Mechanistic study of palladium(II) catalysed oxidation of crotonic acid by periodate in aqueous perchloric acid medium

The Pd(II) homogeneous catalysis of periodates oxidation of crotonic acid (CA) in perchloric acid has been studied. The linear dependence of the reaction rate at lower [IO4−] and [Pd(II)] tends towards zero order at their higher concentrations. The reaction exhibited zero order in [CA]. Negligible effect of change in [H+], ionic strength of medium and varying [Cl−] on rate of reaction is observed. [Pd]2+ and [IO4−] are assumed as the most reactive species of Pd(II) chloride and periodate, respectively. Acetaldehyde and glyoxylic acid have been identified as the main oxidation products of the reaction. Various activation parameters have also been calculated and recorded. On the basis of experimental findings, a suitable mechanism consistent with the observed kinetics was proposed. A comparative study was also made between the kinetic results of the present investigation and those of Pd(II) catalysed oxidation CA by chloramines-T in acidic medium.

The following reaction scheme is proposed for the kinetics of oxidation of crotonic acid by periodate in aqueous perchloric acid medium catalysed by Pd(II) to explain the observed experimental results: .Figure optionsDownload as PowerPoint slide