Rate constants for the oxidation of tert-butyl hydroperoxide anion by several oxidants were determined by pulse radiolysis. Since the reduction potentials of the oxidants are much higher than the t-BuO2, the observed rate constants suggest that the self-exchange rate for t-BuO2/r-BuO2 is very slow and that it would be difficult to establish rapid equilibrium by pulse radiolysis with a suitable redox pair. Therefore, to determine the reduction potential for this peroxy radical, the forward and reverse rate constants for reaction, t-BuO2·+Fe(CN)64- ⇔ t-BuO2-+Fe(CN)63-, were measured independently. The forward rate constant was measured by kinetic spectrophotometric pulse radiolysis in N2O-saturated solutions.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry