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 Solution Manual for Understanding American
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Chapter 1: The American People

CHAPTER CONTENTS

The American People

A Demographic Profile
Immigration and Ethnic Diversity
Immigration and Political Cleavage
Religious Diversity
Economic and Demographic Diversity
Diversity and Identity Politics
Political Culture
The Significance of Political Culture
Learning Political Culture
The Core Values
Individual Liberty
Political Equality
Popular Sovereignty
Majority Rule
Minority Rights
Economic Rights
The American Citizen
Political Participation
Conclusion: Is Government Responsive?

SELECTED SPECIAL FEATURES SECTION

Talking points
A Demographic Profile
Behind the Scenes: The Torch Passes

Learning Objectives

 Explain the impact of immigration and ethnic diversity on American

society.
  Describe the influence of identity politics on local and national
elections.
 Discuss Howard Zinn and Ray Rafael’s analysis of the traditional
accounts of the Founding.
 Explain the significance of political culture.
 Identify and describe the six major core values of American political
culture.

Overview

Americans boast about their form of government—“for the people, of the people, and by
the people.” Immigrants, it has been broadcasted, flock to this nation for “life, liberty,
and the pursuit of happiness.” Yet citizens’ participation in their own governance has, for
the most part, been disappointing.

Chapter 1 focused on the changing demographics of the nation and its impact on the
political process. Identity politics is more evident today with the burgeoning Hispanic
population, and the highly visible shift of women’s involvement in politics. This has had
a profound impact on the political landscape, from the elections of local and national
candidates to appointments to the highest court in the land. Political socialization—
educating citizens, residents and guests alike of the six major core values—is necessary
for understanding the true responsibilities of the American citizen.

Political scientists like Seymour Marin Lipset in his book “American Exceptionalism: A
Double-Edged Sword,” has argued that “Americans’ tendency to view society in
idealized terms is a source of both alienation and progress.” For American democracy to
continue being the preferred form of government by citizens around the world, it is
important that this idealization comes closer to realization.

Critical Thinking Questions for Class Discussion

1. How are immigrants of today treated similarly and differently from

immigrants of the past?
2. Should all fifty states have the power to establish their own immigration
policies? Why or why not?
3. What did the poet Walt Whitman mean when he penned the line, “Here is
not merely a nation but a teeming Nation of nations”? Is his sentiment still
true today?
4. Why has the 2010 census been referred to as the most contested in recent
decades?
5. What is the major difference between Hobbes’ and Locke’s views in
regards to individual liberty and government?
 6. How has religious intolerance in the past and present impacted American
society?

Lecture Launcher

1. After winning independence from the British, the leaders of this new nation did
not mimic the type of governing system that they had fought to free themselves
from. Instead, they opted for a democratic form of government “…of the people,
for the people and by the people.” American society is extremely diverse. It has
been referred to by social scientists as both a “melting pot” and a “salad bowl.”
With such conflicting views as to what constitutes American society, the question
that begs an answer is “Is the U.S. form of government responsive to the people
under its jurisdiction?”

In-Class Activities

Recently, U.S. District Court Judge Susan Bolton blocked the portion of the Arizona
immigration law that would require police to determine the status of people they lawfully
stopped and suspected were in the country illegally.

1. Divide the class in half. Have one group develop arguments to support, and the
other group to oppose the police requirement in the law with specific supporting
examples.

Web Links

 www.census.gov/compendia/statab This is “the authoritative and comprehensive

summary of statistics on the social, political, and economic organization of the
United States.”
 www.civicyouth.org The premier clearinghouse for research and analysis on
civic engagement.
 http://www.conginst.org/ A site that provides up-to-date survey data on the
American political culture
 http://www.loc.gov/ The Library of Congress website; it provides access to over
seventy million historical and contemporary U.S. documents.
 http://www.stateline.org/ A University of Richmond/Pew Charitable Trusts site
dedicated to providing citizens with information on major policy issues.
 http://www.tocqueville.org/ Includes biographical and other references to Alex
de Tocqueville and his writings.

Instructor Resources
Dahl, Robert A. Democracy and Its Critics. New Haven, Conn.: Yale University Press,
1989. One of the most prominent political theorists of our era on the assumptions
of democratic theory. The book provides a justification for democracy as a political
ideal by tracing modern democracy’s evolution from the early nineteenth century
to the present.

Domhoff, William G. Who Rules America? Power and Politics, 4th ed. New York:
McGraw-Hill, 2002. A critical assessment of American government by a leading
proponent of elite theory.

Katz, Michael B., and Mark J. Stern. One Nation Divisible: What America Was and What
It’s Becoming. New York: Russell Sage Foundation, 2006. A penetrating look at
the transformation of American society during the twentieth century.

Lipset, Seymour Martin. American Exceptionalism: A Double-Edged Sword. New York:

Norton, 1996. Argues that Americans’ tendency to view society in idealized terms
is a source of both alienation and progress.

Ravitch, Diane and Abigail Thernstrom, eds. The Democracy Reader. New York: Harper
Collins, 1992. The enduring issues of democracy in a collection of documents,
essays, poems, declarations, and speeches.

Stout, Jeffery. Democracy and Tradition. Princeton, N.J.: Princeton University Press,
2004. An analysis of the moral claims associated with democracy.

Verba, Sidney, Kay Lehman Schlozman, and Henry E. Brady. Voice and Equality: Civic
Volunteerism in American Politics. Cambridge, MA: Harvard University Press,
1995. An analysis of how people come to be activists in their communities, what
issues they raise when they participate, and how activists from various demographic
groups differ.

Important Terms

democracy - derived from the Greek, means “authority of the people”

