Oxidation of alchols by aqueous ceric ions in perchloric acid

Abstract

Oxidation of a number of alcohols, viz n-propyl, n-butyl, isobutyl, isoamyl, isopropyl, sec-butyl, sec-amyl, tert-butyl, tert-amyl and benzyl alcohols and cyclohexanol has been investigated with cerle perchlorate in perchloric acid medium (0.5-2.0 M) in the temperature ranges 5-30˚ C. The reaction have been followed by determining the rates of ceric ion disappearance for variations in [Ce4+],[alcohols], [HClO4+] ionic strength, temperature , etc.Analyses have been made and the stoichiometries, - ∆ Ce4 +/∆ product,have been established. A mechanisms of oxidation of the alcohols based on unimolecular decomposition of complexes (Ce4+ + alcohols) has been put forward to explain the observed results for all alcohols, except for benzyl alcohol,which shows a different behaviour in that it is a second order reaction, first order each in [Ce4+] and [alcohol]. The rate and equilibrium constants.