upon the absorption of the gas in caustic soda solution and the titration of its acidity is now often used instead.

There are many other variations of the heat test. They are sometimes called stability tests, but most of them, it will be noted, involve the self-catalyzed decomposition of the sample in an atmosphere of air or of red fumes. They indicate the comparative stability only of materials which are physically alike. True indications of the stability of nitric esters are to be scoured only by studying the decomposition of the substunees in vacuum. For this purpose the 120° vacuum stability test is most generally preferred.

Ash in nitrocellulose is determined by gelatinizing the sample with acetone which contains 5% of castor oil, setting fire to the colloid, allowing it to burn tranquilly, and igniting the charred residue to constancy of weight. It is sometimes determined as sulfate by dissolving the sample in pure concentrated sulfuric acid and igniting to constant weight.

Nitrogen in nitrocellulose is determined l>y means of the nitrometer, an instrument of great usefulness to the chemist who is working with nitric esters or with nitroamines.

Determination of Nitrogen

Nitric acid and organic ami inorganic nitrates, and in general all substances which contain free nitric acid or yield nitric acid when they are treated with concentrated sulfuric acid, are analyzed by means of the nitrometer. The method depends upon the measurement of the volume of the nitric oxide which is produced when concentrated sulfuric acid acts upon the sample in the presence of mercury. It is satisfactory also for the determination of nitro group nitrogen in certain nitroamines, in nitro-guanidinc and in tetryl but not in methylnitramine. It is not satisfactory in the presence of mononitro aromatic compounds or of other substances which are nitrated readily by a solution of nitric acid in concentrated sulfuyi^acid.

Cold concentrated sulfuric acid docs not attack mercury. Cold nitric acid acts upon mercury to form mercurous nitrate with the evolution of nitric oxide. If concentrated sulfuric acid is present, mercurous nitrate cannot form, and the nitric acid is converted by the mercury quantitatively into nitric oxide. The method appears to have been used for the first time by Walter Crum who applied it at an early date to the analysis of guncotton.

Figures 66 and 67. Georg Lunge and His Nitrometer. Obverse and reverse of commemorative bronze plaquettc by Hans Frei in celebration of Lunge's seventieth birthday.

He introduced the sample of guncotton into a eudiometer filled with mercury and inverted in that liquid, and carried out the reaction and measured the gas volume in the same eudiometer. Since he was unable to separate the guncotton from the air entangled with it, the measured gas volume was too large. The true volume of nitric oxide was determined by admitting a solution of ferrous sulfate to the eudiometer and noting the volume of gas which was absorbed.

The Lunge nitrometer is so designed that the nitrate or nitric ester is dissolved first in concentrated sulfuric acid and the solution, without entrained gas, is afterwards admitted to the re-

Was this article helpful?

0 0

Post a comment