direct democracy - citizens vote on most issues and legislate for themselves
identity politics - the practice of organizing on the basis of one’s ethnic or racial identity,
sex, or sexual orientation to compete for public resources and to influence public
policy
indirect democracy/republic - citizens do not pass laws or make policy; they select policy
makers to make decisions for them
natural rights - are inherent, so they exist as soon as people are born; unalienable, so they
 cannot be taken away by rules; and self-evident, so they can be known to all
political culture - shared body of values and beliefs that shapes perception and attitudes
toward politics and government and in turn influences political behavior
popular sovereignty - rule by the people
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 REDUCTION BY THE ELECTRIC CURRENT.
489. Method of Williams-Warington.—From the losses which naturally occur during
the evaporation of water, even with all the precautions noted, Warington was led to try some
method for the determination of nitrates and nitrites in waters without previous
concentration.[318] The reduction of these bodies by the copper-zinc couple formed the basis
of these experiments, and they resulted in the following method of manipulation, which is
based on a process devised by Williams.[319]
The method consists in boiling rapidly one liter of the rain water in a retort, with a little
magnesia previously raised to a low red heat and then washed, until 250 cubic centimeters
have distilled over. The residue is then made up to 800 cubic centimeters, transferred to a
wide-mouthed, stoppered bottle supplied with strips of copper and zinc forming electric
couples, and set aside, at a constant temperature of from 21°–24°, for three days. A measured
portion of the solution is then distilled, and the ammonia determined in the distillate by
nesslerizing.
This plan has two advantages: First, the ammonia, as well as the nitrogen as nitrates and
nitrites, can be determined in the course of the same operation and in the same sample of
water. For this purpose it is only necessary to fit the retort to an efficient condenser and to
remove all ammonia from the apparatus by boiling distilled water in the retort before
introducing the rain water. The distillate of 250 cubic centimeters from the rain water, as
described above, is well mixed and the ammonia determined, in from twenty-five to one
hundred cubic centimeters thereof, diluted to 150 cubic centimeters with ammonia-free
water. Second, the nitrogen, as nitrates and nitrites, is determined directly and alone; the
error of the determination is as small as nesslerizing admits of, since it is possible, if
necessary, to distill 600 cubic centimeters of the boiled rain water corresponding to 750 cubic
centimeters of the original, and thus obtain a full amount of ammonia for determination,
even when the rain water has been poor in nitrates.
The determination of nitric nitrogen, in a given sample, by the above method gave a mean
quantity of product of 0.162 part per million, while the determination, in the same lot of
samples, by the modified Schloesing method gave 0.125 part per million. This result confirms
the supposition that in the complete evaporation necessary to the manipulation of the
Schloesing method there is a loss of nitrogen. The amount of nitrogen as nitrates and nitrites
in the rain water at Rothamstead, for the twelve months ending April 1, 1888, was found, by
the Schloesing method, to be 0.614 pound per acre, the total rain-fall being 21.96 inches. For
the year ending April 1, 1889, by the copper-zinc method, it amounted to 0.917 pound per
acre, the total rain-fall being 29.27 inches.
The amounts found in other localities are quite different from the above, as for instance,
the mean of seven stations in Germany for thirteen years, beginning in 1864, showed 10.18
pounds of nitrogen per acre. The average amount for ten years at the observatory of Mont
Sauris, near Paris, showed 12.36 pounds of nitrogen per acre. The average for three years at
Lincoln, as determined by Professor G. Gray, shows one and six-tenths pounds of nitrogen
per acre per annum. At Tokio, in Japan, Kellner found, for one year, 1.02 pounds per acre.
490. Determination of the Ammonia.—The method used at Rothamstead is to make
one determination of ammonia in the whole of the distillate obtained, the strength of which is
regulated by varying the amount introduced into the retort, so that it shall be equal to about
two cubic centimeters of the standard ammonia solution. A 150 cubic centimeter cylinder is
first filled with the rain water, and fifty cubic centimeters of nessler reagent added. The depth
of tint indicates what quantity of rain water will be required for distillation. This having been
determined, the appropriate volume of the rain water, provided it do not exceed 600 cubic
centimeters, is placed in the retort described above, and the distillation continued until the
150 cubic centimeter cylinder is filled. The titration is made in the usual way.
491. Preparation of the Copper-Zinc Couple.—For 800 cubic centimeters of boiled
rain water, prepared as described, six strips of zinc foil, four inches long by one and a quarter
inches wide, are taken and bent at right angles along their center to obtain stiffness. The
couple is cleansed and coated by washing in a series of five beakers containing, respectively,
dilute solution of sodium hydroxid, very dilute sulfuric acid, a three per cent solution of
copper sulfate, ordinary distilled water, and distilled water free from ammonia. Through
these five beakers the zinc foil is successively passed. It is rinsed both after the alkali and the
acid. But after the copper has been deposited, the strips are simply drained and carefully
placed in the distilled water, it being difficult to rinse without removing the copper. The
couples should be entirely submerged when placed in the rain water. The strips should
remain in the copper sulfate solution long enough to be well covered with copper.
492. Substitution of an Aluminum-Mercury Couple for Copper-Zinc.—Ormandy
and Cohen have proposed to use an aluminum-mercury couple for the copper-zinc in the
process described above.[320]
This couple acts more quickly than the copper-zinc, and the results are equally as accurate.
Nitrites are reduced in about one hour by this apparatus, while the zinc-copper couple of
Gladstone and Tribe requires about six times as long. Aluminum foil, free of grease, should
be used. The foil should be heated over a bunsen just before amalgamation. The clean, very
thin foil is coated with mercury by shaking with a concentrated solution of mercuric chlorid.
It should be prepared immediately before use.
The amalgamated foil is introduced into the sample of water to be analyzed, and left until
all the aluminum is converted into oxid. The presence of the oxid favors the prevention of
bumping during the subsequent distillation. The distilled ammonia, collected in dilute acid, is
determined by nesslerizing, the free ammonia in the sample having been previously
determined. The increase in ammonia is due to nitrates or nitrites reduced by the couple.
 IODOMETRIC ESTIMATION OF NITRIC ACID IN NITRATES.
493. Method of De Koninck and Nihoul.—This process is applicable only in the
absence of organic bodies and other reducing agents.
The principle on which it rests, as applied by McGowan, is as follows:[321]
When a fairly concentrated solution of a nitrate is warmed with an excess of pure, strong
hydrochloric acid, the nitrate is completely decomposed, and the production of nitrosyl
chlorid and chlorin is quantitative. The reaction, as shown by Tilden, is represented by the
following equation:[322]
HNO₃ + 3HCl = NOCl + Cl₂ + 2H₂O.
One molecule of nitric acid thus yields two atoms of chlorin and one molecule of nitrosyl
chlorid capable of setting free three atoms of iodin. The iodin can be estimated in the usual
manner by titration with sodium thiosulfate. The nitrosyl chlorid is decomposed by the
potassium iodid, nitric oxid escaping.
The apparatus employed is shown in Fig. 87.
A is a small, round-bottomed flask, into the neck of which a glass stopper, x, is accurately
ground (with fine emery and oil). The capacity of the bulb is about forty-six cubic
centimeters, and the length of the neck, from x to y, ninety millimeters. The first condenser is
a simple tube, slightly enlarged at the foot into two small bulbs.[323] The length from a to b is
300 millimeters, from b to c 180 millimeters, and from e to f thirty millimeters. The capacity
of the bulb B is twenty-five cubic centimeters, and the total capacity of the two bulbs and
tube, up to the top of C, forty-one cubic centimeters. This condenser is immersed, up to the
level of c, in a beaker full of water. D is a geissler bulb apparatus, E is a calcium chlorid tube,
filled with broken glass, which acts as a tower and g is a small funnel, attached by rubber and
clip to the branch ⟙ tube h. Between the ⟙ tube i and the wash-bottle for the carbon dioxid is
placed a short piece of glass tubing, s, containing a strip of filter paper, slightly moistened
with iodid of starch solution. This tube s is really hardly necessary, as no chlorin escapes
backwards if a moderate current of carbon dioxid is kept passing, but it serves as a check. A
glance at the joints o, p, and q, which are of narrow india-rubber tubing, is sufficient to show
that, by using this arrangement, practically no rubber is exposed to the action of the chlorin.
The tiny piece of rubber tubing at the joint o may be done away with, the narrower tube there
