Kinetics and mechanism of the reactions of superoxide ion with hydrogen peroxide and hydroperoxides in an aprotic medium

Abstract

The interaction of electrochemically generated superoxide ion with hydrogen peroxide and t-butyl and cumyl hydroperoxide has been studied in acetonitrile. It was shown that the first step of the reaction was the splitting off of a proton. HOO^– which was forming in subsequent steps reacted further with H₂O₂via a chain mechanism again forming O₂^{[graphic omitted]} and possibly HO·. The interaction of excess of O₂^{[graphic omitted]} with alkyl hydroperoxides resulted in an autocatalytic process in which hydroperoxides played the role of catalysts of protonation of superoxide ion. The mechanism and kinetics of this process were studied.