Graphical separation of un-catalyzed and catalyzed reactions in iridium(III) catalyzed oxidation of cinnamaldehyde by cerium(IV) in aqueous acidic medium

When used as a homogeneous catalyst, iridium trichloride was found to change order of the reaction with respect to cerium(IV) sulphate concentrations in the oxidation of 3-phenyl propanal in aqueous acidic medium. Cerium(IV) and organic substrate form complex in the first equilibrium step. This complex decomposes in the rate determining step when iridium(III) is not present in the system while in the presence of iridium(III), it gives rise to another complex, which ultimately gives rise to cinnamic acid as product of reaction. Order of the reaction in the absence of iridium(III) was found to be one with respect to cerium(IV) sulphate concentrations while the reaction follows first order kinetics at low concentrations becoming to zero order at higher concentrations of the oxidant in the presence of catalyst. Both in the presence and the absence of catalyst, after showing first order kinetics in the beginning reaction tends to become independent of organic substrate at its higher concentrations. Rate of the reaction follows direct proportionality with respect to catalyst concentrations. Change in the ionic strength of the medium or concentrations of hydrogen ions, cerium(III) and acetic acid have no effect on the rate. Interestingly with fair degree of accuracy, the rate of un-catalyzed path may be separated graphically with the help of the intercept of catalyst graph. IR spectrum of the product confirmed cinnamic acid as the final oxidation product. Energy of activation, free energy of activation and entropy parameters were calculated.

Addition of catalyst changes the order of reaction in oxidant and its intercept gives the value of the rate of un-catalyzed reaction in IrIII catalyzed oxidation of cinnamaldehyde by CeIV in acidic medium. Cerium(IV) is not reduced before the slow step with cinnamic acid as the oxidation product. Catalyzed path may be given as Figure optionsDownload as PowerPoint slide