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Rate constant for the reaction of the t-butoxyl radical with Fe(II) ion

The rate of the reaction of the tert-butoxyl radical (t-BuO) with Fe2+ was measured using laser flash photolysis of methanolic solutions at room temperature. t-BuO were generated by homolytic photodecomposition of di-tert-butyl peroxide. The rate constant for oxidation of Fe2+ with t-BuO radicals was studied under pseudo-first order contitions. On the basis of competitive kinetics the quantum yield of oxidation, F(Fe3+), was determined as function of Fe2+ concetration by measuring the absorbance of Fe3+as [FeCl]2+complex. By using the literature values of the rate constants of relevant competing reactions, the desired rate constant was determined to be 3.0x108 M-1s-1.

t-Butoxyl radical; laser flash photolysis; ferrous ion oxidation; competitive kinetics; aquochloroiron (III) complex

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