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Exploring the Variety of Random
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 The method of drying practiced at Rothamstead, in order to secure
results as nearly accurate as possible is the following:[293]
The soil is broken up directly after it is taken from the field, and
spread on trays in layers one inch deep. The trays are then placed in
a room at 55°. The drying is completed in twenty-four hours. After
drying, stones and roots are removed, and the soil is finely powdered
and placed in bottles.
For extracting the nitrates, a funnel is prepared by cutting off the
bottom from a bottle four and a half inches in diameter. A nicely
fitting disk of copper gauze is placed in the bottom of this funnel, and
this is covered with two filter papers, the upper one having a slightly
greater diameter than the lower. The paper is first moistened, and
then from 200 to 500 grams of the dry powdered soil introduced.
The funnel is connected with the receiving flask of a filter pump, and
pure water poured on the soil until it is thoroughly saturated. The
water is then added in small quantities. When the filtrate amounts to
100 cubic centimeters the process may be discontinued, since all the
nitrates in the soil will be found in this part of the filtrate.
The extract obtained above is evaporated to convenient bulk for
the determination of nitric nitrogen.
 THE NITRIC OXID PROCESS.
459. Method of Schloesing.—The processes for estimating
nitrogen by combustion with copper oxid and by moist combustion
with sulfuric acid have both been used for the determination of the
quantity of nitrogen existing in a highly oxidized state. These
processes will be fully discussed under the head of fertilizers. In the
case of soil extracts, drainage waters, etc., it will be sufficient to
discuss, for the present, only those processes adapted especially to a
quick and accurate estimation of oxidized nitrogen.
The principle of the method of Schloesing depends on the
decomposition of nitrates in the presence of a ferrous salt and a
strong mineral acid.[294] The nitrogen in the process appears as nitric
oxid, the volume of which may be directly measured, or it may be
converted into nitric acid and titrated by an alkali.
The typical reactions which take place are represented in the
following equation:
6FeCl₂ + 2KNO₃ + 8HCl = 3Fe₂Cl₆ + 2KCl + 4H₂O + 2NO.
460. Schloesing’s Modified Method.—The Schloesing method
as now practiced by the French chemists is conducted in the
apparatus shown in Fig. 75.[295] The carbon dioxid is generated by the
action of the hydrochloric acid in F on the fragments of marble in A.
After passing the wash-bottle the gas enters the small tubulated
retort, C, which contains the nitrate in solution. For ordinary soils
100 grams are placed in an extraction flask, plugged with cotton, and
a layer of the same material is placed over the soil for the purpose of
securing an even distribution of the extracting liquid. This liquid is
distilled water containing in each liter one gram of calcium chlorid.
The purpose of using the calcium chlorid is to prevent the soil from
becoming compacted which would render the extraction of the
nitrate difficult. The extracting liquid is allowed to fall drop by drop
from a mariotte bottle until the filtrate amounts to 500 cubic
centimeters. This volume is concentrated on a sand-bath until it is
reduced to ten or fifteen cubic centimeters when it is transferred to a
flat-bottomed dish and the evaporation finished over steam, care
being taken not to allow the temperature to exceed 100°.

Figure 75. Schloesing’s Apparatus for Nitric Acid.