being accurately ground into the wider one; this makes the condensing apparatus practically
perfect.
The actual operation is performed in the following manner:
The evolution flask is washed and thoroughly dried, and the nitrate (say, about 0.25 gram
of potassium nitrate) is tapped into it from the weighing tube. Two cubic centimeters of water
are now added, and the bulb is gently warmed, so as to bring the nitrate into solution, after
which the stopper of the flask is firmly inserted. About fifteen cubic centimeters of a solution
of potassium iodid (one in four) are run into the first condensing tube, any iodid adhering to
the upper portion of the tube being washed down with a little water, and five cubic
centimeters of the same solution, mixed with eight to ten cubic centimeters of water, are
sucked into the geissler bulbs whilst the glass in the tower E is also thoroughly moistened
with the iodid. The geissler bulbs should be so arranged that gas only bubbles through the
last of them, the liquid in the others remaining quiescent.
All the joints having been made tight the carbon dioxid is turned on briskly and passed
through the apparatus until a small tubeful collected at l, over caustic potash solution, shows
that no appreciable amount of air is left in it. The small outlet tube l, is now replaced by a
calcium chlorid tube, filled with
broken glass which has been
moistened with the above-
mentioned iodid solution, and
closed by a cork through which an
outlet tube passes, the object of this
trap tube being to prevent any air
getting back into the apparatus. The
brisk current of carbon dioxid is
continued for a minute or two
longer, so as to practically expel all
the air from this last tube. The
stream of gas is now stopped for an
instant, and about fifteen cubic
centimeters of pure concentrated
hydrochloric acid, free from chlorin,
run into A through the funnel g
(into the tube of which it is well to
have run a few drops of water before
Figure 87. McGowan’s Apparatus for the Iodometric
beginning to expel the air from the Estimation of Nitric Acid.
apparatus), and A is shaken so as to
mix its contents thoroughly. A slow
current of carbon dioxid is now again turned on (one to two bubbles through the wash-bottle
per second), and A is gently warmed over a burner. It is a distinct advantage that the reaction
does not begin until the mixed solutions are warmed, when the liquid becomes orange-
colored, the color again disappearing after the nitrosyl chlorid and chlorin have been
expelled. The warming should be very gentle at first in order to make sure of the conversion
of all the nitric acid, and also because the first escaping vapors are relatively very rich in
chlorin; afterwards the liquid in A is briskly boiled. A very little practice enables the operator
to judge as to the proper rate of warming. When the volume of liquid in A has been reduced
to about seven cubic centimeters (by which time it is again colorless) the stream of carbon
dioxid is slightly quickened and the apparatus allowed to cool a little. The burner is now set
aside for a few minutes, and two cubic centimeters more of hydrochloric acid, previously
warmed in a test-tube, run in gently through g; there is no fear either of the iodid solution
running back, or of any bubbles of air escaping through y if this is done carefully. This is a
precautionary measure, in case a trace of the liberated chlorin might have lodged in the
comparatively cool liquid in the tube h. The carbon dioxid is once more turned on slowly and
the liquid in A is boiled again until it is reduced to about five cubic centimeters. It is now only
necessary to allow the apparatus to cool, passing carbon dioxid all the time, after which the
contents of the condensers are transferred to a flask and titrated with thiosulfate. At the end
of a properly conducted experiment, the glass in the upper part of tower E should be quite
colorless and there should be only a mere trace of iodin showing in the lower part of the
tower, while the liquid in the last bulb of the geissler apparatus ought to be pale yellow.
During the operation, the stopper of A and the various joints can be tested from time to time
by means of a piece of iodid of starch paper, and before disjointing it is well to test the
escaping gas (say at m) in the same way, to make sure that all nitric oxid has been thoroughly
expelled.
The method is capable of giving accurate results, but it can not be preferred to the
reduction or colorimetric processes.
494. Method of Gooch and Gruener.—The principle on which this method rests
depends on the decomposition of a nitrate in presence of a hot saturated solution of
manganous chlorid and hydrochloric acid in an atmosphere of carbon dioxid.[324] The
products of decomposition are passed into a solution of potassium iodid and the liberated
iodin is titrated with standard sodium thiosulfate. The products of the reaction are chlorin,
nitric oxid, and possibly nitrosyl chlorid, and under proper precautions the iodin set free is
quantitively proportional to the weight of nitrate decomposed. The manganous mixture is
acted on slowly at ordinary temperatures, but on heating, the nitrate is decomposed with the
formation of a higher manganese chlorid and nitric oxid. When the heat is continued a
sufficient length of time the chlorin from the higher chlorids is evolved and only manganous
chlorid remains. During the heating the color of the solution passes from green to black and
at the end the green color is restored. The apparatus employed is shown in Fig. 88.
A plain pipette bent as is shown in the figure
serves as the generating flask and for the
attachment on the one hand to the carbon dioxid
apparatus and on the other to the system of
absorption bulbs for containing the potassium
iodid. The latter should be glass, sealed to the
evolution bulb of the pipette to prevent the action
of the evolved gases on organic materials. The
point of the potassium iodid apparatus is drawn
out so as to be pushed well into the second
receiver, being held in place by a piece of rubber
tubing. The third tube acts simply as a trap to
exclude the air from the absorption apparatus.
The first receiver contains in solution three grams,
the second two, and the third one gram of
potassium iodid. During the reaction the first
Figure 88. Apparatus of Gooch and Gruener.
receiver is kept cool by immersion in water.
Before connecting the apparatus with the carbon
dioxid generator the solution of manganous
chlorid and afterwards the nitrate solution are drawn into the bulb of the pipette by gentle
suction. After connecting the apparatus the current of carbon dioxid is started and kept up
until all the air is expelled. Heat is then applied to the bulb of the pipette and the distillation
continued until all the liquid has passed over. At the end of the reaction the contents of the
receivers are united by disconnecting the apparatus from the carbon dioxid generator and
passing water through the pipette. The introduction of the manganous chlorid into the
mixture does not interfere with the titration of the iodin. This is accomplished in the usual
way with sodium thiosulfate using starch as an indicator. The quantity of material used
should contain about the amount of nitric acid that is found in two-tenths of a gram of
potassium nitrate. This method, so similar to the preceding, is somewhat less complex, and,
to that extent, preferable to it.
 ESTIMATION OF NITRIC ACID BY COLORIMETRIC
COMPARISON.
495. Delicacy of the Method.—The remarkable delicacy of those methods of chemical
analysis, which depend on the production of a pronounced color, which can be compared
with that produced by a known quantity of a given substance, has been long illustrated by the
nesslerizing process for the estimation of ammonia. By such methods minute qualities of
substances can be quantitively determined with great accuracy, when they would escape all
effort for their estimation by gravimetric methods. Processes based on this principle are,
therefore, peculiarly applicable to the detection and estimation of oxidized nitrogen in waters
and soil extracts, whether they be present as nitric, nitrous, or ammoniacal compounds.
In the following paragraphs will be given with sufficient detail for the needs of the analyst,
the principles and practice of the colorimetric comparison methods which have been
approved as best by the experience of analysts. These methods are applicable especially to
cases in which only minute quantities of the substances looked for are present, and where
celerity of determination is especially desirable. They are, therefore, of especial value in the
analysis of rain, drainage, and irrigation waters, and of soil extracts poor in oxidized
nitrogen.
496. Hooker’s Method.—The quantitive action depends upon the deep green coloration
given by nitric acid, when dissolved in sulfuric acid and carbazol.[325] Other oxidizing bodies,
such as iron, chlorin, bromin, chromic acid, etc., give the same reaction, but not in such a
prominent manner. Such bodies with the exception of chlorin and iron, are not often found in
waters. In the application of the process, iron, if present in quantities greater than one-tenth
part per one hundred thousand, must be removed. Chlorids also, even when present in very
small quantities, interfere with the delicacy of the reaction and must be removed. Easily
destructible organic matter tends to lower the result, but not materially, unless present in
large excess. Calcium carbonate and sulfate, soda, and other alkalies, in the quantities in
which they are usually present in water, do not affect the result. The following reagents are
required:

