Chapter XXIII: Introduction (22)

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:

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.

FIGURE 84.

LUNGE’S ANALYTIC APPARATUS.
]

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:

CORRESPONDING TO
———————————— ———————————— ————————————
Cubic Weight in N₂O₃ in HNO₃ in NaNO₃ in
centimeters milligrams. milligrams. milligrams. 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
niter required, between corresponding between the in the
solution cubic amounts of to one cubic nitrogen nitrogen
used. centi- indigo, centimeter of values, values for a
meters. cubic indigo, gram. gram. difference
centi- of one cubic
meters. centi- meter
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.

DETERMINATION OF NITRIC NITROGEN BY REDUCTION TO AMMONIA.

=480. Classification of Methods.=—When nitrogen is present in a highly oxidized state, _e. g._, as nitric acid, it may be quickly and accurately estimated by reduction to ammonia. This action is effected by the reducing power of nascent hydrogen, and this substance may be secured in the active state by the action of an acid or alkali on a metal, or by means of an electric current. The processes depending on the use of a finely divided metal in the presence of an acid or alkali have come into general use within a few years, and are now employed generally instead of the more elaborate estimations depending on the use of copper oxid or indigo.

The typical reaction which takes place in all cases is represented by the following equation:

2HNO₃ + 8H₂ = 2NH₃ + 6H₂O.

The method will be considered under three heads; _viz._, 1. Reduction in an alkaline solution; 2. Reduction in an acid solution; 3. Reduction by means of an electric current.

In the first class of processes the reduction and distillation may go on together. In the second class the reduction is accomplished first and the distillation effected afterwards, with the addition of an alkali. In the third class of operations the reduction is accomplished by means of an electric current and the ammonia subsequently obtained by distillation, or determined by nesslerizing. These processes may be applied to rain and drainage waters, and to soil extracts. On account of the ease with which the analyses are accomplished, the short time required and the accuracy of the results, the reduction methods for nitrates have already commended themselves to analysts, and are quite likely to supersede all others for practical use where weighable quantities of nitrates are present. For the minute traces of nitrates found in rain and drainage waters, and in some soil extracts, the reduction method may also be applied, but in these cases the ammonia which is formed must be determined by colorimetry (nesslerizing) and not by distillation. The processes about to be described are especially applicable to the examination of soils and waters rich in nitrates.

REDUCTION IN ALKALINE SOLUTIONS.

=481. Provisional Method of the Association of Official Agricultural Chemists.=[308]—

_Extraction of the Nitrates._—Place one kilogram of the dried soil, calculated to water-free substance, on a percolator of glass or tin. Moisten the soil thoroughly with pure distilled water, and allow to stand for half an hour. Add fresh portions of pure distilled water until the filtrate secured amounts to one liter. If the first filtrate be cloudy before use it may be refiltered.

_Qualitative Test for Nitrates._—Evaporate five cubic centimeters of the soil extract in a porcelain crucible, having first dissolved a small quantity of pure brucin sulfate therein. When dry, add to the residue a drop of concentrated sulfuric acid free of nitrates. If the nitrate calculated as potassium nitrate does not exceed the two-thousandth part of a milligram only a pink color will be developed; with the three-thousandth part of a milligram a pink color with reddish lines; with the four-thousandth part of a milligram a reddish color; with the five-thousandth part of a milligram a distinct red color.

_Estimation of the Nitrates._—Evaporate 100 cubic centimeters of the soil extract to dryness on a steam-bath. Dissolve the soluble portions of the residue in 100 cubic centimeters of ammonia-free distilled water, filtering out any insoluble residue. Place the solution in a flask, add ten cubic centimeters of sodium amalgam, stopper the flask with a valve which will permit the escape of hydrogen, and allow to stand in a cool room for twenty-four hours. Add fifty cubic centimeters of milk of lime and titrate the ammonia produced by distillation, with standard acid and estimate as nitrogen pentoxid. Where the amount of ammonia is small, nesslerizing may be substituted for titration.

