is asked of mineral waters, the second of po-
 table or drinking waters, and the third of those utilized for economic
 purposes in the industrial arts.
   The universal use of water for drinking would naturally, in the
earlier stages of society, lead men  to distinguish waters simply as
potable or non-potable; but very soon mineral waters would be
separated from the others and divided into classes, according to
their predominant characters, or to those qualities appealing most
strongly to the senses of taste and smell.
   Thus, even in the  time of Aristotle, mineral waters were classi-
fied according to the vapors they contained ; and Pliny, in the first
century, divides them into acidulous, sulphurous, saline, nitrous,
aluminous, and bituminous, very much the same as we do to-day.
  Medicinal, or  mineral waters, having thus been differentiated
long before the dawn of chemical science,  it is not surprising to
find  that the  earliest  water-analyses are of mineral waters, while
potable waters were  neglected until the increasing density of popu-
lation and the necessity of hygienic precaution compelled  attention 
                StdS


36                   Kl'LLETIN  OF THK

to their chemical characters, and, still later, the growth of indus-
trial arts made the chemical examination of certain waters neces-
sary to the successful prosecution of many manufactures.
   Although a comparatively large  number of works on mineral
springs were published during the fifteenth and sixteenth  centu-
ries, none contain any account of accurate chemical examination
of the waters.
   About the latter part of the seventeenth century hosts of authors
all over Europe are found writing enthusiastically of the mineral
waters of their respective countries, and some of them detail  the
early experiments with regard to their analyses.
   These attempts were, of course, extremely crude, and were lim-
ited  mainly to their identification,  as  either acid or alkaline, and
to the determination of such solid substances as iron, sulphur, and
common salt.
   The principal re-agents  in  use during  the early part of  the
eighteenth  century, as stated by Bergmann. were  "' infusion  or
powder of gall,"  ''the juice  of the  flowers of  leffer — iris,"
•'  syrup  of violets,"  " martial  vitriol,"  w' lemon  juice,"  " sal
ammoniac," the '" volatile  hepar sulphur," and  "' vitriolic acid."
   To trace the progressive advances in water-analyses would be to
follow the  steps in  the growth of chemical analyses in general.  A
few general remarks in the  lines of investigation already indicated
will suffice here.
   The first treatise relating to the use and quality of water that
we find printed in America is one with the following title :  The
Curiosities of  Commo>i Water, or the Advantages thereof in
Curing Cholera, Intemperatice, and other JMaladies. by John
Smith, C.  M." was reprinted at Boston, Massachusetts, from the
London edition of  1712, for Joseph Edwards, at the corner shop
on the north side of Town  House, in  1725.  This book  calls es-
pecial attention to the excellency of water as a drink, and enumer-
ates as well its therapeutical attributes.   It cures gout and hypo-
chondriac melancholy ; it benefits gravel and stone in the bladder ;
it makes the child grow strong in the womb, and  increases  the
mother's milk ; it stays hunger ; '• for there was a certain crack-
brained man who, at Leyden, where Dr. Car resided in that Uni-
versity, pretended he could  fast as long as Christ did ; and it was
found that  he held out the time of forty days  without eating any
food, only he drank water and smoked tobacco." 
CHEMICAL SOCIETY.
37
   Water is also of great use to strengthen weak children ; it pre-
 vents swelling from bruises, sickness of the stomach, shortness of
 breath, and vomiting ; it cures fluxes, consumptions, flushes, colic,
 small-pox, &c, &c.
   We are instructed in this quaint volume '• How to distinguish
 water:"  "■ The way to do this is by the  taste and  scent; for if it
 have no taste nor smell, being purely fresh,  not salt, nor sweetish,
 nor ill-scented, it is good, provided it be pure and clear, of which
 kind is the common water used in London, when well settled or
 in fair weather.
   "As for those who are curious and will be at the charge, they may
 procure the best water for drink by distillation, either in an alem-
 bic or in a cold still used in drawing any  cold water from herbs ;
 for no earthy nor metallic  substance, nor any kind  of salt, will
 rise in  distillation ;  so that  the  water so distilled will be pure and
 admirable to drink when cold,  and will keep as long from  stink-