1. Concentrated sulfuric acid.

2. An acetic acid solution of carbazol; diphenylimid, (C₆H₄<br>C₆H₄/ NH.)
3. A sulfuric acid solution of carbazol.
4. Standard solutions of potassium nitrate.
5. A solution of aluminum sulfate.
6. A solution of silver sulfate.
1. The sulfuric acid, used for all purposes in the process, should be entirely free from
nitrogen oxids. It may be readily tested by dissolving in it a small quantity of carbazol. If the
solution be at first golden-yellow or brown, the acid is sufficiently pure; if it be green or
greenish, another and better sample must be taken. It is essential also that the specific gravity
of the acid be fully 1.84, and it is well to ascertain that this is really the case.
2. The acetic acid solution of carbazol is prepared by dissolving six-tenths gram in about
ninety cubic centimeters of strongest acetic acid, by the aid of gentle heat. It is allowed to
cool, and is then made up to 100 cubic centimeters by the further addition of acetic acid. The
exact strength of this solution, is of no material importance to the success of the process, and
the above proportions have been selected principally because they are convenient. The
solution will remain unchanged for several months. The use of this solution merely facilitates
the preparation of that next described, which will not keep, and has, consequently, to be
freshly prepared for each series of determinations.
3. The sulfuric acid solution of carbazol is easily made in a few seconds, but it is advisable
to allow it to stand from one and one-half to two hours before using. It is prepared by rapidly
adding fifteen cubic centimeters of sulfuric acid, to one cubic centimeter of the above-
described acetic acid solution. This quantity usually suffices for from two to three nitrate
estimations. When freshly prepared it is golden-yellow or brown; it changes gradually,
however, and in the course of one and one-half or two hours it becomes olive-green. This
change is probably due to traces of oxidizing agents, which occur in the sulfuric and acetic
acids, and which, although not present in sufficient quantity to act immediately, gradually
bring about the reaction described. The greenish color does not interfere with the process, as
might at first be supposed; on the contrary, the solution is not sensitive to small quantities of
nitric acid until it has undergone the change to olive-green, and it is for this reason, that it
should be prepared about two hours before required for use. This solution may be thoroughly
depended on for six hours after preparation. The intensities of color produced by the more
concentrated solutions of nitrates after this time, gradually approach each other and become
ultimately the same.
4. The standard solutions of potassium nitrate are very readily prepared. The solutions
which are to be compared directly with the waters examined, may be prepared as required,
but if many determinations are to be made with a variety of waters, it will be found best to
prepare a complete series, differing from each other by 0.02 part nitrogen in 100,000. This
series may include solutions containing quantities of nitrogen in 100,000 parts, represented
by all the odd numbers from 0.03 up to 0.39. It will be found convenient to prepare them in
quantities of 100 cubic centimeters at a time, from a stock solution of potassium nitrate
which contains 0.00001 gram nitrogen, or 0.000045 nitric acid in one cubic centimeter.
Each cubic centimeter of this solution, when diluted to 100 cubic centimeters, represents
0.01 nitrogen in 100,000, and consequently if it is desired to make a solution containing 0.35
part nitrogen in 100,000, thirty-five cubic centimeters are taken and made up to 100 cubic
centimeters, and so on. The solution of potassium nitrate (b) is best prepared from a stronger
one (a) containing 0.0001 gram nitrogen to the cubic centimeter, or 0.7214 gram potassium
nitrate to the liter; 100 cubic centimeters of (a) made up to one liter give the solution (b). It is
obvious that the series of solutions, above described, could be made directly from (a), but by
first making (b), greater accuracy is secured.
5. For purposes which will be presently described, a solution of aluminum sulfate is
required, containing five grams to the liter. The salt used must be free from chlorin and iron;
and the solution should give no reaction when tested with carbazol.
6. The solution of silver sulfate is required for the removal of chlorin from the water or soil
extract to be examined. It is prepared by dissolving 4.3943 grams of the salt in pure distilled
water and making up to one liter. The sulfate is preferably obtained by dissolving metallic
silver in pure sulfuric acid. The solution should be tested with carbazol in the same way as
will be presently described for water; if perfectly pure, no reaction will be obtained. As silver
sulfate is often prepared by precipitation from the nitrate, it is very apt to contain nitric acid,
and consequently, if the source of the salt be unknown, this test should on no account be
omitted.
The analytical process is carried on as follows:
Two cubic centimeters of the water are carefully delivered by means of a pipette into the
bottom of a test-tube; four cubic centimeters of sulfuric acid are added, and the solution
thoroughly mixed by the help of a glass rod. The test-tube is then immersed in cold water,
and when well cooled, one cubic centimeter of the sulfuric acid solution of carbazol is added,
and the whole again mixed as before. The intensity of the color is now observed, and a little
experience enables a fairly good opinion to be formed of the quantity of nitric acid present.
Suppose that the water be roughly estimated to contain about 0.15 part nitrogen per
100,000; in such a case solutions of potassium nitrate containing 0.11, 0.15, 0.19 part
nitrogen are selected from the series. Two cubic centimeters are taken from each, and
treated, side by side, with a fresh quantity of the water, precisely as described for the
preliminary experiment, the various operations being performed as nearly simultaneously as
possible with each of the samples, and under precisely similar conditions. Two or three
minutes after the carbazol has been added, the intensity of the color of each is observed. If
that given by the water is matched by any of the standard solutions, the estimation is at an
end. Similarly, if it falls between two of these, the mean may be taken as representing the
nitrogen present in cases in which great accuracy is not required. If this be done, the
maximum error will be 0.02 part nitrogen, or 0.09 part nitric acid per 100,000. If greater
exactness be required, or it be found that the color given by the water is either darker or
lighter than that given by all the standard solutions, a new trial must be made. In such a case
the water must be again tested simultaneously with the solutions with which it is to be
compared. This is rendered necessary principally for the reason that the shade of the
solutions to which the carbazol has been added is apt to change on standing. Hence it is
desirable that the water, and the standard potassium nitrate with which it is to be compared,
should have the carbazol added at as nearly the same time as possible. When finally the color
falls between that given by any two consecutive members of the standard potassium nitrate
series, the estimation may be considered at an end, and the mean of these solutions taken as
representing the nitrogen present.
The greatest neatness should be observed in all steps of the analysis. The quantity of water
operated upon is so small that if the greatest care be not exercised throughout, sources of
error may be readily introduced. The test-tubes should be rinsed out with nitrate-free water
before being used and then dried. The tint should be determined by looking through the tube
and not through the length of the column of liquid.
Influence of Nitrites.—If the quantity of nitrous acid in the water is known a correction can
be applied for nitrates by deducting one-fifth of the number found for nitrites when
estimated as nitrates.
Influence of Iron.—Although ferrous salts give no reaction with carbazol, nitrates are apt to
be overestimated in their presence. Oh the other hand, ferric compounds, like other oxidizing
agents, may give a characteristic green color with carbazol. In all cases when iron is present
in any considerable quantity it is best to remove it by rendering the water slightly alkaline,
evaporating to dryness, and redissolving the soluble residue until the solution reaches the
original volume.
Influence of Chlorids.—The presence of chlorids furnishes by far the most serious source of
error in the process by intensifying the action of the nitric acid. If, however, nitrates be
absent chlorids give no reaction with carbazol. The chlorids are removed by a standard silver
sulfate solution, the quantity of chlorids present having been first determined by a standard
silver nitrate solution. For this purpose an ordinary sugar flask can be employed marked at
100 and 110 cubic centimeters. This flask is filled to the 100 cubic centimeter mark with the
water to be examined; the necessary quantity of silver sulfate is added and then two cubic
centimeters of the solution of aluminum sulfate, previously described, and the contents of the
flask brought up to 110 cubic centimeters by the addition of pure distilled water. The whole is
shaken up and filtered, the first portion of the filtrate being rejected. The aluminum sulfate
by reacting with the carbonates usually present in the water and producing the precipitation
of alumina, facilitates the removal of the precipitated silver chlorid.
The above-described method on account of its delicacy is not well suited to aqueous
solutions of soils except where the quantity of nitric nitrogen present is extremely minute.
 Hooker also first suggested the use of diphenylamin for detecting the presence of nitrates,
[326]
a method afterwards worked out by Spiegel.[327]
In the variation of the method as practiced by Rideal the standard potassium nitrate and
the pure sulfuric acid mentioned below are required, and in addition, the following reagents:
[328]

(a) Silver sulfate solution containing 4.3945 grams per liter.

(b) Aluminum sulfate solution free from chlorids and iron, five grams per liter.
(c) Carbazol solution; six-tenths gram carbazol dissolved in glacial acetic acid and made up
to 100 cubic centimeters with the glacial acid. For use, one cubic centimeter of this solution is
withdrawn by a pipette and mixed with fifteen cubic centimeters of pure redistilled sulfuric
acid.
The process is carried out as follows: To 100 cubic centimeters of water the amount of
chlorin which has been previously ascertained is removed by the silver sulfate solution. Two
cubic centimeters of the aluminum sulfate are added and the whole made up to a convenient
volume, say about 110 cubic centimeters. The liquid is filtered and two cubic centimeters of
the filtrate taken for an estimation of nitrates. To the two cubic centimeters are added four
cubic centimeters of concentrated sulfuric acid and the mixture cooled.
One cubic centimeter of the carbazol solution in sulfuric acid is added and a bright green
color appears in a few moments, if nitrates are present. Comparison is made with solutions of
standard potassium nitrate.
497. Phenylsulfuric Acid Method.—Rideal also proposes a variation of the method
described by Hooker, which consists in the substitution of phenylsulfuric acid for carbazol.
[329]

The solutions required are:

