Peroxyacid oxidations :: kinetics and mechanism of oxidation of α,β-uasaturated ketones by peroxomonophosphoric acid and peroxomonosulfuric acid

The kinetics of oxidation of alpha/beta-unsaturated ketones by peroxomonophosphoric acid and peroxomonosulfuric acid have been studied at different pH over the temperature range 308-328 K. The reactions are of second order; first order each in peroxy acid and in substrate concentrations at constant pH. From the pH-rate data the relative reactivities of different peroxo and substrate species have been determined. The results are interpreted in terms or nucleophilic attack by peroxo species on the neutral as well as protonated forms of the substrate molecule followed by oxygen-oxygen. bond fission. to give the products. Thermodynamic parmeters for the reactions have been evaluated.