Another and more rapid method for dissolving the nitrate, may
also be practiced. In a flask holding about one liter, place 220 grams
of the soil and 660 cubic centimeters of distilled water and shake
vigorously, or enough water to make 660 cubic centimeters together
with the moisture remaining in the air-dried sample taken. All the
nitrates pass into solution. Throw the contents of the flask into a
filter and take 600 cubic centimeters of the filtrate which will contain
all the nitrates in 200 grams of the sample taken. This filtrate is
evaporated as described above.
In the flat dish containing the dried nitrates, pour three or four
cubic centimeters of ferrous chlorid solution and stir with a small
glass rod until complete solution of the nitrate takes place. By means
of a small funnel the solution is poured into C, and the capsule and
funnel are well rinsed with two cubic centimeters of hydrochloric
acid. The washing is repeated three times as above described, and
once with one cubic centimeter of water, which is added cautiously
so as to form a layer over the surface of the heavier liquid. The
tubulated flask is then connected with the carbon dioxid apparatus,
previously freed from air, and the gas allowed to flow evenly until the
whole of the apparatus is completely air-free. The other details of the
method are essentially the same as those adopted by the Commission
of French Agricultural Chemists which will be given below.
461. The French Agricultural Method.—The Schloesing
method as practiced by the French agricultural chemists is very
slightly different from the procedure just described.[296] The process
with soils is carried on as follows:
Five hundred grams of the soil are taken and introduced into a
flask of about two liters capacity and shaken thoroughly with a liter
of distilled water. The whole of the nitrates of the soil is thus passed
into solution. The solution is filtered and 400 cubic centimeters of
the filtrate are taken, which correspond to 200 grams of the soil. This
liquid is evaporated in a flask, adding a fragment of paraffin to
prevent foaming, until its volume is reduced to fifteen or twenty
cubic centimeters. It is afterwards transferred through a filter into a
capsule with a flat bottom in which the evaporation is finished on a
steam-bath, taking care that the temperature does not exceed 100°.
An important precaution is, not to allow the contact of the water with
the soil to be too prolonged, to avoid the reduction of the nitrates
which could take place under the influence of the denitrifying
organisms which are developed with so great a rapidity in moist
earth. The apparatus in which the transformation of the nitrates into
nitric oxid takes place is essentially that already described (Fig. 75).
The carbon dioxid generator is connected by means of a rubber tube
and a small wash-bottle to the small retort in which the reaction
takes place, and from which the exit tube leads to a mercury trough.
The gas which is disengaged is received under a jar drawn out to a
fine point in its upper part, which carries about fifteen cubic
centimeters of potash solution containing two parts of water to one
of potash.
The operation is conducted as follows:
Into the small capsule which contains the dried matter, three or
four cubic centimeters of ferrous chlorid are poured. By means of a
stirring rod the residue sticking to the sides of the capsule is
detached with care and all the matter is thus collected in the bottom.
By means of a small funnel the contents of the capsule are
introduced into the retort. About two cubic centimeters of
hydrochloric acid are used for washing out the materials and this
acid is also introduced into the retort. The washing with hydrochloric
acid is repeated three or four times, and finally the apparatus is
washed with one cubic centimeter of water, which is also poured in
by the small funnel with great care, so that this water may form a
layer over the surface of the liquid. The apparatus is now connected
and filled completely with carbon dioxid. Since it is necessary that
this gas should be completely free of air, the flask, which generates it,
is first filled with the acidulated water from the acid flask, and the air
is thus almost totally displaced by the liquid. The evolution of carbon
dioxid gas which follows, completely frees the apparatus from air.
When this is accomplished the retort is connected with the rest of the
apparatus and the gas allowed to pass for about two minutes until
the air is completely driven out of all the connections. The current is
arrested for a moment by pinching the rubber tube which conducts
the carbon dioxid into the retort, and the vessel which is to receive
the gas is then placed over the delivery-tube, this vessel being filled
with mercury and a strong solution of potash. The communication
between the retort and the carbon dioxid flask is broken and the flask
is heated slightly by means of a small lamp. The first bubbles of gas
evolved should be entirely absorbed by the potash. This will be an
indication of the complete absence of the air. When the liquid is in a
state of ebullition the nitrogen dioxid is set free. The boiling is
regulated in such a way that the evolution is regular and the liquid of
the retort may not, by a too violent boiling, pass into the receiver.
The boiling is continued until the larger part of the liquid is distilled
and only three or four cubic centimeters remain in the retort. At this
time a few bubbles of carbon dioxid are allowed to flow through in
order to cause to pass into the receiver the last traces of nitric oxid.
The gas received is left for some minutes in contact with the potash.
Afterward in a small flask, G, the neck of which is drawn out to a
fine point, and carrying a bulb-tube, H, and a piece of rubber tubing,
there are boiled twenty-five or thirty cubic centimeters of water for
five or six minutes in order to drive all the air out of the flask, and
while the boiling is continued the rubber tubing is fastened to the
drawn-out part of the jar containing the nitric oxid. Within the
rubber tubing the drawn-out point is broken and the vapor of water
is forced into the jar and drives before it the solution of potash which
has filled the capillary part of the drawn-out tube. As soon as the
point is broken, the boiling of the flask is stopped and by its cooling
the nitric oxid passes into it. It is necessary to press the rubber
tubing with the fingers in order that the passage of the gas into the
flask be not too rapid. As the solution of potash rises in the bell-jar
which contains the nitric oxid near to the point where the rubber
tubing covers its drawn-out portion, the fingers are removed and a
clamp put in their place. There still remains a little nitric oxid in the
flask and to drive this out it is necessary to introduce five or six cubic
centimeters of pure hydrogen, which are allowed to pass over into
the receiving flask, by releasing the clamp in the same way as the
nitric oxid. The hydrogen being introduced in successive portions,
finally carries all the nitric oxid into the flask without allowing any of
the potash to enter.
The flask containing the nitric oxid is now connected with a
reservoir of oxygen. The oxygen is allowed to enter, bubble by
bubble, by means of cooling the flask by immersion in water. The
transformation of nitric oxid into nitric acid is not entirely complete
for twenty-four hours. It is necessary, therefore, to wait that long
after the introduction of the oxygen before determining the amount
of nitric acid produced.
The contents of the flask are placed in a titration-jar, the flask
being washed two or three times and a few drops of tincture of litmus
being added. The nitric acid is then determined by a standard
solution of calcium hydroxid or some other standard alkali. From the
titration the content of nitric acid is calculated.
The French Committee further suggests that this method may be
modified in the way of making it more rapid by collecting the nitric
acid in a graduated tube filled with mercury and containing some
potash. The volume of the gas is determined and the pressure of the
barometer and the temperature observed, and the usual calculations
made to reduce the volume to zero and to a pressure of 760
millimeters of mercury. Each cubic centimeter of nitric oxid thus
measured corresponds to 2.417 milligrams of nitric acid. The
presence of organic matter does not interfere with the determination
of nitric acid by either of the methods given above.
462. Modification of Warington.—The method of procedure
and description of apparatus used, as employed by Warington, are as
follows:
The vessel in which the reaction takes place is a small tubulated
receiver, A (Fig. 76), about four centimeters in diameter, mounted
and connected as shown in the illustration. The delivery-tube dips
