167. Tables for Calculating Results.—Where many analyses are to be made by the copper oxid process it has proved convenient to shorten the work of calculating analyses by taking the data given in computation tables.[138] Before using these tables it must be known whether they are calculated on the supposition that the gas is measured in a moist state, partly moist, or wholly dry. Where the nitrogen is collected over water a table must be used in which allowance has been made for the tension of aqueous vapor. In case a saturated solution of a caustic alkali be used in the azotometer it is customary to take no account of the tension and the table employed must be constructed on this supposition. In point of fact even in the strongest alkali solution there is a certain amount of tension but this is so slight as only to affect the results in the second place of percentage decimals. Since, as a rule, only a few analyses are made by this method it will be found safer to use a caustic alkali solution of given strength and to calculate the results from the tables of aqueous tensions given above.
168. The Soda-Lime Process.—This process originally perfected by Varrentrap and Will, and improved by Peligot, was used almost exclusively by analysts until within the last decade for the determination of nitrogen not existing in the nitric form. It is based on the principle that when nitrogen exists as a salt of ammonia, or as an amid, or as proteid matter, it is converted into gaseous ammonia by combustion with an alkali. This ammonia can be carried into a set solution of acid by a stream of gas free of ammonia and the excess of acid remaining after the combustion is complete can be determined by titration against a standard alkali solution. The results under proper conditions are accurate even when a small quantity of nitric nitrogen is present. When, however, there is any considerable quantity of this compound in the sample the method becomes inapplicable by reason of non-reduction of some of the nitrogen oxids produced by the combustion.
In bodies very rich in nitrogen such as urea all the nitrogen is not transformed directly into ammonia at the commencement of the combustion. A portion of it may unite with a part of the carbon to form cyanogen, which may unite with the soda to form sodium cyanid. With an excess of alkali, however, and prolonged combustion this product will be finally decomposed and all the nitrogen be secured as ammonia.
The nascent hydrogen which unites with the nascent nitrogen during the combustion is also derived from the organic matter which always contains enough carbon to decompose the water formed in order to be oxidized to carbon dioxid. While at first, therefore, during combustion, the hydrogen may unite with the oxygen, it becomes again free by the oxidation of the carbon and in this condition unites with the nascent nitrogen to form ammonia. In addition to carbon dioxid, ammonia, and free hydrogen there may also be found among the products of combustion marsh and olefiant gases and other hydrocarbon compounds which dilute, to a greater or less extent, the ammonia formed and help to carry it out of the combustion tube and into the standard acid.
169. The Official Method.—Reagents and Apparatus.—(1) Standard solutions and indicator the same as for the kjeldahl method:
(2) Dry granulated soda-lime, fine enough to pass a 2.5 millimeter sieve:
(3) Soda-lime, fine enough to pass a 1.25 millimeter sieve.[139]
Soda-lime may be easily and cheaply prepared by slaking two and one-half parts of quicklime with a strong solution of one part of commercial caustic soda, care being taken that there is enough water in the solution to slake the lime. The mixture is then dried and heated in an iron pot to incipient fusion, and, when cold, ground and sifted as above.
Instead of soda-lime Johnson’s mixture of sodium and calcium carbonate, or slaked lime may be used. Slaked lime may be granulated by mixing it with a little water to form a thick mass, which is dried in the water-oven until hard and brittle. It is then ground and sifted as above. Slaked lime is much easier to work with than soda-lime, and gives excellent results, though it is probable that more of it should be used in proportion to the substance to be analyzed than is the case with soda-lime.
(4) Asbestos, which has been ignited and kept in a glass-stoppered bottle.