Reduction potential of the tert-butylperoxyl radical in aqueous solutions

Tomi Nath Das, T. Dhanasekaran, Z. B. Alfassi, P. Neta

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Abstract

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.

Original languageEnglish
Pages (from-to)280-284
Number of pages5
JournalJournal of Physical Chemistry A
Volume102
Issue number1
DOIs
Publication statusPublished - 1 Jan 1998

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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