into a jar of mercury in a trough containing the same liquid. The long
supply funnel-tube a is of small bore, holding in all only one-half
cubic centimeter. The connecting tube F, carrying a clamp, is also of
small diameter and serves to connect the apparatus with a supply of
carbon dioxid.
In practice, the supply-tube a is
first filled with strong hydrochloric
acid and carbon dioxid passed
through the apparatus until the air is
all expelled. This is indicated when a
portion of the gas collected over the
mercury, is entirely absorbed by
caustic alkali.
At this point the current of carbon
dioxid is stopped by the clamp C,
and a bath of calcium chlorid, B,
Figure 76. Warington’s Apparatus heated to 140° is brought under the
for Nitric Acid.
bulb A, until the latter is half
immersed therein. The temperature
of the bath is maintained by a lamp. By allowing a few drops of
hydrochloric acid to enter the receiver, the carbon dioxid is almost
wholly expelled. The end of the delivery-tube is then connected with
the tube, T, filled with mercury, and the apparatus is ready for use.
The nitrate, in which the nitric acid is to be determined, in a dry
state, is dissolved in two cubic centimeters of the ferrous chlorid
solution (one gram of iron in ten cubic centimeters), one cubic
centimeter of strong hydrochloric acid is added, and the whole is
then introduced into the receiver through the supply-tube, being
followed by successive rinsings with hydrochloric acid, each rinsing
not exceeding one-half cubic centimeter. The contents of the receiver
are, in a few moments, boiled to dryness; a little carbon dioxid is
admitted before dryness is reached, and again afterwards to drive
over all remains of nitric oxid. In the recovered gas the carbon dioxid
is first absorbed by caustic potash, and afterwards the nitric oxid by
ferrous chlorid. All measurements of the gas are made in Frankland’s
modification of Regnault’s apparatus. The carbon dioxid should be as
free as possible from oxygen. The carbon dioxid generator is formed
of two vessels, the lower one consisting of a bottle with a tubule in
the side near the bottom; this bottle is supported in an inverted
position and contains the marble from which the gas is generated.
The upper vessel consists of a similar bottle standing upright and
containing the hydrochloric acid required to act on the marble. The
two vessels are connected by a glass tube passing from the side
tubule of the upper vessel to the inverted mouth of the lower vessel.
The acid from the upper vessel thus enters below the marble. Carbon
dioxid is generated and removed at pleasure by opening a stop-cock
attached to the side tubule of the lower vessel thus allowing
hydrochloric acid to descend and come in contact with the marble. A
good Kipp’s generator of any approved form may also be used
instead of the simple apparatus, above described.
The fragments of marble used are previously boiled in water in a
strong flask. After boiling has proceeded for some time, a rubber
stopper is fixed in the neck of the flask and the flame removed.
Boiling will then continue for some time in a partial vacuum.
The hydrochloric acid is also well boiled and has dissolved in it a
moderate quantity of cuprous chlorid. As soon as the acid has been
placed in the upper reservoir, it is covered by a layer of oil. The
apparatus being thus charged is at once set in active work by opening
the stop-cock of the marble reservoir; the acid descends, enters the
marble reservoir, and the carbon dioxid produced drives out the air.
As the acid reservoir is kept on a higher level than the marble
reservoir, the latter is always under internal pressure, and leakage of
air from without, into the apparatus, cannot occur.
The presence of the cuprous chlorid in the hydrochloric acid not
only insures the removal of dissolved oxygen, but affords an
indication to the eye of the maintenance of this condition. While the
acid remains of an olive tint, oxygen is absent; but should the color
change to a blue-green, more cuprous chlorid must be added. All the
reagents employed should be previously boiled.
In order to secure absolute freedom from air, the following
modifications on the above process have been adopted by
Warington: The apparatus having been mounted as described, the
funnel-tube attached to the bulb retort is filled with water, and the
apparatus connected with the carbon dioxid generator. Carbon
dioxid is then passed through the apparatus until a moderate stream
of bubbles rises in the mercury trough. The stop-cock is left in this
position, and the admission of gas is controlled by the pinch-cock.
The bath of calcium chlorid is so adjusted as to cause the bulb retort
to be almost entirely submerged, and the temperature of the bath is
kept at 130° to 140°. Small quantities of water are next admitted into
the bulb and expelled as steam in the current of carbon dioxid, the
supply of this gas being shut off before the evaporation is entirely
completed, so as to leave as little carbon dioxid as possible in the
apparatus. Previous to very delicate experiments it is advisable to
introduce through the funnel-tube a small quantity of potassium
nitrate, ferrous chlorid, and hydrochloric acid, rinsing the tube with
the latter reagent. Any trace of oxygen remaining in the apparatus is
then consumed by the nitric oxid formed; and after boiling to
dryness and driving out the nitric acid with carbon dioxid, the
apparatus is in a perfect condition for a quantitative experiment.
463. Preparation of the Materials to be Analyzed.—
According to Warington, soil extracts may be used without other
preparation than concentration.
Vegetable juices which coagulate when heated, require to be boiled
and filtered or else evaporated to a thin sirup, treated with alcohol,
and filtered. A clear solution being thus obtained, it is concentrated
over a water-bath to a minimum volume in a beaker of small size. As
soon as cool, it is mixed with one cubic centimeter of a cold saturated
solution of ferrous chlorid and one cubic centimeter of hydrochloric
acid, both reagents having been boiled and cooled immediately
before use.
In mixing with the reagents, care must be taken that bubbles of air
are not entangled, which is apt to occur with viscid extracts.
The quantity of ferrous chlorid mentioned is amply sufficient for
most soil extracts, but it is well to use two cubic centimeters in the
first experiment, the presence of a considerable excess of ferrous
chlorid in the retort being thus insured. With bulky vegetable
extracts more ferrous chlorid should be employed. To the sirup from
twenty grams of mangel-wurzel sap, five cubic centimeters of ferrous
chlorid and two cubic centimeters of hydrochloric acid are usually
added.
464. Measurement of the Gas.—The measurement of the gas
was for some time conducted by the use of concentrated potash for
absorbing the carbon dioxid, and ferrous chlorid for absorbing the
nitric oxid. The use of the ferrous chlorid, however, was found to
introduce a source of error. The treatment of the gas with oxygen and
pyrogallol over potash has therefore been substituted by Warington
for its absorption by ferrous chlorid.
The chief source of error attending the oxygen process lies in the
small quantity of carbon monoxid produced during the absorption
with pyrogallol; this error becomes negligible if the oxygen be only
used in small excess. The amount of oxygen employed can be
regulated by the use of Bischof’s gas delivery-tube. This may be made
of a test-tube having a small perforation half an inch from the
mouth. The tube is partly filled with oxygen over mercury, and its
mouth is then closed by a finely perforated stopper made from a
piece of wide tube and fitted tightly into the test-tube by means of a
covering of rubber. When this tube is inclined, the side perforation
being downwards, the oxygen is discharged in small bubbles from
the perforated stopper, while mercury enters through the opening.
Using this tube, the supply of oxygen is perfectly under control and
can be stopped as soon as a fresh bubble ceases to produce a red
tinge on entering. Warington concludes his description by stating
that in the reaction proposed by Schloesing the analyst has a means
of determining a very small quantity of nitric acid with considerable
accuracy, even in the presence of organic matter; but to accomplish
this, the various simplifications consisting in the omission of the
stream of carbon dioxid, and the collection of the gas over caustic
soda must be abandoned, and special precautions must be taken to
exclude all traces of oxygen from the apparatus.
465. Spiegel’s Modification.—Spiegel noticed inaccuracies in
the results of the ferrous chlorid method of estimating nitric acid
when carbon dioxid is used, which sometimes amounted to three per
cent of the nitric acid present in the sample. The following