 ing as any of the  cold distilled water in the apothecaries' shops,
 according to what Dr. Quincy hath affirmed about it  in  his Dis-
 pensatory.
   '" Those who have not the convenience of distillation may boil it
 a little  as they do  for tea ; for then, when kept awhile after it  is
 cold, it will become more fine, by suffering any mixture contained
 in it to settle to the bottom  of the vessel wherein  it is contained,
 and that will  render it still more pure ;  in  short,  all water that
 will make good lather with soap is wholesome to  drink  without
 boiling, but none  else."
   This book was written 175 years ago, and we  still treat  water
 by  distillation, by boiling, and by soap.
  In 1771 Dr.  Percival made an analysis of the hard pump-water
 of Manchester, England.
  In 1793 and 1794 Dr. Franklin called attention to the necessity
 of pure water in  Philadelphia, because of the ravages  of  con-
 tagious diseases, and in his will  (dated  1879)  he recommends
 that at the end  of  100 years, if not before, they  be  supplied by
 water brought  in pipes from the WissaJiickon.
  Dr. Brown,  of N. Y., in  1798, reports  on the character of the
 water,  and declares  it to  be the cause of  contagious diseases,
especially  of yellow  fever,  from which the city had lately suf-
fered.
  Thomas Ewell,  M. D., of Virginia, in a series  of discourses on 
38
BULLETIN OF THE
chemistry, calls attention to  the necessity of purification of filthy
waters, and recommends filtering.
  In France, in 1808, it was decreed that no one should dig a well
within 100 metres of any cemetery.
  In 1824. Dr. Charles T. Jackson, State assayer  of Massachu-
setts, speaks of examining a specimen of drinking water that con-
tained  lead ; and similar reports were made by him in the follow-
ing years.
  The water of Cochituate lake, with view to utilizing  it to sup-
ply Boston, was examined in 1834, at  which  time  only the total
residue left on evaporation was  reported.   In 1837, and  three
times in 1845, other examinations, more critical, were made, and
the reports were much in the general form now used.
  Prof. Boye analyzed the water  of Schuylkill river in  1842, and
Prof. L. C. Phillips in 1870,  and  the two results were stated  in
the same terms.
  In 1S45 a report was made as to the best  method of supplying
the city of Boston with  water, and examinations  made by Dr.
Jackson and Mr. Hayes stated  the results of their analyses  in
parts per  100,000.
  This report involved the permanent  supply of water to Boston.
Yet, in reading over the minutes  of the proceedings of the water
board, while  considering  this question,  it strikes one that the
chemical question was a  subordinate one.  For instance: "• The
foreign matters in this water are in such small proportions as in
no way to impair its healthfulness as a drink, nor will they prove
injurious in washing clothes."
  In 1849 analyses  of the  well waters in Brooklyn, N. Y., were
made by Drs. Torrey and Chilton.
  The analysis  of  Fresh  pond,  that  now supplies  Cambridge,
Mass., with water,  was  first made in 1853, and  not again  till
1872 ;  but between  1872 and  1880 sixty-three complete examina-
tions are reported.
  The Board of Health of Troy,  N. Y., in 1856, had  the hydrant-
water examined by Prof. Wm. Elderhorst, and in 1858 the water of
two of the principal wells of that city were also examined.  These
examinations were conducted with metric weights and measures,
but the reports were made in  grains per gallon.  The results re-
ported in these analyses differ but little from those now made
except in  relation to organic matter. 
CHEMICAL SOCIETY
39
  In this same year  a chemical report of the  waters supplied to
London (Eng.) was made by Prof. A. VV. Hoffman to the Pres-
ident of the General Board of Health.
  In 1859 tne waters of an artesian well at Louisville,  Ky., were
examined, and the result reported in grains per gallon, with a state-
ment in terms of the various salts found.
  Although the oldest water company of London was founded in
the latter part of the sixteenth century,  it was  not until 1827 that
attention was called  to the quality of the water supplied from the
Thames.   In 1828 a commission was  appointed to  inquire into
its condition, and two chemists were  employed, viz., Dr.  Pearson
and Dr. Gardner, who made analyses of the water.
  Analyses were also made in 1834, an<J m :^44 a royal commis-
sion was issued to inquire into the state of large towns  and popu-
lous districts of England  and Wales.  The instructions included