(a) A standard solution of potassium nitrate containing 0.7215 gram of the pure
crystallized salt in a liter of water.
(b) Phenylsulfuric acid, (acid phenyl sulfate,) prepared by dissolving fifteen grams of pure
crystallized phenol in 92.5 cubic centimeters of pure, redistilled sulfuric acid free from
nitrates and diluted with seven and one-half cubic centimeters of water.
The process is conducted as follows:
A known volume of water, from twenty-five to one hundred cubic centimeters, according to
its richness in nitrates, is evaporated to dryness in a porcelain dish, one cubic centimeter of
phenylsulfuric acid added then one cubic centimeter of pure water and three drops of strong
sulfuric acid and the mixture gently warmed. A yellow color shows the presence of nitrates.
Dilute to about twenty-five cubic centimeters with water and add ammonia in slight excess.
Pour into a narrow nessler tube and add the washings and make up to 100 cubic centimeters.
Imitate the color of the solution with the standard potassium nitrate treated with the same
reagents.
The phenylsulfuric acid should be prepared some time before use, as the fresh solution
imparts a greenish tint to the yellow of the ammonium picrate formed.
498. Variation of Leffmann and Beam.—The phenyl sulfate process, as described by
Leffmann and Beam, is conducted as follows:[330]
Solutions Required.—Acid phenyl sulfate: 18.5 cubic centimeters of strong sulfuric acid are
added to one and one-half cubic centimeters of water and three grams of pure phenol.
Preserve in a tightly-stoppered bottle.
Standard potassium nitrate: 0.722 gram of potassium nitrate, previously heated to a
temperature just sufficient to fuse it, is dissolved in water, and the solution made up to 1000
cubic centimeters. One cubic centimeter of this solution will contain 0.0001 gram of
nitrogen.
 Analytical Process.—A measured volume of the water is evaporated just to dryness in a
platinum or porcelain basin. One cubic centimeter of the acid phenyl sulfate is added and
thoroughly mixed with the residue by means of a glass rod. One cubic centimeter of water,
and three drops of strong sulfuric acid are added, and the dish gently warmed. The liquid is
then diluted with about twenty-five cubic centimeters of water, ammonium hydroxid added
in excess, and the solution made up to 100 cubic centimeters.
The reactions are:

Acid phenyl sulfate. Trinitrophenol (picric acid).

HC₆H₅SO₄ + 3HNO₃ = HC₆H₂(NO₂)₃O + H₂SO₄ + 2H₂O.

Ammonium picrate.
HC₆H₂(NO₂)₃O + NH₄HO = NH₄C₆H₂(NO₂)₃O + H₂O.

The ammonium picrate imparts to the solution a yellow color, the intensity of which is
proportional to the amount present.
Five cubic centimeters of the standard solution of potassium nitrate are similarly
evaporated in a platinum dish, treated as above, and made up to 100 cubic centimeters. The
color produced is compared to that given by the water, and one or the other of the solutions
diluted until the tints of the two agree. The comparative volumes of the liquids furnish the
necessary data for determining the amount of nitrate present, as the following example will
show:
Five cubic centimeters of standard nitrate are treated as above, and made up to 100 cubic
centimeters, representing 0.0005 gram nitrogen.
Suppose 100 cubic centimeters of water similarly treated are found to require dilution to
150 cubic centimeters before the tint will match that of the standard; then
100 : 150 :: 0.005 : 0.0075
i. e., the water contains seven and one-half milligrams of nitrogen as nitrate per liter.
The ammonium picrate solution keeps very well, especially in the dark. A good plan,
therefore, is to make up a standard solution equivalent to, say, ten milligrams of nitrogen as
nitrate per liter, to which the color obtained from the water may be directly compared.
The results obtained by this method are quite accurate. Care should be taken that the same
quantity of acid phenyl sulfate be used for the water and for the comparison liquid, otherwise
different tints instead of depths of tints are produced.
With subsoil and other waters probably containing much nitrates, ten cubic centimeters of
the sample will be sufficient for the test, but with river and spring waters, twenty-five to one
hundred cubic centimeters may be used. When the organic matter is sufficient to color the
residue, it will be well to purify the water by addition of alum and subsequent filtration,
before evaporating. The method may also be used to determine small quantities of nitrates in
aqueous extracts of soils when the quantity is too small for estimation by the ferrous chlorid
or reduction processes.
499. Variation of Johnson.—The ammonium picrate method has given very
satisfactory results as practiced by Johnson, who varies the process as described below.[331]
The standard solution of potassium nitrate is prepared by dissolving 0.7215 gram of the
pure salt in a liter of distilled water. Dilute 100 cubic centimeters of this solution to one liter
with distilled water. Ten cubic centimeters of this dilute solution contain nitrogen equivalent
to one part as nitrates in 100,000.
 The Solution of Acid Phenyl Sulfate.—This is prepared by pouring two parts by measure of
pure crystallized phenol liquefied by hot water into five parts by measure of pure
concentrated sulfuric acid and digesting the whole in the water-bath for eight hours. After
cooling, add one and one-half volumes of distilled water and one-half volume strong
hydrochloric acid to each volume of the above mixture.
The analytical processes are carried on as follows: Ten cubic centimeters of the water under
examination and ten cubic centimeters of the standard potassium nitrate are placed in small
beakers and put near the edge of a hot plate. When nearly evaporated they are put on the top
of the water-bath and left there until completely dry. The residue, in each case, is then treated
with one cubic centimeter of the acid phenyl sulfate and the beakers placed on the top of the
water-bath. In good water, a red color ought not to appear for about ten minutes.
After standing about fifteen minutes, the beakers are removed, the contents of each washed
successively into 100 cubic centimeter flasks, about twenty cubic centimeters of 0.96 per
cent. ammonia added, and the 100 cubic centimeters made up by the addition of water and
the yellow liquid transferred to the nessler glass and the tints appropriately compared.
500. Estimation of Nitric in Presence of Nitrous Acid.—The detection of nitrous in
presence of nitric acid can be accomplished by the method proposed by Griess, as described
further on, through the development of azocolors, with metaphenylenediamin and other
bodies, which are not produced under similar conditions by nitric acid. The detection and
estimation of nitric in the presence of nitrous acid, however, is not so easy. Lunge and Lwoff
propose brucin for this purpose, which, contrary to most authorities, does not give the red-
yellow color with nitrous acid.[332] The reagent is prepared by dissolving two-tenths gram of
brucin in 100 cubic centimeters of sulfuric acid, pure and concentrated. It is almost
impossible to prepare a sulfuric acid which does not give a trace of color with brucin; but with
the purest acids this trace may be neglected.
A solution of nitrate is also prepared containing 0.01 milligram of nitrogen as nitric acid in
one cubic centimeter. It is made by dissolving 0.0721 gram of pure potassium nitrate in 100
cubic centimeters of distilled water, and diluting ten cubic centimeters thereof with pure
concentrated sulfuric acid to 100 cubic centimeters. Both solutions are conveniently
preserved in burettes with glass stop-cocks. The liquid to be tested for nitric acid should be
mixed with sulfuric acid in such a way that the mixture will have a specific gravity of one and
seven-tenths. If the liquid to be tested is water, this concentration is reached by adding three
times its volume of the strong acid. For the comparison of colors, cylinders of colorless glass
are employed, marked at fifty cubic centimeters. They should be about twenty-four
centimeters high and extend about ten centimeters above the mark. There is placed in the
cylinder one cubic centimeter of the solution of nitrate in sulfuric acid, and the same quantity
of the brucin mixture, and it is filled to the mark with pure sulfuric acid. The contents of the
cylinder are poured into a flask and warmed at from 70°–80°, until the final yellow tint is
secured, and then poured into the cylinder again. The liquid to be tested is treated in exactly
the same way. The tints are then equalized by pouring out a part of the contents of the deeper
colored cylinder, taking account of the volume, and filling up with pure concentrated sulfuric
acid.
In this manner the content of nitric acid in the liquid under examination can be compared
directly with the solution of potassium nitrate of known strength. The coloration is distinctly
produced with 0.01 milligram in fifty cubic centimeters of liquid, at least three-fourths of
which must be sulfuric acid.
501. Piccini Process.—The method proposed by Piccini may also be used.[333]
About five cubic centimeters of the nitrite solution are placed in a small beaker, some pure
urea dissolved therein and a few drops of sulfuric acid, and then held in boiling water for
three minutes. The nitrous acid is thus completely destroyed. Ammonium chlorid may be
substituted for urea. The reaction is given on page 478. The nitric acid present is then
determined by diphenylamin or other suitable reagents. Diphenylamin reacts both with
nitrous and nitric acids, producing a violet tint. Warington calls attention to a slight
difference, however, in its deportment with these two acids. When the solution of the reagent
is not too strong a drop of it produces but little turbidity when added to water or to a solution
containing nitric acid. When, however, nitrous acid is present, a cream-colored turbidity is
produced. The violet color also appears at once on adding sulfuric acid when a nitrite is
present, while in the case of nitrates, more sulfuric acid is required, except when the solution
is very strong. In this connection, it must not be forgotten that in heating nitrites with urea or
ammonium chlorid in the presence of a slight excess of sulfuric acid a trace of nitric acid may
be formed.
 ESTIMATION OF NITROUS ACID BY COLORIMETRIC
COMPARISON.
502. Application of the Method.—The most minute traces of nitrous acid may be
detected by colorimetric methods and the determination of the quantity present may be
approximated with great exactness by comparison with a solution of a nitrite of known
strength. Especially in following the progress of nitrification is this method, in some of its
forms, of essential importance. In delicacy and celerity it has the same advantages as the
colorimetric methods for the determination of nitric acid.
503. Metaphenylenediamin Method.—This process depends upon the development of
a yellow color in water containing nitrous acid on the addition of a reagent containing
metaphenylenediamin; m-C₆H₄(NH₂)₂. This variety of the phenylenediamins is readily
obtained from common dinitrobenzene. It melts at 63° and boils at 287°. In order to preserve
the reagent in shape for use it should be prepared in the following manner:
Dissolve two grams of the chlorid in ten cubic centimeters of ammonia, and place the
solution in a glass-stoppered flask. To this solution are added five grams of powdered animal-
black, and the whole vigorously shaken. After allowing to settle, the shaking is repeated at
intervals of an hour, three or four times, and the flask then allowed to remain at rest for
twenty-four hours.
The supernatant liquid is generally sufficiently decolorized by this treatment. If not, the
shaking and subsidence must be repeated until a completely colorless liquid is obtained. The
solution can be kept, indefinitely, in contact with the animal-black. Aqueous and alcoholic
solutions of the salt can not be kept.
The test is applied by mixing five drops of the reagent with five cubic centimeters of
sulfuric acid. The mixture must be colorless. To the mixture add 100 cubic centimeters of the
water to be tested, and heat on the water-bath for five minutes. A yellow coloration indicates
the presence of nitrous acid.
The metaphenylenediamin test is fairly satisfactory in perfectly colorless waters and
aqueous extracts. Many waters and soil extracts, however, have a yellowish tint, and this
interferes in a marked way with a proper judgment of the yellow triaminazobenzol developed
in the application of the above test.
The decoloration of such waters by means of sodium carbonate or hydroxid and alum, is a
matter of some difficulty and not wholly without action on the nitrites which may be present.
The method, therefore, is inferior to the one next described.
504. Sulfanilic Acid and Naphthylamin Test for Nitrous Acid.—A very delicate
test for the presence of nitrous acid, first described by Griess, is the coloration produced
thereby in an acid solution of sulfanilic acid and naphthylamin.[334]
Sulfuric or acetic acid may be used as the acidifying agent, preferably the latter. The
solutions are prepared as follows:
(1) Dissolve one-half gram of sulfanilic acid in 150 cubic centimeters of dilute acetic acid.
(2) Boil one-tenth gram of naphthylamin with twenty cubic centimeters of water, decant
the colorless solution from the residue and acidify it with 150 cubic centimeters of dilute
acetic acid.
The two solutions may at once be mixed and preserved in a well-stoppered flask. The
action of light on the mixture is not hurtful, but air should be carefully excluded because of
the traces of nitrous acid which it may contain. Whenever the mixed solutions show a red tint
it is an indication that they have absorbed some nitrous acid. The red color may be
discharged and the solution again fitted for use by the introduction of a little zinc dust, and
shaking.
The water, or aqueous solution of a soil, to be tested for nitrites, in portions of about
twenty cubic centimeters, is treated with a few cubic centimeters of the mixed reagent and
warmed to 70°–80°. If nitrous acid, in the proportion of one part to one million be present,
the red color will appear in a few minutes. If the content of nitrous acid be greater, e. g., one
part in one thousand, only a yellow color will be produced, unless a greater quantity of the
reagent be used.
Leffmann and Beam recommend the following method of conducting the determinations.
[335]