suggestions are made by him for the improvement of the process:[297]
As regards the use of carbon dioxid in the operation, the first
difficulty consists in obtaining it entirely free from air. By the use of
small pieces of marble, which, before being placed in the Kipp
apparatus, are kept for a long while in boiling water, a product is
obtained which, after thirty minutes of moderate evolution, leaves
only a trace of unabsorbed gas in contact with potash-lye. The
apparatus used is illustrated in Fig. 77.
A is a round flask of about 150
cubic centimeters capacity, furnished
with a well-fitting rubber stopper
provided with two holes, one for the
entrance of the funnel-tube B and the
other for the delivery-tube C. The
tube B ends about two centimeters
above the bottom of A and carries a
bulb-shaped funnel at its top capable
of holding about fifty cubic
centimeters. The gas-tube D is ground
into the bulb of B as shown in the
figure.
After the flask had been filled with
the solution to be examined, carbon
dioxid is conducted through D and
the flask is heated to boiling until the
gas which escapes through C no
longer contains any air. The
measuring tube is brought over the
end of the delivery-tube C, in the Figure 77. Spiegel’s Apparatus
usual manner, but not shown in the for Nitric Acid.
figure. In the funnel of B are placed
twenty cubic centimeters of previously prepared and boiled ferrous
chlorid solution and this liquid is allowed to flow partly into A by
lifting slightly the gas-tube, D. About forty cubic centimeters of
concentrated, boiled hydrochloric acid are afterwards added to it in
the same way. As soon as the liquid in the flask A is again boiling, the
stream of carbon dioxid is shut off and allowed to flow again only
towards the end of the operation, when the contents of the flask are
reduced almost to dryness. As will be seen from the above directions
no unboiled liquids of any kind are to be used as reagents in the
apparatus described. If the flask A were made much smaller the
efficiency of this apparatus would be increased. It appears to have
few, if any, advantages over Warington’s process.
 466. Schulze-Tiemann Method.—The modification of
Schulze-Tiemann in the ferrous salt method consists chiefly in the
omission of the use of carbon dioxid, and in the simplified form of
apparatus, which permits rapid work and gives, also, according to
some authorities, very exact and reliable results.[298] The extract,
representing 500 grams of the fine soil, is reduced by evaporation to
100 cubic centimeters and placed in a glass flask, A (Fig. 78), of 500
cubic centimeters capacity. The flask is closed with a rubber stopper,
carrying two bent glass tubes which pass through it. The tube a b c is
drawn out into a point at a and reaches about two centimeters below
the surface of the rubber stopper. The tube e f g passes just to the
lower surface of the rubber stopper. The two tubes mentioned are
connected, by means of rubber tubes and pinch-cocks, with the tubes
d and h. The pinch-cocks at c and g must be capable of closing the
tubes air-tight. The end of the tube g h passes into a crystallizing
dish, B, and is bent upward to a point passing two to three
centimeters into the measuring tube C. The point within the tube is
covered with a piece of rubber tubing. The measuring tube C is
divided into tenths of a cubic centimeter, and together with the
crystallizing dish B, is filled with a ten per cent solution of boiled
soda-lye, which is obtained by dissolving 12.9 parts of sodium
hydroxid in 100 parts of water.
The liquid which is to be
examined for nitric acid, the
pinch-cocks being opened and
the tube g h not dipping into
the crystallizing dish, is boiled
for one hour in order to drive
the air out of the flask A. The
end of the tube e f g h is then
brought into the crystallizing
dish containing the sodium
hydroxid solution so that the
steam escaping from the flask
A, escapes partly through the
tube b c d, and partly through
the tube f g h, not allowing,
Figure 78. Schulze-Tiemann’s Nitric however, the bubbles to enter
Acid Apparatus. the measuring tube C. To
determine whether the air is all expelled, the pinch-cock at g is
closed and the soda-lye will thereupon rise to g in case no air
interferes. It is best to close the tube at g first with the thumb and
finger and then the rise of the soda-lye to that point can be
determined by the impulse felt. The tube is then firmly closed by
means of the pinch-cock g. The rest of the steam is allowed to escape
through the tube a b c d, and the evaporation is continued until the
contents of the flask are evaporated to about ten cubic centimeters.
The flask into which the tube c d dips, is filled with freshly boiled
water. The lamp is removed from the flask A, the pinch-cock is
closed, whereupon the tube c d becomes filled with the freshly boiled
water. The measuring tube C, filled with freshly boiled soda-lye is
closed with the thumb and brought into the dish B, care being taken
that no bubble of air enters. It is placed over the end of the tube g h.
The pressure of the external air will now flatten the rubber tubes at
c and g. The flask at the end of c d holding freshly boiled water is
then replaced with one filled with a nearly saturated solution of
ferrous chlorid containing some hydrochloric acid. The flask
containing the ferrous chlorid solution should be graduated so that
the amount which is sucked into the flask A can be determined. The
pinch-cock c is opened and from fifteen to twenty cubic centimeters
of the ferrous chlorid solution allowed to flow into A. The end of the
tube c d is then placed in another flask containing strong
hydrochloric acid, and the latter allowed to flow into the tube in
small quantities at a time until all the ferrous chlorid is washed out
of the tube b c d into A. At the point b there is sometimes formed a
little bubble of hydrochloric acid in the state of gas, which by heating
the flask A completely disappears.
The flask A is next warmed gently until the rubber tubes at the
pinch-cocks begin to assume their normal condition. The pinch-cock
at g is now replaced by the thumb and finger, and as soon as the
pressure within the flask A is somewhat stronger, caused by the
nitric oxid gas evolved from the mixture, it is allowed to pass through
the tube e f g h and escape into the measuring cylinder C. By a
manipulation of the finger and thumb at g, it is possible to prevent
regurgitation of the sodium hydroxid into A, and at the same time to
relieve the pressure of the nitric oxid in A, which would be difficult to
do by means of the pinch-cock alone.
 The boiling of the liquid is continued until there is no longer any
increase of the volume of gas in the measuring cylinder C. After the
end of the operation the tube g h is removed from the dish B and the
measuring tube C is closed by means of the thumb while its end is
still beneath the surface of the soda-lye, and it is shaken until all
traces of any hydrochloric acid, which may have escaped absorption,
are removed. It is then placed in a large glass cylinder filled with
water at the temperature at which the volume of gas is to be read.
After being kept at this constant temperature for about half an hour
the volume of the nitric oxid can be read. For this purpose the
measuring cylinder C is sunk into the water of the large cylinder until
the level of the liquids within and without the tube is the same. The
usual correction for pressure of the atmosphere, as determined by
the barometer, and for the tension of the aqueous vapor at the
temperature at which the reading is made, is applied. The correction
is made by means of the following formula:
V′ = (V × 273 × (B − f)) ÷ ((273 + t) × 760)
In this formula V′ denotes the volume of the gas at the
temperature of zero, and at 760 millimeters barometric pressure; V
the volume of the gas as read at the barometric pressure observed, B,
and the temperature observed, t, while f denotes the tension of the
aqueous vapor in millimeters of mercury pressure at the observed
temperature t. The tension of the aqueous vapor at temperatures
from zero to 26°, expressed in millimeters of mercury, is given in the
following table:
 Temp. ° Tension in mm. mercury.
0 4.6
1 4.9
2 5.3
3 5.7
4 6.1
5 6.5
6 6.9
7 7.4
8 8.0
9 8.5
10 9.1
11 9.7
12 10.4
13 11.1
14 11.9
15 12.7
16 13.5
17 14.4
18 15.3
19 16.3
20 17.4
21 18.5
22 19.6
23 20.9
24 22.2
25 23.5
26 25.0
From the gas volume reduced by the above formula the nitric acid
is calculated as follows:
One cubic centimeter of nitric oxid weighs at 0° and 760
millimeters barometric pressure 1.343 milligrams.
Since two molecules of NO (molecular weight sixty) correspond to
one molecule of N₂O₅ (108) we have the following equation: 60 : 108
= 1.343 : x. Whence x = 2.417 milligrams, the weight of nitric acid
corresponding to one cubic centimeter of nitric oxid.
 Figure 79. De Konick’s Apparatus.

