Mechanism of the permanganate oxidation of unsaturated compounds. Part 8. Kinetics of the oxidation of halogenomaleic acids

A study of the short-lived intermediates of the permanganate oxidation of halogenomaleic acids has revealed that an initial 4-electron process occurs, followed by reactions between manganese(III) and the organic intermediates. According to stopped-flow kinetic measurements, the reaction is of the first order with respect to both reactants. The pH dependence of the second-order rate constant is constant with the reactivity order: monoanion > acid > dianion. The reactivity trendt reflected by the individual rate constants indicate the predominance of steric over electronic effects.