On the thermal decomposition of methyl nitrite

Abstract

Steacie and Shaw have made a study of the thermal decomposition of a series of alkyl nitrites at temperatures between 170° and 240°. Their results are contained in the series of papers to which reference is made; but of these only the first is at present significant, for in it they consider the decomposition of methyl nitrite, and give their reasons for the conclusions which they arrive at regarding the nature of the decomposition process, which they assume to be common to the whole series. Their results led them to the conclusion that the decomposition process proceeds in accordance with the equation, 2CH 3 NO 2 = CH 2 O + CH 4 O + 2NO, (1) the process being of the first order. Assuming that this was so, the critical increment calculated from the temperature coefficient was found to be 36⋅4 kcals. If the decomposition process really does take place in accordance with the equation written above, the conclusion that the process is uni-molecular is confusing rather than helpful. It appeared possible that a study of the problem by methods more detailed than that applied by Steacie and Shaw might throw further light upon it, and with that object in view the present work was undertaken.