467. DeKonick’s Modification of Schloesing’s

Method.—This modification consists in an
arrangement of the gas delivery-tube, whereby the
regurgitation of the water in the measuring burette into
the evolution flask is prevented by a device for sealing
the delivery-tube with mercury.[299] The apparatus is
arranged as shown in Fig. 79. The flask in which the
Figure 80. decomposition takes place is provided with a long neck,
End of
Delivery-
into which a side tube is sealed and bent upwards,
Tube. carrying a small funnel attached to it by rubber tubing.
The piece of rubber tubing carries a pinch-cock, by
means of which the solution containing the nitrate and
hydrochloric acid can be introduced into the flask. The small gas
delivery-tube is arranged as shown in the figure, and carries at the
end next the burette a device shown in Fig. 80. The cork represented
in this device has radial notches cut in it, so as to permit of a free
communication between the water in the burette and in the
pneumatic trough. The open end of the burette, when the apparatus
is mounted ready for use, rests on the notched surface of the cork,
and the end of the delivery-tube is placed in the crystallizing dish
resting on the bottom of the pneumatic trough.
The end of the delivery-tube, as indicated, has fused onto it a
vertical tube open at both ends and six to seven centimeters in
length, and carrying the notched cork already described. The
crystallizing dish in the bottom of the pneumatic trough is filled with
mercury until the point of union of the delivery-tube with the vertical
end is sealed to the depth of a few millimeters. As the gas is evolved
it bubbles up through the mercury into the measuring tube and the
displaced water passes out through the notches in the cork. Should
any back pressure supervene the mercury at once rises in the
delivery-tube which is of such a length as to prevent its entrance into
the flask. The operation can then be carried on with absolute safety.
To make an estimation there are placed in the flask about forty
cubic centimeters of ferrous chlorid solution containing about 200
grams of iron to the liter, and also an equal volume of hydrochloric
acid of one and one-tenth specific gravity. The side tube is also filled
up to the funnel with the acid. The contents of the flask are boiled
until all air is expelled, which can be determined by holding a test-
tube filled with water over the end of the delivery-tube. The solution
containing the nitrate is next placed in the funnel, the pinch-cock
opened and the liquid allowed to run into the flask by means of the
partial vacuum produced by stopping the boiling and allowing the
mercury to rise in the delivery-tube. All the solution is washed into
the flask by successive rinsings of the funnel with hydrochloric acid,
being careful to allow no bubble of air to enter. The contents of the
flask are again raised to the boiling-point and the nitric oxid evolved
collected in the nitrometer. The solution examined should contain
enough nitrate to afford from sixty to eighty cubic centimeters of gas.
Without refilling the flask, from eight to nine determinations can be
made by regenerating the ferrous chlorid by treatment with zinc
chlorid. Care must be exercised not to add the zinc chlorid in excess,
otherwise ammonia and not nitric oxid will be produced. The side
tube and funnel must also be carefully freed from zinc chlorid by
washing with hydrochloric acid.
 468. Schmidt’s Process.—In the case of a water, or the aqueous
extract of a soil, according to the content of nitric acid, from fifty to
one hundred cubic centimeters are evaporated to thirty cubic
centimeters, and the residue sucked into the generating flask of the
apparatus, Fig. 81, and, with the rinsings with distilled water,
evaporated again to from twenty to thirty cubic centimeters, and the
flask then connected, as shown in the figure, to a Schliff measuring
apparatus, B.[300] This apparatus is previously filled to i with
mercury, and the bulb g connected with k by a rubber tube.
The apparatus is then
filled with a twenty per
cent, previously boiled
and still warm, caustic
soda solution until the
bulb g is partially filled
when raised a little above
the cock h. Then h is
closed and g held, by an
appropriate support, on
about the same level with
h. The cock at b is then
closed and e opened.
Meanwhile the ebullition
in the flask is continued,
and the air bubbles rising
in the Schliff apparatus
are removed, from time
Figure 81. Schmidt’s Apparatus.
to time, by carefully
opening h and raising g.
When bubbles no longer come over, the cock at e is closed and at b
opened, and the steam issuing at a is conducted through a mixture of
ferrous chlorid and strong hydrochloric acid to free it, as far as
possible, from air. When the contents of the flask have been
evaporated to about five cubic centimeters, b is closed and the lamp
at once removed.
By carefully opening b about ten cubic centimeters of a mixture of
ferrous chlorid and hydrochloric acid are allowed to enter the flask,
when b is closed and the flask slowly heated until the positive
pressure is restored. The pinch-cock e is then opened and the
contents of the flask evaporated nearly to dryness. The cock e is
again closed and the flame removed. Another quantity (fifteen cubic
centimeters) of ferrous chlorid and hydrochloric acid solution is
sucked into the flask and the process of distillation repeated,
whereby the whole of the nitric oxid is collected in h. The nitric oxid
evolved is measured in the usual way and calculated to nitric acid,
one cubic centimeter of nitrogen dioxid being equal to 2.417
milligrams of nitric acid.
469. Merits of the Ferrous Chlorid Process.—The possibility
of an accurate determination of nitrates; by decomposition with a
ferrous salt in presence of an excess of acid, has been established by
many years of experience and by the testimony of many analysts. The
method is applicable especially where the quantity of nitrate is not
too small and when organic matter is present. In the case of minute
quantities of nitrate, however, the process is inapplicable and must
give way to some of the colorimetric methods to be hereafter
described.
In respect of the apparatus modern practice has led to the
preference of that form which does not require the use of carbon
dioxid for displacing the air. Steam appears to be quite as effective as
carbon dioxid and is much more easily employed. That form of
apparatus should be used which is the simplest in construction and
has the least cubical content.
The measurement of the evolved gas is most simply made by
collecting over lye in an azotometer, reading the volume, noting the
reading of the barometer and thermometer and then reducing to
standard conditions of pressure and temperature by the customary
calculations. Where a very strong lye is used the tension of the
aqueous vapor may be neglected. While every analyst should have a
thorough knowledge of the ferrous chlorid method and the principles
on which it is based it can not be compared in simplicity to the later
methods with pure nitrates which are based on the conversion of the
nitric acid into ammonia by the action of nascent hydrogen. In
accuracy, moreover, it does not appear to have any marked
advantage over the reduction methods.
470. Mercury and Sulfuric Acid Method.—This simple and
accurate method of determining nitric acid in the absence of organic
matter is known as the Crum-Frankland process.[301]
The method rests on the principle of converting nitric acid into
nitric oxid by the action of mercury in the presence of sulfuric acid.
The operation as at first described is conducted in a glass jar eight
inches long by one and a half inches in diameter filled with mercury
and inverted in a trough containing the same liquid. The nitrate to be
examined, in a solid form, is passed into the tube together with three
cubic centimeters of water and five of sulfuric acid. With occasional
shaking, two hours are allowed for the disengagement of the gas,
which is then measured.
471. Warington’s Modification.—A graduated shaking tube is
employed which allows the nitrate solution and oil of vitriol to be
brought to a definite volume. The nitrate solution, with rinsings, is
always two cubic centimeters and enough sulfuric acid is added to
increase the volume to five cubic centimeters. The sulfuric acid
should give no gas when shaken with distilled water. Any gas given
off in the apparatus before shaking, is not expelled but is included in
the final result. The persistent froth sometimes noticed where some
kinds of organic matter are present, is reduced by the addition of a
few drops of hot water through the stop-cock of the apparatus. The
nitric oxid is finally measured in Frankland’s modification of
Regnault’s apparatus.
This method, accurate for pure nitrates, unfortunately fails in the
presence of any considerable amount of organic matter.
According to Warington’s observations the presence of chlorids is
no hindrance to the accurate determination of both nitric and nitrous
acids by the mercury method. This simplifies the operation as carried
on by Frankland who directs that any chlorin present, be removed
before the determination of the nitric acid is commenced.
472. Noyes’ Method.—In the analyses made by Noyes for the
National Board of Health, the Crum-Frankland method was
employed.[302] The apparatus used was essentially that which is now
known as Lunge’s nitrometer and it will be described in the next
paragraph. No correction is made by Noyes for the tension of
aqueous vapor in the measurement of the nitric oxid because of the
moderate dilution of the sulfuric acid by the liquid holding the nitric
compounds in solution. The chlorin was not removed from the dry
residue of the evaporated water as its presence in moderate quantity
does not interfere with the accuracy of the process. In order to obtain
the amount of nitrogen in the form of nitrates, the total volume of
nitric oxid must be diminished by that due to nitrites present, which
must be determined in a separate analysis. The method of
manipulation is given in the following paragraph.
 473. Lunge’s Nitrometer.—The apparatus
employed by Noyes, in a somewhat more elaborate
form, is known as Lunge’s nitrometer.[303] This
apparatus is shown in Fig. 82. It consists of a burette,
a, divided into one-fifth cubic centimeters. At its
upper end it is expanded into a cup-shaped funnel
attached by a three-way glass stop-cock. Below, the
burette is joined to a plain tube, b, of similar size, by
means of rubber tubing. The apparatus is first filled
with mercury through the tube b, the stop-cock being
so adjusted as to allow the mercury to fill the cup at
the top of a. The cock is then turned until the mercury
in the cup flows out through the side tube carrying
the rubber tube and clamp. The three-way cock is
closed, and the solution containing the nitrate placed
in the cup. By lowering the tube b and opening the
cock the liquid is carefully passed into a, being careful
to close the cock before all the liquid has passed out
of the cup. By repeated rinsings with pure
concentrated sulfuric acid, every particle of the nitric
compound is finally introduced into a, together with a
large excess of sulfuric acid. The total volume of the
introduced liquid should not exceed ten cubic
Figure 82. Lunge’s Nitrometer. centimeters. The mixture of the mercury, nitric
compound, and sulfuric acid is effected by detaching
a from its support, compressing the rubber
connection between a and b, placing a nearly in a horizontal position, and quickly bringing it
into a vertical position with vigorous shaking.
After about five minutes the reaction is complete, and the level of the liquids in the two
tubes is so adjusted as to compensate for the difference in specific gravity between the acid
mixture in a and the mercury in b; in other words, the mercury column in b should stand
above the mercury column in a one-seventh of the length of the acid mixture in a. This
secures atmospheric pressure on the nitric oxid which has been collected in a. The measured
volume of nitric oxid should be reduced to 0° and 760 millimeters barometric pressure. Each
cubic centimeter of nitric oxid thus obtained corresponds to 1.343 milligrams NO; 2.417
milligrams N₂O₅; 4.521 milligrams KNO₃; 1.701 milligrams N₂O₃; 2.820 milligrams HNO₃;
and 3.805 milligrams NaNO₃.
474. Lunge’s Improved Apparatus.—Lunge has lately improved his apparatus for
generating and measuring gases and extended its applicability.[304] The part of it designed to
measure the volume of a gas is the same in all cases. For generating the gas, the apparatus
varies according to the character of the substance under examination.
The measuring apparatus is shown in Fig. 83. It is composed essentially of three tubes,
conveniently mounted on a wooden holder with a box base for securing any spilled mercury.
The support is not shown in the illustration.
The tubes A, B, C, are mutually connected by means of a three-way tube and rubber tubing
with very thick walls to safely hold the mercury without expansion. In the middle of the
measuring tube A, is found a bulb of seventy cubic centimeters capacity. Above and below the
bulb the tube is divided into tenths of a cubic centimeter, and its diameter is such, viz., 11.3
millimeters, that each cubic centimeter occupies a length of one centimeter. The upper end of
A is closed with a glass cock with two oblique perforations, by means of which
communication can be established at will, either through e with the apparatus for generating
the gas, or through d with the absorption apparatus, or the opening be completely closed.
The volume of air under the observed conditions which would
measure exactly 100 cubic centimeters at 0° and 760
millimeters pressure of mercury, is calculated by the formula
V = 100(273 + t)760
273(b − f) ;