Solutions required:
Naphthylammonium Chlorid.—Saturated solution in water free from nitrites. It should be
colorless; a small quantity of animal charcoal allowed to remain in the bottle will keep it in
this condition.
Paraamidobenzene Sulfonic Acid (Sulfanilic Acid).—Saturated solution in water, free from
nitrites.
Hydrochloric Acid.—Twenty-five cubic centimeters of concentrated pure hydrochloric acid
added to seventy-five cubic centimeters of water, free from nitrites.
Standard Sodium Nitrite.—0.275 gram pure silver nitrite is dissolved in pure water, and a
dilute solution of pure sodium chlorid added until the precipitate ceases to form. It is then
diluted with pure water to 250 cubic centimeters and allowed to stand until clear. For use, ten
cubic centimeters of this solution are diluted to 100. It is to be kept in the dark.
One cubic centimeter of the dilute solution is equivalent to 0.00001 gram of nitrogen.
The silver nitrite is prepared in the following manner: A hot concentrated solution of silver
nitrate is added to a concentrated solution of the purest sodium or potassium nitrite
available, filtered while hot and allowed to cool. The silver nitrite will separate in fine needle-
like crystals, which are freed from the mother-liquor by filtration with the aid of a filter
pump. The crystals are dissolved in the smallest possible quantity of hot water, allowed to
cool and crystallize, and again separated by means of the pump. They are then thoroughly
dried in the water-bath, and preserved in a tightly-stoppered bottle away from the light. Their
purity may be tested by heating a weighed quantity to redness in a tared, porcelain crucible
and noting the weight of the metallic silver. One hundred and fifty-four parts of silver nitrite
leave a residue of 108 parts of silver.
Analytical Process.—One hundred cubic centimeters of the water are placed in one of the
color-comparison cylinders, the measuring vessel and cylinder having previously been rinsed
with the water to be tested. By means of a pipette, one cubic centimeter each of the solutions
of sulfanilic acid, dilute hydrochloric acid, and naphthylammonium chlorid is dropped into
the water in the order named. It is convenient to have three pipettes for this test, and to use
them for no other purpose. In any case the pipette must be rinsed out thoroughly with nitrite-
free water each time before using, as nitrites, in quantity sufficient to give a distinct reaction,
may be taken up from the air.
One cubic centimeter of the standard nitrite solution is placed in another clean cylinder,
made up with nitrite-free water to 100 cubic centimeters and treated with the reagents, as
above.
In the presence of nitrites a pink color is produced, which, in dilute solutions, may require
half an hour for complete development. At the end of this time the two solutions are
compared, the colors equalized by diluting the darker, and the calculation made as explained
under the estimation of nitrates.
 The following are the reactions:

Paraamidobenzene Nitrous acid. Paradiazobenzene sulfonic acid.

sulfonic acid.
C₆H₄NH₂HSO₃ + HNO₂ = C₆H₄N₂SO₃ + 2H₂O.

Naphthylammonium Azoalphaamidonaphthalene
chlorid. parazobenzene sulfonic acid.
C₆H₄N₂SO₃ + C₁₀H₇NH₃Cl = C₁₀H₆(NH₂)NNC₆H₄HSO₃ + HCl.