the examination of the water-supply in such towns  and districts.
Three distinguished chemists—Professors  Graham, Miller, and
Hoffman—aided in  making the  report.
  The cholera visitation to England, in 1847,  brought  forth from
the Queen the Public Health Act (11 and  12 Vict., p. 63)  of 1848.
whereby one-tenth of the inhabitants of any city or town, by petition
to the General Board of Health, could secure a thorough  sanitary
inspection -of such  city or town.   Numerous places  were thus
brought under observation, and the numerous  cases of water pol-
lution from various  causes attracted  attention  everywhere.   The
epidemic of cholera  which so soon followed (1854) was marked by
some special  facts in regard  to water contamination, and the real
importance of a close scrutiny of  all  sources of water supply was
clearly established.
  There was introduced, in 1864, in Parliament the first  River
Pollution  Prevention Bill, but  it failed to pass the Commons.
The following year  it was amended and again offered, and again it
failed ; but a  royal commission was appointed to inquire into the
best means of preventing the pollution of the rivers, which reported
the following year.   Nothing was  effected, and, in 1868, a new-
commission was appointed, but it was not till  1876 that an act
was passed which protected in any way the  various  sources of
water-supply  from  contamination.   At the present time a bill  is
before Parliament for the better protection of the rivers from pol-
lution. 
40
BULLETIN OF THE
  From 1872 to the present water-analyses have been of common
occurrence, and individual cases are not worth especial mention.
The interest in this question of the purity of water was  excited
by the extensive information obtained by the inquiries of the royal
commission, and chemists  were stimulated to seek more  exact
methods for determining the presence and character  of  organic
matters.   Aside from  the determination of the presence of these
organic compounds, the results of a chemical  analysis of water
to-day differs in no  material  respect from  results of fifty years
ago.
  The industrial applications of water very often require chemical
examination of  its purity, and amendment of its quality by chem-
ical processes.   The principal arts in which the  character of the
water is of essential importance are dyeing, tanning, paper-making,
and the management of steam-boilers.  Dyeing is one of the old-
est arts, and the importance of pure water is mentioned by every
one who has written upon the subject.  In the earlier books the
terms " soft water,"  usually meaning rain-water,  " fair  water,"
and " clean water," are commonly used.   In the later works on
dyeing directions are  usually given  which  conform  more  or
less perfectly to the  methods described  in  analytical chemical
books of the same  or an  earlier  date, and  which are more or
less  complete,  for the examination  and purification of water.
The  same remarks will apply to the arts of tanning and paper-
making.
   So important, from an industrial point of view, does pure water
become, that it is said a large paper-mill built near Holyoke, Mass.,
found itself unable to carry on its business profitably merely  be-
cause the water supply contained more impurities than those of
neighboring mills ; the excess of chemicals required to correct the
water costing more than the usual profit amounted  to, thus neces-
sitating an abandonment of the enterprise.
   Most of the peculiar  processes for the purification of water have
been adopted to treat the feed-water of steam-boilers, which are so
extensively used everywhere.  The effect of organic impurities in
any quantity is to cause the water to froth and foam, and thereby
cause it to be mechanically carried  along with  the steam, while
the presence of earthy  salts causes  a  deposit on the shell of the
boiler that prevents the passage of heat to the water, and is tech-
nically known as *' scale." 
CHEMICAL SOCIETY.
41
   The  methods of prevention or  cure  of these  difficulties  are
 mechanical or  chemical,  and necessarily  vary  according to  the
 nature  of the water ;  those which are  mechanical either relat-
 ing to filters through which the water passes before entering  the
 boiler,  or to  devices  which skim oft' and remove the scum  be-
 fore it settles.
   The processes that are chemical include  compositions  or treat-
 ment for  purifying  the  water  before  entering the boiler, as  the
 addition of lime, soda, &c, or for softening or holding in solution
 the scale, so that it may  frequently be removed  by the process