where t equals observed temperature, b the barometric pressure

less the correction noted above and f the tension of the vapor of
water under existing conditions. For example:

Figure. 83.

Lunge’s Improved Apparatus.

Let the temperature be 18°

Barometric reading 755
Correction for t 2
Corrected barometer 753
Vapor of water tension 16

Then V = 100(273 + 18)760

273(753 − 16) = 109.9.

This indicates that 109.9 cubic centimeters of air would occupy a volume of 100 cubic
centimeters when subjected to standard conditions.
The tubes A, B, and C are filled with mercury of which about two and a half kilograms will
be required. By means of the leveling tube B, the stopper in C being opened, the mercury in C
is brought exactly to 109.9 cubic centimeters. The stopper in C is then closed, mercury
poured into D, which is then closed with a rubber stopper, carrying a small glass tube as
indicated in the figure.
 The leveling tube B serves to regulate the pressure on the gas in A and this is secured by
depressing or elevating it as the case may require.
The tube for reducing the volume to standard conditions of temperature and pressure, viz.,
0° and 760 millimeters of mercury, is shown in C. In its narrow part which has the same
internal diameter as A it is graduated into tenths of a cubic centimeter. The upper end of C is
furnished with a heavy glass neck D surmounted by a glass cup. In the neck is placed a
ground-glass stopper, carrying a groove below, which corresponds to a similar groove above
in the side of the neck whereby communication can be established at will between the
interior of C and the exterior. The joint is also sealed by pouring mercury into D as is shown
in the figure. When the stopper is well ground and greased the reduction tube may be raised
or lowered as much as may be necessary without any danger of escape or entrance of gas. To
determine the position of the reduction tube C the reading of the barometer and
thermometer at room temperature is taken. From the reading of the barometer subtract one
millimeter if the temperature be below 12°, two millimeters at a temperature from 12° to 19°,
three from 20° to 25°, and four above 25°.
When a gas has been introduced into the measuring tube A it is brought to the volume
which it would assume under standard conditions by adjusting the tube C in such a way as to
bring the level of mercury in C and A to the same point and the level of the mercury in C is
exactly at 100 cubic centimeters. The gas in A is then at the volume which it would occupy
under standard conditions and this volume can be directly read. This adjustment is secured
by moving the tubes B and C up or down. If gases are to be measured wet, a drop of water
should be put on the side of the upper part of C, and, if dry, of sulfuric acid, before the
adjustment for temperature and pressure.
475. Method of Manipulation.—By the action of mercury in the presence of sulfuric
acid, the nitrogen in nitrates, nitrites, nitrosulfates, nitroses, nitrocellulose, nitroglycerol,
and the greater number of explosives, may be obtained and measured as nitric oxid. The
nitrogen compounds are decomposed in the apparatus shown in Fig. 84.
To make an analysis, the apparatus is filled with mercury, through F, until the two
openings in the cock and i are entirely occupied with that liquid. The cock h is then closed,
and the nitrogen compound, in solution, introduced through g, care being taken that no air
enters g when F is depressed and h opened to admit the sample. The funnel g is washed
several times with a few drops of sulfuric acid, which are successively introduced into G. The
total liquid introduced should not exceed ten to fifteen cubic centimeters, of which the
greater part should be sulfuric acid. The rubber tube connecting G and F is carefully closed
with a clamp and G violently shaken for a few minutes until no further evolution of nitric
oxid takes place. In shaking, the apparatus should be so held as to prevent the escape of the
mercury from the small tube i by keeping it closed with the finger or drawing over it a rubber
cap.
After the evolution of the gas has ceased, the tube e, Fig. 83, is brought into contact with i,
Fig. 84, and the two are joined by a tight-fitting piece of rubber tubing in such a way as to
exclude any particle of air. The tube F, Fig. 84, is lifted and B and C, Fig. 83, depressed. On
carefully opening the cocks h and b and bringing i and e into union, the gas is passed from G
into A. When all the gas has entered A and the acid mixture from G has reached b the latter is
closed, and also h. The apparatus G is disconnected and removed. The gas in A is then
reduced to normal conditions by manipulating the reduction tube C in the manner already
described.
The gas in A is measured dry by reason of having been generated in presence of rather
strong sulfuric acid. Consequently, for this operation the adjustment of the volume of gas in
C should be made in contact with a drop of strong sulfuric acid. In order to make the
readings, a quantity of material must be taken which will give less than thirty or from 100 to
140 cubic centimeters of nitric oxid.
 The quantities of the different compounds of nitric acid corresponding
to the number of cubic centimeters of nitric oxid, measured under
standard conditions, are shown in the following table:

Figure 84.

Lunge’s Analytic
Apparatus.