The last named body gives the color to the liquid.

The method pursued by Tanner, in the preparation of the reagent, is as follows:
Sulfanilic acid is prepared by mixing thirty grams of anilin slowly, with sixty grams of
fuming sulfuric acid, in a porcelain dish. The brown, sirupy liquid formed is carefully heated
until quite dark in color, and until the evolution of sulfurous fumes is noticed. After cooling,
the thick, semi-fluid mass is poured into half a liter of cold water and allowed to stand for
some hours. The liquid portion is then decanted from the nearly black undissolved crystalline
mass. To the residue half a liter of hot water is added and allowed to stand until cold, and the
liquid again decanted. The undissolved portion is then treated with one liter of hot water and
filtered. The filtrate is treated with animal charcoal to decolorize it, and allowed to stand for
twenty-four hours and again filtered, the filtrate diluted to 1,500 cubic centimeters and used
as required. This solution tends to turn pink on keeping, and thus its color interferes with the
delicacy of the test, and a small amount of animal-char is kept in a small bottle containing the
portion for immediate use, and this bottle is filled, from time to time, from the larger one.
The solution of naphthylamin hydrochlorate is made with one gram of the salt dissolved in
100 cubic centimeters of water. The solution is to be occasionally filtered, and not more than
100 cubic centimeters should be prepared at a time.
The analytical operations are carried on as follows:
A standard solution of pure potassium nitrite, made from the silver salt in distilled water
perfectly free from nitrites, is placed in a color-glass, similar to those used in the nessler
reaction, together with a second glass containing the water to be tested. These glasses should
be marked to hold 100 cubic centimeters at the same depth. To each of the tubes a few drops
of pure hydrochloric acid are added and two cubic centimeters of the sulfanilic solution.
Afterwards, to each tube are added two cubic centimeters of the solution of naphthylamin
hydrochlorate, and it is allowed to stand for twenty minutes, at the end of which time the
color should be fully developed. Each tube is covered by a piece of glass in order to prevent
access of air. It is unnecessary to add that the standard solutions of nitrite of different
strength should be employed until the one is found which resembles, as nearly as possible,
the color developed in the sample of water under examination.
505. Lunge and Lwoff’s Process for Nitrous Acid.—The reaction of nitrous acid with
α naphthylamin, first described by Griess, may be made reliable, quantitatively, by
proceeding as below:[336]
Boil 0.100 gram of pure white α naphthylamin for fifteen minutes with 100 cubic
centimeters of water, add five cubic centimeters of glacial acetic acid, or its equivalent of
dilute acid, and afterwards one gram of sulfanilic acid dissolved in 100 cubic centimeters of
hot water. The mixture is kept in a well-closed flask. A slight red tint in the mixture is of no
significance, inasmuch as this completely disappears when one part of it is mixed with fifty
parts of the liquid to be examined. If the coloration be very strong it can be removed by
adding a little zinc dust. One cubic centimeter of this reagent will give a distinct coloration
with 0.001 milligram of nitrous nitrogen in 100 cubic centimeters of water.
 The analysis is conducted in cylinders of white glass marked at fifty cubic centimeters. One
cubic centimeter of the above reagent is placed in each of two cylinders with forty cubic
centimeters of water and five grams of solid sodium acetate. In one of the cylinders is placed
one cubic centimeter of a normal solution of a nitrite prepared by dissolving 0.0493 gram of
pure sodium nitrite corresponding to ten milligrams of nitrogen in 100 cubic centimeters of
water, and adding ten cubic centimeters of this solution to ninety cubic centimeters of pure
sulfuric acid. This secures a normal solution of nitrosylsulfuric acid, of which each cubic
centimeter corresponds to 0.01 milligram of nitrogen.
In the other cylinder is placed one cubic centimeter of the solution to be examined, and the
contents of both cylinders are well mixed so that the nitrous acid in a nascent state may act
on the reagent. The colors are compared after any convenient period, but, as a rule, after five
minutes.
The chief improvement made by Lunge and Lwoff on the method of Griess is in keeping the
reagent in a mixed state ready for use, by means of which any nitrous impurities in the
components thereof are surely indicated. Its advantage over the method of Ilosvay[337]
consists in using the comparative normal nitrite solution as nitrosylsulfuric acid, in which
state it is much more stable.
506. Estimation of Nitrous Acid with Starch as Indicator.—The method of
procedure, depending on the blue color produced in a solution of starch in presence of a
nitrite and zinc iodid when treated with sulfuric acid, is not of wide application on account of
the interference produced by organic matter. The soil extract or water is treated in a test-
tube, with a few drops of starch solution and some zinc iodid, to which is added some sulfuric
acid. The decomposition of the nitrite is attended with the setting free of an equivalent
amount of iodin which gives a blue coloration to the starch solution. The depth of the tint is
imitated by treating a standard solution of nitrite in a similar way until the proper quantity is
found, which gives at once the proportion of nitrite in the sample examined. This process,
however, is scarcely more than a qualitative one.
507. Estimation of Nitrites by the Method of Chabrier.—In order to make the
estimation of the evolved nitrous acid more definite by the iodin method, Chabrier has
elaborated a plan for titrating it with a reducing agent.[338]
The substance chosen for this purpose is sodium hyposulfite. In point of fact, it is not the
nitrous acid which is attacked by the hyposulfite, but the equivalent amount of free iodin
representing it. In the case of a soil where the quantity of nitrites is usually very small, it is
well to take as much as one kilogram. The extraction should be made rapidly, with water, free
of nitrites, in order to avoid any reducing action on the nitrates which may be present. In the
case of water, from five to ten liters should be evaporated to a small volume. The
concentration should take place in a large flask, rather than in an open dish, in order to avoid
any possibility of the absorption of nitrites produced by combustion. When the volume has
been reduced to about 100 cubic centimeters it is transferred to a small flask and the
concentration continued until only ten or fifteen cubic centimeters are left. The residue is
filtered into a woulff bottle, F, Fig. 89, of about 100 cubic centimeters capacity.
One of the side tubulures carries a burette, B, containing five per cent sulfuric acid, the
other one filled with a hyposulfite solution of known strength. The middle tubule serves to
introduce a glass tube through which carbon dioxid or illuminating gas passes for the
purpose of driving out the air from the solution and the flask. If carbon dioxid be used it
should be generated by the action of sulfuric acid on marble. The cork holding this is
furnished with a slot or valve to permit the exit of the air and the excess of the gas.
Before inserting the middle stopper, a few cubic centimeters of potassium iodid solution
and a few drops of thin starch paste are added, the potassium salt being always used in excess
of the nitrite supposed to be present.
 Figure 89. Method of Chabrier.