 called w' blowing-off."  For the  latter purpose  very  many sin-
 gular and arbitrary compounds  have been used,  such as tan-
 liquor, potato  water,  malt extract,  &c,  and  combinations of
 these or  similar substances with alkaline, earthy, or iron salts,
 for varieties of which  more than  ioo U. S. patents have been
 granted.
   Bergman, the celebrated Swedish chemist of  the 18th century.
 in his paper published about 1788,  was the first to  outline a sys-
 tematic scheme of  water-analysis.   He examined water  in two
 ways, viz., by precipitants and by evaporation,  and says if accu-
 racy is necessary, both should  be  used, and the analyses should be
 confirmed by synthesis.   He begins with the examination of the
 physical quantities,  and distinguishes the matters held in solution
 from  those mechanically suspended.  He also succeeded in mak-
 ing artificial mineral waters by combining  the elements similar to
 those found in well-known springs.  Dr. John  Murray, in 1816,
 still  further systematized  the  plan of water-analysis.   He pub-
 lished a general formula for the analyses of mineral waters, and
 took the ground that the salts existing in a  water need not  be  the
 same as those obtained  upon evaporation,  for salts viewed as in-
 compatible may co-exist in a state of  weak solution.  According
 to Murray, the analysis of a  mineral water consists in nothing
 more than the determination of the several  acids  and bases it con-
 tains, although he  combined  the acids  and bases so found, ac-
 cording to their solubility, into compounds which  he supposed to
 be the most probable actual ingredients in the water.
  Berzelius contended that everything beyond the  mere statement
of the acids and bases  being mere matters of hypothesis, nothing
should be set down but the respective  weights of those acids and
bases. 
42
BULLETIN OF THE
  Almost all  the modern  works  on chemical analysis present
schemes for water-analyses: among them may  be  mentioned,
••Reid,  1836."  "Parnell,  1845."  -Rose, 1843-1851."  - Noad.
1S64,"  "Fresenius  (5th  edition),  in 1S70." 1  "Sutton  (3d edi-
tion), 1876," and "Church, 1877."
  Although complete instructions  for water-analyses  are usually
given, very little is said as to the method of stating results.
  Henry Noad, in his manual of chemical analysis, published in
1864, treats of the arrangements of the results of the analyses.  He
advises  that the electro-negative and electro-positive ingredients be
arranged, as established by direct experiment,  into binary combi-
nations, in the ratio of their mutual  affinities,  the strongest acid
being combined with the strongest base, paying attention, also, to
the fact pointed out by Berthollet, that the force of affinity is con-
siderably modified by the degree of solubility of the salts. He also
says that the direct results should  be given, and the total amount
of the fixed constituents must agree with  the joint amounts  of the
several  ingredients.   Such examples of analyses  as are given are
expressed in grains  to the imperial gallon.
   Perhaps it  is not too strong a statement to say  that  the  intro-
duction of the Nessler process, for the determination of ammonia.
bv Messrs. Hardow and Miller, and its adaptation by Frankland and
by Wanklyn, as described in their works on water-analysis,  is one
of the most important improvements in modern analytical chem-
istry.2
   Indeed,  the researches of Clark, Frankland, Armstrong, Miller,
Wanklyn, and others, within recent years, have brought the sub-
ject of water-analvsis into such satisfactory form  that little  seems
to be desired in addition, except some  uniformity as  to the state-
ment of results.
   It may be of interest  to  present  here two analyses  made  by
Bergman (1777-90) as showing how some  of the earlier analy-
ses were stated.   The first, an analysis of sea-water,  is as fol-
lows :
  1 The earlier editions do not appear to treat of water-analyses separately.
The English edition of 1870-71 contains full instructions.
  -'The test discovered by Nessler was first applied to quantitative deter-
mination by the late Profs. Hardow and Miller, and more recently has been
adopted by Dr. Frankland and by Professors Wanklyn  and Chapman.__
Parlies' Hvgienc, ^th edition, 1878. 
CHEMICAL SOCIETY.
43
In one Kanne (Swedish measure).*
Of common salt
Of salited magnesia
Of gypsum
Ounces.
Graim
 433
 380
In one	Ka	nne.
7	cu	bic inches
• o±	grains.	
14		"
3i		i'
14		''
rvt		
            Total.......3        378
  The second is of the water from a mineral  spring in Denmark
Parish, near I'psola, in Sweden, and is expressed as follows:

