Ten cubic centimeters of a normal saltpeter solution, containing two and a half grams of pure sodium nitrate in 100 cubic centimeters are placed in the funnel and, with continued boiling, allowed to pass, drop by drop, into the flask. When almost all has run out the funnel is washed three times with ten cubic centimeters of ten per cent hydrochloric acid and this is allowed to pass, drop by drop, into the flask. When no more nitric oxid is evolved the measuring-tube is transferred to a large jar filled with distilled water.
The solution of the substance to be examined should be taken in such quantity as will give about the same quantity of gas as is furnished by the ten cubic centimeters test nitrate solution before described; viz., about seventy cubic centimeters. Eight or ten determinations can be made, one following the other, and at the end another determination with normal sodium nitrate solution should be made as a check. At the end of the operation all of the measuring-tubes are in the large jar filled with distilled water. The temperature of the surrounding water will soon be imparted to the contents of each tube and the volume of nitric oxid is read by bringing the level within and without the measuring-tube to the same point. The percentages are calculated for the given temperature and barometer pressure in the usual way; or to avoid computation the volume can be compared directly with the volume furnished by a normal nitrate solution, which is a much simpler method.
208. Schmitt’s Modified Method.—The method is a modification of that already described by the author in which a mixture of powdered zinc and iron is used as a reducing agent.[176] The process is carried out as follows: Ten grams of the nitrate are dissolved and the volume made up to half a liter. Ten cubic centimeters of glacial acetic acid and ten grams of the fine metallic powder, iron and zinc, are placed in a flask of a capacity of about three-quarters of a liter and twenty-five cubic centimeters of the solution of the nitrate added. The flask is covered during the reduction to prevent loss by spraying, and after the solution is complete, which is the case in about ten minutes, the contents of the flask are diluted with from 200 to 300 cubic centimeters of water, thirty cubic centimeters of caustic soda of 1.25 specific gravity added, and the whole distilled as in the kjeldahl process. It must be noted that it is essential that the iron be finely divided; it is mixed with the powdered zinc in equal parts. The total nitrogen can be determined in guanos and nitrate mixtures by the following simple alteration in procedure: One gram of the substance is dissolved in water, five cubic centimeters of glacial acetic acid, and from two to three grams of the mixed metallic powder added, and the whole gently heated for ten or fifteen minutes. After the contents of the flask have cooled, twenty-five cubic centimeters of sulfuric acid are cautiously added in small portions, undue frothing being restrained by the addition of a fragment of paraffin wax. The acetic acid is then driven off by heating, and the remaining contents of the flask boiled until the organic matter is completely decomposed, as in the kjeldahl process. About two hours boiling is required. Neutralization and distillation are then practiced as in the ordinary manner. The method is also applicable to the determination of nitrates in drinking water, provided nitrites and ammonia be absent.
209. Krüger’s Method for Nitric Acid.—About three-tenths gram of the substance dissolved in water is mixed with twenty cubic centimeters of a hydrochloric acid solution of stannous chlorid holding 150 grams of tin per liter.[177] One and a half grams of spongy tin prepared by the action of zinc on stannous chlorid are added. The flask containing the mixture is heated until the tin is dissolved, by which time the nitric acid is completely reduced. The subsequent distillation and titration are accomplished as usual. In the case of nitro and nitroso compounds, after the solution of the tin, twenty cubic centimeters of sulfuric acid are added and heated until sulfuric vapors escape. After cooling, the amido substances formed are oxidized by potassium bichromate before the distillation takes place.
Krüger also estimates the nitrogen in benzol, pyridin, and chinolin derivatives by dissolving them in sulfuric acid, using from two-tenths to eight-tenths of a gram of the alkaloidal bodies and, after cooling the solution, oxidizing by adding finely powdered potassium bichromate.[178] About half a gram more of the potassium bichromate should be used than is necessary for the oxidation of the substances in solution. The entire oxidation does not consume more than from fifteen to thirty minutes.
SODIUM NITRATE.
210. Functions of Sodium Nitrate.—Practically the only form of oxidized nitrogen which is of importance from an agronomic point of view is sodium nitrate, often known in commerce by the name Chile saltpeter. Applied to a growing crop it at once becomes dissolved at the first rainfall or by the natural moisture of the soil. It carries thus to the rootlets of plants a supply of nitrogen in the most highly available state. There is perhaps no other kind of plant food which is offered to the living vegetable in a more completely predigested state, and none to which a quicker response will be given. By reason of its high availability, however, it must be used with care. A too free use of such a stimulating food may have, in the end, an injurious effect upon the crop, and is quite certain to lead to the waste of a considerable portion of expensive material. For this reason sodium nitrate should be applied with extreme care, in small quantities at a time and only when it is needed by the growing crop. It would be useless, for instance, to apply this fertilizer in the autumn with the expectation of its benefitting the crop to a maximum degree the following spring. Again, if the application of this salt should be made just previous to a heavy rain almost or quite the whole of it would be removed beyond the reach of the absorbing organs of the plant.
When once the nitric acid has been absorbed by the living rootlet it is held with great tenacity. Living plants macerated in water give up only a trace of nitric acid, but if they be previously killed with chloroform the nitric acid they contain is easily leached out.
The molecule of sodium nitrate is decomposed in the process of the absorption of the nitric acid. The acid enters the plant organism and the soda is excreted and left to combine with the soil acids. The nascent soda may thus play a role of some importance in decomposing particles of minerals containing potash or phosphoric acid. It is probable that the decomposition of the sodium nitrate takes place in the cells of the absorbing plant organs for it is difficult to understand how it could be accomplished externally. While the soda therefore is of no importance as a direct plant food it can hardly be dismissed as of no value whatever in the process of fertilization. Many of the salts of soda as, for instance, common salt, are quite hygroscopic and serve to attract moisture from the air and thus become carriers of water between the plant and the air in seasons of drought; and sodium nitrate itself is so hygroscopic as not to be suited to the manufacture of gunpowder.
To recapitulate: The chief functions of sodium nitrate are to give to the plant a supply of oxidized nitrogen ready for absorption into its tissues and incidentally to aid, by the residual soda, in the decomposition of silt particles containing potash or phosphoric acid and in supplying to the soil salts of a more or less deliquescent nature.