Abstract

Abstract The kinetics of Baeyer-Villiger oxidation of biacetyl and benzil by peroxomonophosphoric acid and peroxomonosulfuric acid have been studied in different pH ranges at 308 K. The reactions are second order; first order each in peroxy acid and in diketone concentrations at constant pH. The oxidation rate is strongly pH-dependent; the rate increases with increase in pH. From the pH-rate data the reactivity of different peroxo species, in the oxidation, has been determined. A mechanism consistent with rate-determining nucleophilic attack of peroxo species on carbonyl carbon of the diketone molecule has been proposed. Acetic acid and benzoic acid are respectively found to be the products of oxidation of biacetyl and benzil.

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