After the air has all been expelled from the flask the analytical process is commenced, the carbon dioxid current being slowly continued. At first, a few drops of the dilute sulfuric acid are allowed to flow into the flask. As soon as the liquid is colored blue a sufficient quantity of the thiosulfate solution is added to discharge the color. The successive addition of acid and thiosulfate is continued until another portion of the acid fails to develop the blue color, thus indicating that all the nitrite has been decomposed. From the volume of thiosulfate used the quantity of nitrite is calculated.

The Thiosulfate Solution.—The thiosulfate solution is conveniently prepared, when a large number of analyses is to be made, by dissolving twenty-five grams of pure crystallized sodium thiosulfate in 100 cubic centimeters of water and diluting any convenient part thereof to 100 or 1,000 cubic centimeters, according to the supposed strength of nitrite solution under examination.

For fixing the strength of the solution dissolve 3 348 grams of pure iodin in a solution of potassium iodid and make the volume up to one liter. Each cubic centimeter of this solution corresponds to one milligram of nitrous acid. A given volume of the iodin solution is titrated against the thiosulfate, but it is best not to add the starch paste until the greater part of the iodin has been removed. The starch paste is then added and the titration continued until the blue color has been discharged. Ten cubic centimeters of the iodin solution is a convenient quantity for the titration and the thiosulfate should be diluted by adding to ten cubic centimeters of the solution mentioned above, 990 cubic centimeters of water. Each liter of this dilute solution contains two and a half grams of the sodium thiosulphate.

Example.—Let us suppose that it has required 21.3 cubic centimeters of thiosulfate to absorb ten cubic centimeters of the iodin solution; further that ten liters of water have been evaporated and titrated as described above, and that the volume of thiosulfate employed was 13.8 cubic centimeters. From this is derived the following formula: 13.8 × 10
21.3 = 6.48 milligrams of nitrous acid; or 0.648 milligram per liter.

508. Estimation of Nitrous Acid By Coloration of Solution of Ferrous Salt.—This method, due to Picini is based on the production of the well-known brown color formed by the action of nitric oxid on a ferrous salt.^[339] The nitrite is decomposed by heating with acetic acid while nitrates thus treated do not develop the reaction. The tint produced is imitated as above by testing against a standard solution of nitrite. Ferrous chlorid is to be preferred to other ferrous salts for the above purpose. The process should be carried on in solutions free of air.

509. Estimation of Nitrous Acid By Decomposition with Potassium Ferrocyanid.—The method of Schaeffer was first described in 1851, but little attention has been paid to it since. The method has lately been brought into notice again by Deventer.^[340]

The reaction depends upon the decomposition of nitrous acid by potassium ferrocyanid in the presence of acetic acid with the formation of potassium ferricyanid and acetate, and nitric oxid. The reaction is expressed by the following equation:

A eudiometer with a glass stop-cock is arranged as shown in Fig. 90. The lower part of the eudiometer is closed with a rubber stopper carrying a glass tube which ends in the pan f as shown at e. The eudiometer is filled to the stop-cock with a solution of potassium ferrocyanid of about fourteen per cent strength. The dish f is also filled up to the height indicated in the figure with the same solution. The solution of nitrite is used in such quantities that the nitric oxid evolved will occupy a space of about twenty cubic centimeters. The whole eudiometer should contain about fifty-seven cubic centimeters. The nitrite solution is added to the eudiometer by means of a funnel, a. The vessel containing it is washed out with a little water and then with acetic acid and finally with a few cubic centimeters of strong potassium ferrocyanid solution. The last fluid flows through the solution of nitrite and acetic acid and thus mixes it with the solution already in the eudiometer. The liquids reacting on each other float together on the strong ferrocyanid solution and each one of them is at once pressed downward by the gases which are evolved. When the evolution of gas becomes slower the apparatus should be shaken for about twenty minutes, moving it back and forth without taking the bottom of it out of the dish. When there is no longer any evolution of gas, water is added through a slowly, until the heavy potassium ferrocyanid solution is almost completely driven out of the eudiometer. The opening of the tube at e is then closed with the thumb, the apparatus is taken out of the dish, shaken for some time in a vertical direction and again placed in the dish. Water of any required temperature is now allowed to flow through the jacket, g, h, until the temperature is constant, when the volume of nitric oxid is read. The whole experiment can be performed in less than an hour. Operating in this way, at the end there is in the eudiometer a liquid which is not very different from water and one whose coefficient of solubility for nitric oxid is practically the same as that of water. The gas volume read is to be corrected for temperature, pressure, tension of the aqueous vapor, height of the water column in the eudiometer, and, after the end of the calculation, five per cent of the volume of water remaining in the eudiometer is to be added to the volume of gas obtained. This is to compensate for the volume of the gas absorbed by the water. The method gives good quantitive results.

510. Method of Collecting Samples of Rain Water for Analysis.—Warington collects rain water in a large leaden gauge having an area of 0.001 of an acre.^[341] Of the daily collection of rain, dew, and snow water, an aliquot part amounting to a gallon for each inch of precipitation is placed in a carboy; at the end of each month the contents of the carboy are mixed, and a sample taken for analysis. In the carboy receiving the rain for nitric acid estimation a little mercuric chlorid is placed each month with the view of preventing any change of ammonia into nitric acid. It may be doubted, however, if this precaution is necessary, as the rain water thus collected always contains a very appreciable amount of lead; and experiments have shown that on the whole, rain water more frequently gains than loses ammonia by keeping.

Preparation of the Sample.—The method first employed by Warington was to concentrate ten pounds of the rain water in a retort, a little magnesia being used to decompose any ammonium nitrite or nitrate present. Concentration by evaporation in the open air, and especially over gas, results in a distinct addition to nitrites present. When concentrated to a small bulk, the water is filtered and evaporated to dryness in a very small beaker. The nitrogen as nitrates and nitrites is then determined by means of the methods already described.

DETERMINATION OF FREE AND ALBUMINOID AMMONIA IN RAIN AND DRAINAGE WATERS AND SOIL EXTRACTS.

511. Nessler Process.—The quantities of free ammonia in rain and most drainage waters are minute, but may reach considerable magnitude in some sewages. By reason of these minute proportions, gravi- and volumetric methods are not suitable for its quantitive determination. Recourse is therefore had to the delicate colorimetric reaction first proposed by Nessler. This reaction is based on the yellowish-brown coloration produced by ammonia in a solution of mercuric iodid in potassium iodid. The coloration is due to the formation of oxydimercuric ammonium iodid, NH₂Hg₂OI, and takes place between the molecule of free ammonia and the mercuric iodid dissolved in the alkaline potassium iodid as represented by the following equation:

Nessler Reagent.—Dissolve thirty-five grams of potassium iodid in 100 cubic centimeters of water. Add to this solution gradually a solution of seventeen grams of mercuric chlorid in 300 cubic centimeters of water until a permanent precipitate of mercuric iodid is formed. Add now enough of a twenty per cent solution of sodium hydroxid to make 1000 cubic centimeters.

The mixed solutions, at room temperature, are treated with additional mercuric chlorid until the precipitate formed, after thorough stirring, remains undissolved. This precipitate is then allowed to subside, and when the supernatant liquid is perfectly clear, it is decanted or filtered through asbestos and kept in a well-stoppered bottle in a dark place. The part in use should be transferred to a smaller bottle as required. The solution should be made for a few days before using, since its delicacy is increased by keeping. The nessler reagent should show a faint yellow tint. If colorless it is not delicate, and shows the addition of an insufficient quantity of mercuric chlorid. When properly prepared, two cubic centimeters of the reagent poured into fifty cubic centimeters of water containing 0.05 milligram of ammonia will at once develop a yellowish-brown tint.