CORRESPONDING TO
———————————— ———————————— ————————————
Cubic Weight in N₂O₃ in milligrams. HNO₃ in milligrams. NaNO₃ in milligrams.
centimeters milligrams.
of NO.
1 1.343 1.701 2.820 3.805
2 2.682 3.402 5.640 7.610
3 4.029 5.103 8.460 11.415
4 5.372 6.804 11.280 15.220
5 6.715 8.506 14.100 19.025
6 8.058 10.206 16.920 22.830
7 9.401 11.907 19.740 26.635
8 10.744 13.608 22.560 30.440
9 12.087 15.309 25.380 34.245

476. Utility of the Method.—Where it is desirable that the nitric oxid method be used,
and at the same time heating be avoided, the decomposition of a nitrate by means of metallic
mercury and sulfuric acid affords a convenient and accurate procedure. But, as a rule, there
is no objection to the application of the lamp, and in such cases the mercury method appears
to have no advantage over the ferrous chlorid process. Nevertheless, in the hands of a skilled
worker the results are reliable, and the process is a quicker one, on the whole, than by
distillation with ferrous chlorid and hydrochloric acid. This method, however, can not be
recommended as in any way superior to the reduction methods to be hereinafter described.
 ESTIMATION OF NITRIC ACID BY OXIDATION OF A
COLORED SOLUTION.
477. Method of Boussingault.—The process for the estimation of nitric acid by the
decoloration of a solution of indigo is due originally to Boussingault.[305] In this method the
extract, obtained by washing slowly 200 grams of soil until the filtrate amounts to 300 cubic
centimeters, is evaporated until its volume is no greater than two or three cubic centimeters,
and it is transferred to a test-tube, with washings, and again evaporated in the tube until the
volume is not greater than that last mentioned. A few drops of solution of indigo are added,
and then two cubic centimeters of pure hydrochloric acid; the whole is then heated. As the
color of the indigo disappears more is added. When the color ceases to fade, the liquid in the
test-tube is concentrated by boiling. If concentration fail to destroy the blue or green color,
another one-half cubic centimeter of hydrochloric acid is introduced. The reaction is
completed when neither concentration nor fresh addition of hydrochloric acid destroys the
excess of indigo present. The color produced by a small excess of indigo is a bright sap-green;
this tint is the final reaction sought. The small excess of indigo necessary to produce a green
color is deducted in every experiment.
When more than mere traces of organic matter are present, Boussingault advises that the
nitric acid be first separated by distillation and then reduced by the indigo solution. For this
purpose the concentrated solution of the nitrate, two or three cubic centimeters, is placed in
a small tubulated retort with two grams of manganese dioxid in fine powder. The retort is
next half filled with fragments of broken glass, over which is poured one cubic centimeter of
concentrated sulfuric acid. The retort is heated carefully by means of a small flame, which is
kept in motion so as to successively come in contact with all parts of the bottom of the retort.
The distillate is received in a graduated test-tube which is kept cool. The distillation is
continued until the vapors of sulfuric acid begin to appear. The apparatus is allowed to cool,
the stopper of the retort removed, two cubic centimeters of water introduced, and the
distillation again made until fumes of sulfuric acid are again seen. The distillation with water
is made twice in order to remove every trace of nitric acid from the retort. The distillate is
neutralized with a solution of potassium hydroxid and concentrated to two cubic
centimeters, and the nitric acid estimated in the manner already described. The manganese
dioxid used should be previously well washed and the sulfuric must be free of nitric acid.
Preparation of the Indigo Solution.—Fifty grams of indigo in fine powder are digested for
twenty-four hours, at 40°, in a liter of distilled water. The water is then poured off and
replaced with a fresh supply. After the second decantation the residue is treated with 750
cubic centimeters of equal parts of water and pure concentrated hydrochloric acid and boiled
for an hour. After cooling, the undissolved portion is collected on a filter and washed at first
with hot, and afterwards with cold water, until the filtrate is no longer colored and is free of
acid. The dried residue is treated with ether under a bell-jar, or in a continuous extraction
apparatus, until the ether is only of a faint blue tint. The fifty grams of indigo at first taken
will give about twenty-five grams of the purified article, which, however, will still leave a little
ash on combustion.
Solution in Sulfuric Acid.—Five grams of the purified indigo are placed in a flask having a
ground-glass stopper, treated with twenty-five grams of fuming sulfuric acid, and allowed to
digest two or three days at a temperature of from 50° to 60°. From seventy to 200 drops of
the solution thus made are placed in 100 cubic centimeters of water for use in the process.
Standardization of the Indigo Solution.—The solution as prepared above is standardized
by a solution of one gram of pure potassium nitrate in 1,000 cubic centimeters of distilled
water. The oxidation of the indigo solution is accomplished as described above. For this
strength of standard nitrate solution two cubic centimeters are taken corresponding to two
milligrams of potassium nitrate. The indigo solution for this strength should have only
twenty drops of the sulfuric acid solution of indigo to 100 cubic centimeters of water. If
twenty grams of potassium nitrate are taken for 1,000 cubic centimeters of the standard
solution then 200 drops of the sulfindigotic acid should be used to 100 cubic centimeters of
water.
478. Method of Marx.—As usually practiced, the indigo method is conducted according
to the variation described by Marx.[306] There are required for the process the following
reagents and apparatus:
a. A solution of pure potassium nitrate containing 1.8724 grams per liter. One cubic
centimeter of the solution is equivalent to one milligram of nitric anhydrid (N₂O₅).
b. A solution of the best indigo carmine in water which should be approximately
standardized by solution in the manner described hereafter, and then diluted so that six to
eight cubic centimeters equal one milligram of nitric acid.
c. Chemically pure sulfuric acid of specific gravity 1.842, perfectly free from sulfurous and
arsenious acids and nitrogen oxids.
d. Several thin flasks of about 200 cubic centimeters capacity.
e. A small cylindrical measure holding fifty cubic centimeters and divided into cubic
centimeters.
f. A Mohr’s burette divided into tenths of a cubic centimeter.
g. A twenty-five cubic centimeter pipette or another burette.
h. A five cubic centimeter pipette divided into cubic centimeters or half cubic centimeters.
i. A measuring flask of 250 cubic centimeters capacity.
Preliminary Trial.—Twenty-five cubic centimeters of the sample are transferred to a flask;
the fifty cubic centimeter measure is filled with sulfuric acid and the burette with indigo
solution. The sulfuric acid is added to the sample all at once, shaken for a moment, and the
indigo run in as quickly as possible with shaking until a permanent greenish tint is produced.
If the sample do not require more than twenty cubic centimeters of indigo solution of the
above strength, it can be titrated directly, otherwise it must be diluted with a proper quantity
of pure water, and subjected again to the preliminary trial.
The Actual Titration.—(1) Twenty-five cubic centimeters of the sample properly diluted if
necessary, are measured and poured into a flask, and as much indigo as was used in the
preliminary trial, is added; a quantity of sulfuric acid, equal in volume to the liquid in the
flask, is added all at once, the mixture shaken, and indigo solution run in quickly out of the
burette until the liquid remains permanently of a greenish tint.
(2) The last experiment is repeated as often as may be necessary adding to the water at
first half a cubic centimeter less indigo than the total quantity used previously, afterwards
proceeding as in (1) until the final test shows too little indigo used.
(3) From the rough titration of the indigo, calculate the amount of potassium nitrate
solution corresponding with the indigo solution used in (2), multiply the result by ten,
transfer this quantity of the standard nitrate solution to a 250 cubic centimeter flask, fill with
pure water to the mark, and titrate twenty-five cubic centimeters of this fluid with indigo as
in (2). If the quantity of indigo solution used is nearly the same as that required in (2), its
exact value may be calculated, but if it is not, another nitrate solution may be made up in the
250 cubic centimeter flask, more closely resembling the sample in strength, and the titration
with the indigo solution must be repeated.
(4) If the water contain any considerable amount of organic matter, it must first be
destroyed by potassium permanganate. In this case, the estimation of the organic matter and
nitric acid may be conveniently combined.
The use of permanganate in the above case is likely to introduce an error as has been
shown by Warington. The method therefore can not be recommended in the presence of
organic matter.
479. Method of Warington.—The modification of the indigo method as used by
Warington, applicable only in absence of organic matter, is the one chiefly employed in
England.[307]
Instead of the ordinary indigo of commerce, indigotin is used. The normal solution of the
coloring matter is made of such a strength as to be equivalent to a solution of potassium
nitrate containing 0.14 gram of nitrogen per liter. Where large quantities of the coloring
matter are to be used it is advisable to prepare it about four times the strength given above
and then dilute it as required. Four grams of sublimed indigotin will furnish more than two
liters of the color solution.
The solution is prepared as follows:
Four grams of indigotin are digested for a few hours with five times that weight of
Nordhausen sulfuric acid, diluted with water, filtered, and made up to a volume of two liters.
The strength of the indigotin solution is determined with a solution of potassium nitrate of
the strength mentioned above. The process is performed as follows:
From ten to twenty cubic centimeters of the standard nitrate solution are placed in a wide-
mouthed flask of about 150 cubic centimeters capacity. A portion of the indigotin solution is
next added, such as will be deemed sufficient for the process, and the whole is well mixed.
Strong sulfuric acid is next measured out from a burette into a test-tube, in volume equal to
the united volumes of the nitrate solution and indigotin. The whole of the sulfuric acid is
then poured as quickly as possible, into the solution in the flask and rapidly mixed, and the
flask transferred to a calcium chlorid bath, the temperature of which should be maintained at
140°. It is essential to the success of the operation that the sulfuric acid should be mixed with
the greatest rapidity. It should be poured in at once and the whole well shaken without
waiting for the test-tube containing the acid, to drain. The flask should be covered by a
watch-glass while it is held in the bath. As soon as the larger part of the indigotin is oxidized
the flask in the bath should be gently rotated. With very weak solutions of nitrate it may be
necessary sometimes to keep the flask in the bath for five minutes. When the indigo color is
quickly discharged it shows the presence of nitric acid in considerable excess and a
considerably larger quantity of indigo must be taken in the next experiment. The
experiments are continued until just the quantity of indigo necessary to consume the nitric
acid is taken, the amount of indigo being in very slight excess, not exceeding one-tenth cubic
centimeter of the indigo solution used. The tint produced by the small excess of indigo
remaining is best seen by filling the flask with water. On substances of approximately known
strength about four experiments are usually necessary to determine the amount of indigo to
be taken, but with unknown substances a larger number may be necessary.
Usually in determinations of this kind it is directed to use double the volume of sulfuric
acid mentioned above. In this case not only is the quantity of indigo oxidized much greater
than with a smaller portion of acid, but the prejudicial effect of organic matter is also greater
than when the smaller quantity of acid is employed.
An indigo solution standardized as above is strictly to be used for a solution of nitrate of
the strength employed during the standardization. The quantity of indigo oxidized in
proportion to the nitric acid present diminishes as the nitrate solution becomes more dilute.
Instead of determining this during each series of experiments it may be estimated once for all
and a table of corrections used.
The following table is based upon experimental determinations:
 Strength of Indigo Difference Nitrogen Difference Difference in the
niter solution required, between corresponding to between the nitrogen values for
used. cubic amounts of one cubic nitrogen a difference of one
centimeters. indigo, cubic centimeter of values, gram. cubic centimeter
centimeters. indigo, gram. in the amount of
indigo, gram.
⁸⁄₆₄ Normal 10.00 0.000035000
⁷⁄₆₄ „ 8.71 1.29 0.000035161 0.000000161 0.000000125
⁶⁄₆₄ „ 7.43 1.28 0.000035330 0.000000169 0.000000132
⁵⁄₆₄ „ 6.14 1.29 0.000035627 0.000000298 0.000000231
⁴⁄₆₄ „ 4.86 1.28 0.000036008 0.000000381 0.000000298
³⁄₆₄ „ 3.57 1.29 0.000036763 0.000000756 0.000000586
²⁄₆₄ „ 2.29 1.28 0.000038209 0.000001445 0.000001129
¹⁄₆₄ „ 1.00 1.29 0.000043750 0.000005541 0.000004295