After the air has all been expelled from the flask the analytical process is commenced, the
carbon dioxid current being slowly continued. At first, a few drops of the dilute sulfuric acid
are allowed to flow into the flask. As soon as the liquid is colored blue a sufficient quantity of
the thiosulfate solution is added to discharge the color. The successive addition of acid and
thiosulfate is continued until another portion of the acid fails to develop the blue color, thus
indicating that all the nitrite has been decomposed. From the volume of thiosulfate used the
quantity of nitrite is calculated.
The Thiosulfate Solution.—The thiosulfate solution is conveniently prepared, when a large
number of analyses is to be made, by dissolving twenty-five grams of pure crystallized sodium
thiosulfate in 100 cubic centimeters of water and diluting any convenient part thereof to 100
or 1,000 cubic centimeters, according to the supposed strength of nitrite solution under
examination.
For fixing the strength of the solution dissolve 3 348 grams of pure iodin in a solution of
potassium iodid and make the volume up to one liter. Each cubic centimeter of this solution
corresponds to one milligram of nitrous acid. A given volume of the iodin solution is titrated
against the thiosulfate, but it is best not to add the starch paste until the greater part of the
iodin has been removed. The starch paste is then added and the titration continued until the
blue color has been discharged. Ten cubic centimeters of the iodin solution is a convenient
quantity for the titration and the thiosulfate should be diluted by adding to ten cubic
centimeters of the solution mentioned above, 990 cubic centimeters of water. Each liter of
this dilute solution contains two and a half grams of the sodium thiosulphate.
Example.—Let us suppose that it has required 21.3 cubic centimeters of thiosulfate to
absorb ten cubic centimeters of the iodin solution; further that ten liters of water have been
evaporated and titrated as described above, and that the volume of thiosulfate employed was
13.8 cubic centimeters. From this is derived the following formula: 13.821.3
× 10
= 6.48 milligrams
of nitrous acid; or 0.648 milligram per liter.
508. Estimation of Nitrous Acid By Coloration of Solution of Ferrous Salt.—
This method, due to Picini is based on the production of the well-known brown color formed
by the action of nitric oxid on a ferrous salt.[339] The nitrite is decomposed by heating with
acetic acid while nitrates thus treated do not develop the reaction. The tint produced is
imitated as above by testing against a standard solution of nitrite. Ferrous chlorid is to be
preferred to other ferrous salts for the above purpose. The process should be carried on in
solutions free of air.
509. Estimation of Nitrous Acid By Decomposition with Potassium
Ferrocyanid.—The method of Schaeffer was first described in 1851, but little attention has
been paid to it since. The method has lately been brought into notice again by Deventer.[340]
The reaction depends upon the decomposition of nitrous acid by potassium ferrocyanid in
the presence of acetic acid with the formation of potassium ferricyanid and acetate, and nitric
oxid. The reaction is expressed by the following equation:
2K₄FeCy₆ + 2HNO₂ + 2C₂H₄O₂
= K₆Fe₂Cy₁₂ + 2KC₂H₃O₂ + 2NO + 2H₂O.
A eudiometer with a glass stop-cock is arranged as shown in
Fig. 90. The lower part of the eudiometer is closed with a rubber
stopper carrying a glass tube which ends in the pan f as shown at
e. The eudiometer is filled to the stop-cock with a solution of
potassium ferrocyanid of about fourteen per cent strength. The
dish f is also filled up to the height indicated in the figure with the
same solution. The solution of nitrite is used in such quantities
that the nitric oxid evolved will occupy a space of about twenty
cubic centimeters. The whole eudiometer should contain about
fifty-seven cubic centimeters. The nitrite solution is added to the
eudiometer by means of a funnel, a. The vessel containing it is
washed out with a little water and then with acetic acid and finally
with a few cubic centimeters of strong potassium ferrocyanid
solution. The last fluid flows through the solution of nitrite and
acetic acid and thus mixes it with the solution already in the
eudiometer. The liquids reacting on each other float together on
the strong ferrocyanid solution and each one of them is at once
pressed downward by the gases which are evolved. When the
evolution of gas becomes slower the apparatus should be shaken
for about twenty minutes, moving it back and forth without taking
the bottom of it out of the dish. When there is no longer any
evolution of gas, water is added through a slowly, until the heavy
potassium ferrocyanid solution is almost completely driven out of
the eudiometer. The opening of the tube at e is then closed with
Figure 90.
the thumb, the apparatus is taken out of the dish, shaken for some
Schaeffer’s Nitrous Acid time in a vertical direction and again placed in the dish. Water of
Method. any required temperature is now allowed to flow through the
jacket, g, h, until the temperature is constant, when the volume of
nitric oxid is read. The whole experiment can be performed in less
than an hour. Operating in this way, at the end there is in the eudiometer a liquid which is
not very different from water and one whose coefficient of solubility for nitric oxid is
practically the same as that of water. The gas volume read is to be corrected for temperature,
pressure, tension of the aqueous vapor, height of the water column in the eudiometer, and,
after the end of the calculation, five per cent of the volume of water remaining in the
eudiometer is to be added to the volume of gas obtained. This is to compensate for the
volume of the gas absorbed by the water. The method gives good quantitive results.
510. Method of Collecting Samples of Rain Water for Analysis.—Warington
collects rain water in a large leaden gauge having an area of 0.001 of an acre.[341] Of the daily
collection of rain, dew, and snow water, an aliquot part amounting to a gallon for each inch of
precipitation is placed in a carboy; at the end of each month the contents of the carboy are
mixed, and a sample taken for analysis. In the carboy receiving the rain for nitric acid
estimation a little mercuric chlorid is placed each month with the view of preventing any
change of ammonia into nitric acid. It may be doubted, however, if this precaution is
necessary, as the rain water thus collected always contains a very appreciable amount of lead;
and experiments have shown that on the whole, rain water more frequently gains than loses
ammonia by keeping.
Preparation of the Sample.—The method first employed by Warington was to concentrate
ten pounds of the rain water in a retort, a little magnesia being used to decompose any
ammonium nitrite or nitrate present. Concentration by evaporation in the open air, and
especially over gas, results in a distinct addition to nitrites present. When concentrated to a
small bulk, the water is filtered and evaporated to dryness in a very small beaker. The
nitrogen as nitrates and nitrites is then determined by means of the methods already
described.
 DETERMINATION OF FREE AND ALBUMINOID AMMONIA
IN RAIN AND DRAINAGE WATERS AND SOIL EXTRACTS.
511. Nessler Process.—The quantities of free ammonia in rain and most drainage waters
are minute, but may reach considerable magnitude in some sewages. By reason of these
minute proportions, gravi- and volumetric methods are not suitable for its quantitive
determination. Recourse is therefore had to the delicate colorimetric reaction first proposed
by Nessler. This reaction is based on the yellowish-brown coloration produced by ammonia
in a solution of mercuric iodid in potassium iodid. The coloration is due to the formation of
oxydimercuric ammonium iodid, NH₂Hg₂OI, and takes place between the molecule of free
ammonia and the mercuric iodid dissolved in the alkaline potassium iodid as represented by
the following equation:

Hg—O—Hg—I Hg
/ / \
O + 2H₂N = 2O NH₂I + H₂O
\ \ /
Hg—O—Hg—I HG

Nessler Reagent.—Dissolve thirty-five grams of potassium iodid in 100 cubic centimeters

of water. Add to this solution gradually a solution of seventeen grams of mercuric chlorid in
300 cubic centimeters of water until a permanent precipitate of mercuric iodid is formed.
Add now enough of a twenty per cent solution of sodium hydroxid to make 1000 cubic
centimeters.
The mixed solutions, at room temperature, are treated with additional mercuric chlorid
until the precipitate formed, after thorough stirring, remains undissolved. This precipitate is
then allowed to subside, and when the supernatant liquid is perfectly clear, it is decanted or
filtered through asbestos and kept in a well-stoppered bottle in a dark place. The part in use
should be transferred to a smaller bottle as required. The solution should be made for a few
days before using, since its delicacy is increased by keeping. The nessler reagent should show
a faint yellow tint. If colorless it is not delicate, and shows the addition of an insufficient
quantity of mercuric chlorid. When properly prepared, two cubic centimeters of the reagent
poured into fifty cubic centimeters of water containing 0.05 milligram of ammonia will at
once develop a yellowish-brown tint.
Preparation of Ammonia-Free Water.—To pure distilled water add pure, recently-ignited
sodium carbonate, from one to two grams per one liter, and distill. When one-fourth of the
whole has passed over, the distillate may be regarded as free from ammonia; fifty cubic
centimeters of the following distillate should give no reaction with the nessler reagent. The
distillation should be continued until the residual volume in the retort is about one-fourth of
the original, and the distillate free of ammonia is carefully preserved in close glass-stoppered
bottles previously washed with ammonia-free water. Pure water, free of ammonia may also
be obtained by distilling with sulfuric acid.
Comparative Solution of Ammonium Chlorid containing 0.00001 gram Ammonia in one
cubic centimeter.—Dissolve 3.15 grams H₄NCl in ammonia-free water and make the volume
up to one liter. Take ten cubic centimeters of the above solution and dilute to 1000 with
water, free from ammonia.