Kinetics and mechanism of periodate oxidation of aniline and O-chloroaniline

The kinetics of oxidation of aniline and o-chloroaniline by periodate have been investigated in acid medium by spectrophotometric means. The rate constant increases with increasing amine concentration, independent of periodate concentration and inhibited by hydrogen ion concentration in the presence of aniline while catalyzed by it in the presence of o-chloroaniline. The mechanism proposed and the derived rate law are consistent with the observed kinetics. The rate constants predicted using the derived rate law in agreement with the observed rate constants, thus justifying this rate law and hence the proposed mechanistic scheme. The activation enthalpies and activation entropies were calculated from the temperature dependence of the specific rate constants.