The table is used as follows:

Suppose that twenty cubic centimeters of water under examination have required 5.36
cubic centimeters of indigo solution for the oxidation of the nitric acid contained therein. By
inspection of the table it is seen that this number is five-tenths cubic centimeter above the
nearest quantity given; viz., 4.86 cubic centimeters. From the last column in the table it is
found that the correction for five-tenths cubic centimeter of indigo solution is 0.000000149
cubic centimeter, being half that for the one cubic centimeter given in the table. This is to be
subtracted from the unit value in nitrogen given in the first “gram” column of the table; viz.,
0.000036008. It is thus seen that the 5.86 cubic centimeters of indigo solution are
equivalent to 0.000035859 gram of nitrogen per cubic centimeter. The water under
examination, therefore, contains nine and six-tenths parts of nitrogen as nitric acid per
million.
Attention must also be paid in standardizing indigo solutions to the initial temperature of
the solutions. A rise in the initial temperature will be attended by a diminution in the
quantity of indigo oxidized. Experiments with a room temperature of 10° and a room
temperature of 20°, being the initial temperatures of the experiments, showed that at the
higher temperature the amount of indigo consumed was about five per cent less when the
strong solutions of nitrate were employed. The indigo solution should, therefore, be
standardized at the same temperature at which the determinations are made.
If twenty cubic centimeters of the standard nitrate solution employed be used in setting
the indigo solution, this standard will enable the operator to determine nitric acid up to 17.5
parts of nitrogen per million in water or soil extracts.
The presence of an abundance of chlorids in the water under examination tends to
diminish the content of nitric acid found, and also tends to introduce an error, which is
sometimes of a plus and sometimes of a minus quantity, according to the strength of the
nitric acid present. The reaction is shortened in weak solutions by the presence of chlorids,
and the quantity of indigo consumed is consequently increased. The error introduced by
chlorids is usually of an insignificant nature.
On account of the interference of organic matters with the reaction of indigo it is not of
much use in the examination of nitrates washed out of soils, although in some cases the
results may be quite accurate. This method must, therefore, be considered as applicable, in
general, to waters or soil extracts which contain little or no organic matter.
In analytical work pertaining particularly to agriculture, the use of the indigo method for
determining nitric acid has been largely employed, both in the analyses of soil extracts and
drainage and irrigation waters. The method, however, can hardly survive as an important
one in such work in competition with more modern and speedy processes of analysis.