Preparation of Ammonia-Free Water.—To pure distilled water add pure, recently-ignited sodium carbonate, from one to two grams per one liter, and distill. When one-fourth of the whole has passed over, the distillate may be regarded as free from ammonia; fifty cubic centimeters of the following distillate should give no reaction with the nessler reagent. The distillation should be continued until the residual volume in the retort is about one-fourth of the original, and the distillate free of ammonia is carefully preserved in close glass-stoppered bottles previously washed with ammonia-free water. Pure water, free of ammonia may also be obtained by distilling with sulfuric acid.

Comparative Solution of Ammonium Chlorid containing 0.00001 gram Ammonia in one cubic centimeter.—Dissolve 3.15 grams H₄NCl in ammonia-free water and make the volume up to one liter. Take ten cubic centimeters of the above solution and dilute to 1000 with water, free from ammonia.

Solution containing 0.00001 gram Nitrogen in one cubic centimeter.—Dissolve 3.82 grams H₄NCl in water, free from ammonia and dilute with same to 1000 cubic centimeters. Dilute ten cubic centimeters of the above solution to 1000.

The Distillation.—Any kind of suitable retort or flask connected with a good condenser may be used. The capacity of the retort should be from 700 to 1,000 cubic centimeters. The retort and condenser preferred by Leffmann and Beam are shown in Fig. 91. Any good lamp may be used in which the flame is under complete control. The gauze burner shown in the figure is easily controlled and distributes the heat evenly over the surface of the retort thus diminishing the danger of fracture. The apparatus having been previously rinsed with distilled water receives 500 cubic centimeters of the liquid to be tested for ammonia, together with a few pieces of recently ignited pumice stone to prevent bumping and five cubic centimeters of the twenty percent sodium carbonate solution to render its contents alkaline. The water is raised to the boiling-point and with gentle ebullition fifty cubic centimeters of distillate collected. The distillate is conveniently collected in a color-comparison cylinder of thin white glass and flat bottom, about two and a half centimeters in diameter, and marked at fifty and one hundred cubic centimeters. Two cubic centimeters of the nessler reagent are added and if ammonia be present a yellowish-brown color will be developed, the intensity of which is matched by taking portions of the ammonium chlorid solution, diluting to fifty cubic centimeters with pure water and treating with the same quantity of the nessler reagent. The process is repeated until a distillate is obtained which gives no reaction for ammonia. The sum of the quantities obtained in the several distillates gives the total amount of ammonia in the 500 cubic centimeters of the water taken. In most cases practically all the ammonia is obtained in three or four portions of the distillate.

Albuminoid Ammonia.—The residue from the process just described is employed for the purpose of determining the albuminoid ammonia. Two hundred grams of potassium hydroxid and eight grams of potassium permanganate are dissolved in 1,000 parts of distilled water. Fifty cubic centimeters of the solution are placed in a porcelain dish with 100 cubic centimeters of distilled water and evaporated to fifty cubic centimeters. This liquid is placed in the retort and the distillation resumed and continued until an ammonia-free distillate is obtained. The total albuminoid ammonia is determined by taking the sum of the quantities in the several distillates.

512. Nessler Reagent of Ilosvay.—To secure greater delicacy in nesslerizing, Ilosvay uses a reagent prepared as follows:^[342]

Dissolve two grams of potassium iodid in five cubic centimeters of water, heat the solution gently, and add three grams of mercuric iodid. After the solution is cooled, add an additional portion of three grams of the mercury salt, and then twenty cubic centimeters of water, and wait until the precipitation is complete. After filtering, there are added to the filtrate from twenty to thirty cubic centimeters of a twenty per cent solution of potassium hydroxid. Only the limpid supernatant liquid is used in the analytical work. With this reagent, Ilosvay has been able to detect 0.02 milligram of ammonia in 110 cubic centimeters of water.

AUTHORITIES CITED IN PART SEVENTH.

Note.—On page 158, paragraph 172, third line, insert, “and determining matters dissolved therein,” after “flow.”