Gas-phase oxidation of alkenes: decomposition of hydroxy-substituted peroxyl radicals

Abstract

Carbonyl compounds are the main products of the low-temperature gas-phase oxidation of alkenes. It is suggested that they are formed by consecutive addition of a hydroxyl radical and an oxygen molecule to the alkene, the hydroxy-substituted peroxyl radical subsequently decomposing to yield two molecules of carbonyl compounds and the chain carrier. A model system has been investigated, the fuel chosen being 2,3-dimethylbutan-2-ol which gives acetone as the major product at 578 K. In reactions with [¹⁸O]-2,3-dimethylbutan-2-ol and oxygen, the ketone is enriched by ca. 50%, and this result is consistent with the decomposition of the radical (II). [graphic omitted]