_Preparation of Sodium Amalgam._—Place 100 cubic centimeters of mercury in a flask of half a liter capacity; warm until paraffin will remain melted over the surface; drop successively in the paraffin-covered mercury, pieces of metallic sodium of the size of a pea until 6.75 grams have united with the mercury. The amalgam contains then 0.5 per cent of metallic sodium and may be preserved indefinitely under the covering of paraffin.

=482. Method of the Experiment Station at Möckern.=[309]—The principle of this reaction is based on the reducing action exercised by nascent hydrogen on a nitrate, the hydrogen being generated by the action of soda-lye on a mixture of zinc dust and finely divided iron.

Ten grams of nitrate are dissolved in 500 cubic centimeters of water. Of this solution twenty-five cubic centimeters, corresponding to one-half gram, are placed in a distillation flask of about 400 cubic centimeters capacity, 120 cubic centimeters of water added, and about five grams of well-washed and dried zinc dust and an equal weight of reduced iron. To the solution are added eighty cubic centimeters of soda-lye of 32° B. The flask is then connected with the condensing apparatus and the distillation carried on synchronously with the reduction, the ammonia being collected in twenty cubic centimeters of titrated sulfuric acid. The distillation is continued from one to two hours, or until 100 cubic centimeters have been distilled, and the remaining sulfuric acid is titrated in the usual way. Soil extracts and sewage waters should be concentrated until they have approximately the proportion of nitrates given above.

=483. Method of Devarda.=—The inconvenience due to slow action and other causes, arising from the use of pure metals in the reduction of nitrates to ammonia, has been overcome, to some extent, by Devarda, by use of an alloy, in a state of fine powder, consisting of aluminum, copper, and zinc.[310] The alloy consists of forty-five per cent of aluminum, fifty per cent of copper, and five per cent of zinc. In dissolving, the copper is left in a finely divided state, which is a great help in distillation in preventing bumping.

The analytical process is carried out as follows: The solution containing the nitrate, in quantity equivalent to about one-half gram of potassium nitrate, is placed in a flask having a capacity of about one liter, and diluted with sixty cubic centimeters of water and five cubic centimeters of alcohol, and then forty cubic centimeters of caustic potash solution added of specific gravity one and three-tenths. From two to two and one-half grams of the alloy, described above, are introduced, and the flask attached to a condenser with a receiver containing standard acid. The connection between the flask and the condenser is made by means of a tube having on the limb next the flask a bulb filled with glass beads to prevent the contents of the flask splashing over into the receiver, and on the other limb another bulb to prevent the acid in the receiver finding its way into the distillation flask, should regurgitation occur. When the flask has been thus connected with the condenser it is gently heated for half an hour, at the end of which time the evolution of hydrogen will have slackened or ceased, and then the distillation is begun, at first cautiously, until the zinc of the alloy has completely dissolved, and then more vigorously, the time necessary being about twenty minutes from the time when the contents of the flask begin to boil. The distillate is caught in standard acid and the ammonia determined by backward titration in the ordinary way. It is to be noted that the strength of the alkali used is of importance, as if it be too strong, the action on the alloy is unduly vigorous at the beginning of the operation, and if too weak, the contents of the flask have to be heated overmuch, the result in both cases being the formation of a fine spray of caustic solution, which is very difficult to stop, even with complicated washing attachments to the distilling flask. The test analyses on pure nitrates are satisfactory. This method has been used with satisfaction in the laboratory of the Department of Agriculture, but does not appear to have any special advantage over the process of Ulsch, to be described further on.

=484. Variation of Stoklassa.=—Stoklassa has subjected the method of Devarda to a comparative test with the following methods:[311]

1. Wagner’s Schloesing-Grandeau method.

2. Lunge’s nitrometer method.

3. Stutzer’s method.

FIGURE 85. STOKLASSA’S NITRIC ACID APPARATUS.
]

The reduction takes place in a copper erlenmeyer, A, Fig. 85, in which, in addition to the solution containing the nitrate, are placed 200 cubic centimeters of water, forty cubic centimeters of potassium hydroxid solution of 33° B., five cubic centimeters of alcohol, and finally two and one-half grams of the finely powdered Devarda alloy. The distillate passes through a tube, B, filled with glass pearls and into the condenser D, through the bulbs, C C′.

