The Homogeneous Unimolecular Decomposition of Gaseous Alkyl Nitrites VIII. The Decomposition of Ethyl and n-Propyl Nitrites at Low Pressures Together with a General Discussion of the Results for the Entire Series

The kinetics of the decomposition of ethyl and n-propyl nitrites have been investigated at low pressures. The results, together with those for the other members of the nitrite series, are discussed from the point of view of the Kassel theory. Attention is focused particularly on the effect of increasing molecular complexity as one ascends an homologous series, since the nitrites furnish an ideal series for such a discussion. It is concluded that the Kassel theory furnishes a complete explanation of the facts insofar as the effect of pressure on the rate is concerned. On the other hand, there is no satisfactory quantitative explanation of the increase in the high pressure rate with increasing molecular complexity. The factors which might contribute to such an increase are discussed, and it is concluded that the main factor is probably a progressive change in binding energy as one ascends an homologous series.