The Reaction of Oxygen Atoms with Dimethyl Ether

The gas-phase reaction of dimethyl ether with oxygen atoms produced by the mercury photosensitized decomposition of nitrous oxide has been studied by means of quantitative determinations of the reaction products. Characteristic products are water, methanol, formaldehyde, carbon monoxide, methoxy ethanol and methyl formate. The possible mechanisms of the oxygen attack on the substrate have been considered, and the following steps postulated on the basis of the relative importance of these products and their time variations: O+CH3OCH3 – OH+CH3OCH2, OH+CH3OCH3 –→ H2O+CH3OCH2 and CH3OCH2+OH –→ CH3O+CH2OH. The rate constant, kE, of the first step has been determined in the competitive reaction with n-butane as: k E=6.3×1010exp(−4700/RT) 1. mol−1 sec−1·