Reactions of oxygenated radicals in the gas phase. Part 10.—Self-reactions of ethylperoxy radicals

Abstract

The photo-oxidation of azoethane has been studied by molecular modulation spectroscopy in order to determine the overall rate constant for the second-order removal of ethylperoxy radicals between 303 and 457 K. The principal molecular products of the reaction between 302 and 373 K are acetaldehyde, ethanol and ethyl hydroperoxide. From the reaction rate data and analytical results, the following results have been obtained for the reactions 2C₂H₅O₂^˙→ CH₂CHO + C₂H₅OH + O₂. (3a) 2C₂H₅O₂^˙→ 2C₂H₅O^˙+ O₂. (3b)k_3b/k_3a increases with temperature from 1.75 ± 0.05 at 302 K to 2.45 ± 0.15 at 373 K. Arrhenius expressions for reactions (3a) and (3b) have been estimated.