        Of aerial acid  ...
        Of aerated iron   ....
        Of vitriol of iron
        Of Glauber's salt
        Of selenite    ....
        Of common salt, at most
        Of siliceous, nearly

            Total   ......   32! grains.

Which,  as  Bergman says,  " considerably  exceeded the weight of
the residuum, which was  201 grains ;" the  difference, he  says,
arising from the water  of crystallization.  The majority of the

earlier analyses are expressed  in the  form of the most  probable

combination of these elements, and in many cases the entire  pro-
cess of the analysis is given in detail.   The following list of 42

methods of statement or expression is based  upon an inspection

of about a  thousand analyses :

                                 ing of the figures.
                                    As Grains in one quart.
                                     " Grains in three quarts.
                                     " Grains in gallon.
                                      ' Grains in gallon of 231 cu. in.
                                     " Grains in wine gallon.
                                     " Grains in U. S. gallon.
                                     " Grains in American gallon.
                                     " Grains in standard gallon.
                                     " Grains in gal.  of 70,000 grains.
                                     •' Grains in imperial gallon.
                                     " Grains in about 7 gallons.
                                     " Grains in 1,000 parts.
                                     " Grains in 1,000.
                                     " Grains in 6,000.
                                     '•' Grains in 8,000.
                                     " Grains in 50,000, or nearly 7 pts.
                                     " Grains per litre.
                                     ■' Pounds in 100,000 U. S. gallons.
                                     " Grammes per litre.
                                     " Grammes to 1,000 grammes.
                                     " Milligrammes per litre.
  With no statement as to the mean
As per cent.
                 100.
               1,000.
              10,000.
             100,000.
   Parts in 1,000,000.
   Parts in      100 grains.
               1,000 centimetres.
                 100 grammes,  or
                    1 hectogram.
                  64 cubic inches.
                 100 cubic inches.
                 200 cubic inches.
Parts in
Parts in
Parts in
Parts in
Parts in
Parts in
Grains in
Grains in
Grains in
Grains to the pint.
Grains in wine pint.
Grains in imperial pint.
Troy grains in pint.
Grains in 5 pints.
Grains in 28 Parisian pints.
Grains in 16 ounces of water.
Grains in 20 ounces of water.
  1 A Swedish kanne is given as about 6 English pints, 100 cubic  inches,
or 3 quarts. 
44
BULLETIN (IF THE
   In some places three scales were found in the same table, a part
expressed as grains per gallon, another part as milligrammes per
litre and the hardness in Clark's degrees.   These can nearly all be
reduced to one or another of four common methods of expression
as detailed by Nichols, viz :
  /st.  Grains per English  or imperial gallon (277  cubic inches or 10
lbs. = 70,000 grains of pure water).
  2d. In grains to the U. S. or wine  gallon (231 cubic inches = 58,372 +
grains of pure water).
  3d. On a decimal basis as  parts per  100, 1,000, 1,000,000, &c.  This is
generally used in France and Germany, also in the reports of the " Rivers
Pollution Committee of Great Britain," and in this country in reports of
the " National Board of Health,' and  of many  State Boards of Health.
  4th. As so many milligrammes  to the litre.  (This would be the same
as parts in 1,000,000 if the water had the same density as pure water, /'. e.,
if the litre actually weighed 1,000 grammes).
   The variation of specific gravity in the  case  of "potable waters
would be of little account, but in the case of waters more highly
mineralized the difference between parts per million and  milli-
grammes per litre  would be too great to be disregarded, and pre-
cludes the combination in the same analyses of measure by weight
and measure by volume  in any  way, if analyses are to be made
exact and mutually comparable.   Of about  eight  hundred analy-
ses of mineral waters of the  United States, 60%  were expressed
according to the second method,  about 7"o in the English or first
method, and about 3% according to the fourth method, while 22%
are expressed in the  decimal or third method.
   After careful consideration  the  Committee would  recommend
the following conclusions, viz :
   1 st. That water analyses be uniformly reported in  parts  per
million or  milligrammes per kilogramme, with the temperature
stated, and that Clark's scale and  all other systems be abandoned."
   2d.  That all analyses should be stated in terms  of the radicals
found, whether elementary or compound.'
  3d.  The  constituent radicals should  be arranged  in electro-
chemical series, the positive radicals first.
  4th. The combinations  deemed most probable  by the chemist
making the  analysis should be stated, both by symbols  and by
name.'
                                       A. C.  PEALE,
                                       WM.  H.  SEAMAN.
                                       C. H.  WHITE.
Washington. D. C. Feb. nth.  1886. 
CHEMICAL SOCIETY.
45
                    Notes on  Recommendations.

