A kinetic and mechanistic study on the silver (I)-catalyzed oxidation of l-alanine by cerium (IV) in sulfuric acid medium

Abstract

The kinetics and mechanism of Ag(I)-catalyzed oxidation of l-alanine by cerium (IV) in sulfuric acid media have been investigated by titrimetric technique of redox in the temperature range of 298–313K. It is found that the reaction is of first order with respect to Ce(IV) and l-alanine, and it is of a positive fractional order with respect to Ag(I). It is found that the pseudo first order ([l-alanine]≫[Ce(IV)]≫[Ag(I)]) rate constant k′ increases with the increase of[H+]. The major oxidation product of alanine has been identified as acetaldehyde by an 1H NMR and IR spectroscopy. Under the experimental conditions, the kinetically active species has been found to be Ce4+. Under nitrogen atmosphere, the reaction system can initiate the polymerization of acrylonitrile, indicating generation of free radicals. On the basis of the experimental results, a suitable mechanism has been proposed. The rate constants of the rate-determining step together with the activation parameters were evaluated.