A study of the chain reaction in the thermal decomposition of diethyl ether.

Abstract

In a recent paper (Hobbs and Hinshelwood 1938), information about the chain mechanisms involved in the thermal decomposition of ethane was obtained by studying the variation with the ethane concentration of the shape of the curve which represents in the reaction rate as a function of minute quantities of added nitric oxide. This paper describes the results of a similar investigation carried out with diethyl ether, the behaviour of which shows an interesting contrast with that of ethane. The thermal decomposition of diethyl ether in the neighbourhood of 500° C. occurs partly by a chain mechanism in which free radicals are formed, and partly by intramolecular rearrangement (Staveley and Hinshelwood 1936, 1937). The end- products of the decomposition are methane, ethane, and carbon monoxide, with small amounts of hydrogen and unsaturated substances. Acetaldehyde is an intermediate product formed either in the rearrangement process, or, as in the mechanism put formed below, during the chain reaction (Fletcher and Rollefson 1936). The acetaldehyde, however, decomposes rapidly under the experimental conditions and the initial rate is sensibly that of the decomposition of the ether into final products.