  a. The Committee were unable to agree with the recommendation of
the Society of Public Analysts of London, that water analyses should be
reported in grains per gallon, because the Committee believe that parts
per million will  be  better understood by  non-professional readers  than
grains per gallon, which, in themselves, are incommensurable quantities,
because not of the same denomination ;  while to professional chemists the
decimal form of report is much preferable.  The general form  recom-
mended by the London society  is herewith appended for  the  benefit of
those to whom their reports are  not readily accessible :

               Form in -which analyses should be reported.

(As recommended by  committee of the  Society of Public Analysts of
         London.— The Analyst, London, vol. 6, 1881, p. 139).
                                                       O rains per gallon
Description of sample,                        ...................__............
Drawn,                                ..........______..................________
Temperature when drawn,
Appearance in two-foot tube,........................................................................................
Smell when heated to ioo° F.                 ...................................................
Chlorine in chlorides,
Phosphoric acid  in phosphates,
Nitrogen in nitrates,
Ammonia,
Albuminoid ammonia,
Oxygen absorbed in fifteen minutes at 8o°  F.
Oxygen absorbed in four hours at 8o° F...................
Hardness before boiling (Clark's scale),
Hardness after boiling (Clark's  scale),
Total solid matters dried at 2120 F.
Microscopical appearance of deposit,
Remarks,

  b. By terms of the radical found is to  be  understood the immediate re-
sults of the actual analysis.  For example: It  is usual to determine am-
monia as such, and it should be stated  as  ammonia (N H3) ;  if nitrogen
(N) alone for any reason is found as an  element, it should be so stated;  if
carbonic acid (C  Os) is found as such,  put it down so,  in order  that any
one examining the analytical results may have the same facts as the chemist
who made the analyses.
  c. The Committee have been careful to avoid any recommendation as to
the manner of combination of the analytical results, because the  views of
chemists would probably differ so much  that uniformity in this respect
could not at present be obtained.  The use of  symbols is recommended to
avoid obscurity in compounds, such as the salts of iron,  etc. 
WAA C512r 1887
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