The mechanism of the oxidation of alcohols and aldehydes with peroxydisulphate ion

Abstract

The kinetics of the reactions of peroxydisulphate with alcohols (methanol, ethanol, propan-1-ol, propan-2-ol, and butanol) and with acetaldehyde have been studied. Their radical-chain behaviour has been established. Using a radical-scavenger method it has been shown that the chain-initiating step is the monomolecular homolysis of the peroxydisulphate anion. The ‘limiting’ concentration of the reducing agents, the mean kinetic chain length, and the overall energy of activation have been determined. The mechanism of the autoinhibition of the reaction of primary alcohol with peroxydisulphate has been discussed.