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.