After the flask is connected with the distilling apparatus, it is gently warmed and the reduction is ended in about twenty minutes. The ammonia which is formed is then distilled into E, containing the standard acid, S, requiring about twenty minutes more. The comparative results given, show that the Devarda method is equally as accurate as any of the other methods mentioned, giving practically theoretical results.

In so far, however, as speed of an analysis, is concerned the first place is awarded to the Lunge nitrometer method, with which a complete analysis can be made in from thirty to forty minutes. In the second rank, so far as speed is concerned, the Devarda method is recommended. All the methods give accurate results.

=485. Method of Sievert.=[312]—Two grams of potassium or sodium nitrate are dissolved and made up to 1,000 cubic centimeters. Fifty cubic centimeters of the solution are placed in a 600 cubic centimeter flask and diluted with fifty cubic centimeters of water, and from eighteen to twenty grams of caustic alkali added. After the alkali is dissolved, seventy-five cubic centimeters of ninety-six per cent alcohol are added and a few pieces of bone-black to prevent foaming. From ten to fifteen grams of zinc or iron dust are then added to the flask which is closed and connected with a =ᥩ= tube holding about 200 cubic centimeters, which contains about ten cubic centimeters of normal sulfuric acid. This =ᥩ= tube is kept cool by being immersed in water. The whole mixture is now allowed to stand for three or four hours and then the alcohol is distilled slowly and the ammonia formed by the reduction of the nitrates is carried over with it. The distillation lasts for about two hours. The contents of the =ᥩ= tube are carefully rinsed into a dish and the excess of sulfuric acid titrated with one-fourth normal soda-lye.

For soil extracts and substances containing unknown quantities of nitric acid, a preliminary test will indicate approximately the amount thereof, and this will be an indication for the quantity to be used in the analysis.

The method of Stutzer differs from the foregoing in the substitution of aluminum dust instead of iron or zinc.[313] The reducing power of aluminum, however, varies greatly according to the method in which the metal has been prepared. Pure aluminum prepared by the electric method, reduces the nitric acid much less vigorously than the metal prepared by the older methods of fusion with sodium. For this reason the method of Stutzer is not to be preferred to that of Sievert.

REDUCTION IN AN ACID SOLUTION.

=486. Variation of the Sodium Amalgam Process.=—This method is described by Monnier and Auriol.[314]

FIGURE 86. VARIATION OF THE SODIUM AMALGAM PROCESS.
]

The principle of the operation depends on the reduction of the dissolved nitrate by titrated sodium amalgam in presence of an acid, and the estimation of the quantity of nitric acid present from the deficit in the volume of hydrogen. The apparatus employed is conveniently mounted as shown in Fig. 86. The brass vessel A is movable by means of the cord on the pulley B, in such a way as to be fixed at any required altitude. It is filled with water and connected by a rubber tube to the cooling tube D. Within the cooling tube there is a graduated cylinder open at its lower end. Its upper end is connected directly with the apparatus C. The cooling tube D has a small side tube, _c_, near its upper end, by means of which the air can enter or escape when the position of A is changed. The apparatus C, in which the reaction takes place, is a glass cylinder. Its upper end is continuous with the =⟙= tube provided with the stop-cocks _a_ and _b_. One arm of the =⟙= permits connection with the graduated measuring tube by means of a rubber union. The lower end of C is closed with a large hollow ground-glass stopper, carrying a small receptacle within, so that it forms two separate water-tight compartments, open at the top.

The sodium amalgam is prepared as follows:

