Nitrosonium perchlorate, decomposition

The decomposition of nitronium perchlorate between 70° and 112° C. has been reported by Cordes (2) to proceed to the gaseous products NO2, Cl2, C102, NO3CI, and 02. As a result of some screening experiments we were aware that at 65° C. in sealed tubes, nitrosonium perchlorate was a major decomposition product. We were also aware that dinitrogen tetroxide, at least in the liquid phase, would quantitatively convert nitronium perchlorate to nitrosonium perchlorate. Thus, a mechanism involving only gaseous products appeared unlikely. 

On the other hand, values of 31.3 and 3.9 are possible from the production and decomposition, respectively, of nitrosonium perchlorate. 

A study of the decomposition of NOCIO4 under conditions identical to this study gave the following results (1) nitrosonium perchlorate decomposes with no noticeable induction period, giving only the gaseous products, N02, C102, Cl2 and 02 nitronium perchlorate is reported as a... 

When a critical concentration of N02 has been reached from the decomposition of nitrosonium perchlorate, this catalytic conversion rapidly becomes the predominating reaction in the mechanism. Previous work had shown this reaction to be quantitative in the presence of liquid N2O4 (9). In the course of this investigation, gaseous N204 at ambient temperature in less than equimolar quantities was also shown to effect the quantitative conversion, presumably by the above mechanism (9). 

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