The kinetics of organic decomposition reactions.

The thermal decomposition of gaseous n-butyl nitrite was investigated from 5 to 40 cm. pressure in the temperature range 170 to 212°C.The reaction is homogeneous and first order. The mechanism is, in the main, the same as with the lower members of the series.The reaction is, however, complicated by the formation of condensation products and the results are therefore less accurate than thoseobtained for lower members of the series. The activation energy is approximately the same as those of the other nitrites. The velocity constantat lb9.9°C is 8.19 10"4see_1 as compared with .97 for methyl, 1.89 for ethyl, and 3.95 for n-propyl nitrite. The results are discussed inthe light of unimolecular theory, both of Kassel's treatment and the more absolute treatment of Eyring and Rice and Gershinowitz.It is concluded that the main factor contributing to the increase in the high pressure rate with molecular complexity is the progressive diminutionin binding energy as the homologous series is ascended. [...