In a clay crucible are heated 400 grams of mercury, and, little by little, with constant stirring, four grams of dry sodium are added. When cold, the amalgam is placed in a burette, having a ground-glass stopper, and covered with petroleum. The strength of the amalgam is established in the following manner. A small glass thimble, ground even at the top, is filled with the amalgam and struck off even with a ground-glass straight edge. In this way the same quantity of amalgam is taken for each test. This measured portion of the amalgam is placed in the inner vessel of the glass stopper to C. Ten cubic centimeters of water, containing sixty centigrams of tartaric acid, are placed on the outer ring of the glass stopper, which is then inserted, well oiled, in C, closing it air- and water-tight. The tartaric acid solution also carries a piece of litmus paper, so that its constant acidity may be insured. The vessel A is then fixed in a position which brings the water in the graduated burette and tube D exactly to the 0 mark. The cock _a_ is next closed, _b_ opened, and C is inverted until all the amalgam is poured into the solution of tartaric acid. The evolved hydrogen mixed with the air contained in the apparatus, is passed into the graduated burette. After fifteen minutes, the reaction is ended. The water level within and without the graduated tube is restored and the volume of gas evolved noted and reduced by the usual tables to 0° and 760 millimeters pressure of the barometer.

An amalgam prepared as above will give about three cubic centimeters of hydrogen for each gram. The thimble should hold from twelve to fifteen grams.

The estimation of nitric acid should be made in a solution containing about one-tenth per cent of nitrate. Ten cubic centimeters are taken, to which six-tenths gram of tartaric acid is added, and placed in the outer part of the glass stopper. The rest of the process is conducted exactly as described above. The deficit in hydrogen is calculated to nitrogen pentoxid.

The reduction by sodium amalgam is not so convenient a form of estimating nitric acid as many of the other forms of using nascent hydrogen. As practiced by calculating from the deficit of hydrogen, however, it has some advantages by reason of the fact that no heating is required. The presence of organic neutral bodies, or even those of an acid nature, like humus, does not, therefore, interfere with the work. Likewise, mineral bodies in solution, which are not reduced by nascent hydrogen, do not interfere with the accuracy of the reaction.

=487. Method of Schmitt.=—In the method of Schmitt forty cubic centimeters of glacial acetic acid are placed in a flask of 600 cubic centimeters content, and fifteen grams of a mixture of zinc and iron dust added.[315] To this a quantity of the solution containing the nitrate, representing about half a gram of the pure nitrate, is added with constant shaking, in portions which do not evolve hydrogen too rapidly. After about fifteen minutes when the evolution of nitrogen has somewhat diminished, an additional fifteen grams of the metal dust are added. If the contents of the flask should become thick they can be diluted with thirty cubic centimeters of water. The reduction is complete in from thirty to forty minutes. The contents of the flask are now saturated with enough soda-lye not only to neutralize the excess of acetic acid, but to keep the zinc hydroxid also in solution. For this purpose about 200 cubic centimeters of soda-lye of 1.25 specific gravity are necessary. The ammonia is obtained by distillation into standard acid in the usual way.

=488. Method of Ulsch.=—In practice the method of Ulsch has come into general use.[316]

For the determination of nitrogen by this method half a gram of saltpeter or four-tenths gram of sodium nitrate is taken and dissolved in twenty five cubic centimeters of water, in a flask with a content of about 600 cubic centimeters. Five grams of iron reduced by hydrogen, and ten cubic centimeters of sulfuric acid diluted with two volumes of water are then added to the flask. To avoid mechanical losses during the evolution of hydrogen a pear-shaped glass stopper is hung in the neck of the flask. After the first violent evolution of hydrogen has passed, the flask is slowly heated until in about four minutes it is brought to a gentle boil. The boiling is continued for about six minutes when the reduction is complete. About fifty cubic centimeters of water are then added; also an excess of soda-lye and a few particles of zinc and the ammonia is distilled and collected in standard acid in the usual way.

The method of Ulsch can also be applied, according to Fricke, to the analysis of nitrates contained in drinking and drainage waters, and it is regarded by him as one of the best methods to be employed in such investigations.[317]

The method of Ulsch in this laboratory has given entirely satisfactory results, and is generally used in preference to other methods in cases where a considerable quantity of nitrates is present. It is based on the following reactions:

2KNO₃ + H₂SO₄ = K₂SO₄ + 2HNO₃
2HNO₃ + 8H₂ = 2NH₃ + 6H₂O
2NH₃ + H₂SO₄ = (NH₄)₂SO₄.

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.

FIGURE 87. MCGOWAN’S APPARATUS FOR THE IODOMETRIC ESTIMATION OF NITRIC
ACID.
]

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.