The kinetics of the liquid phase decomposition of HNOs in the temperature range 54 to 88°s uggests that the unimolecular decomposition of N2Os which is known to exist in fuming nitric acid solutions plays a significant role in the rate-determining step. A rate mechanism experimentally indistinguishable from that of the N2Os hypothesis involves the product (N02+)-(NOs-). The effect of several inorganic additives, namely, H20, N204, N206, KNOs, KHSO<, NOHSOi, H2SO< and HCIO4, on the rate of decomposition was in agreement with these postulated rate mechanisms. The inhibition of the decomposition rate by various additives tested was found to be insufficient to prevent the eventual attainment of high equilibrium pressures resulting from the decomposition of fuming nitric acid when stored in closed containers for periods of about a month in the temperature range 54 to 88°. Of all the additives tested on both a molal and a weight basis, H20 gave the most pronounced inhibiting effect on HNOa decomposition.

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The influence of excess primary amine on the water solubilities is not quite so pronounced as that of acetic acid. Because of the extremely limited solubility of the higher amines in water (8), the presence of impurity shifts the boundary BD to lower concentrations. CONCLUSIONSIt can be deduced that, in general, the apparently enhanced solubility of the commercial amine acetates is attributable to the solubilizing influence of homologs. Although other substances, such as excess acetic acid, and water, nitrile, amide, etc., exert considerable influence on the physical behavior of these materials, they are ordinarily present to a relatively minor extent, and consequently their effects are limited to unique behavior in isolated LITER4TURE CITED(1) Harwood, H.

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