Kinetics and mechanism of oxidation of amyl alcohol by pyridinium bromochromate

The kinetics of oxidation of amyl alcohol(AA) by pyridinium bromo chromate(PBC) has been studied in 50% acetic acid - water (v/v) medium in the presence of perchloric acid at 303K. The reaction is first order each in pyridinium bromochromate and amyl alcohol. The reaction is not depends on the hydrogen ion concentration . It shows zero order with respect to hydrogen ion concentration. The rate of oxidation increases with decrease in dielectric constant of solvent suggests ion-diople interaction. Increase in ionic strength by the addition of sodium perchlorate has no effect on the rate constant. There is no polymerization with acrylonitrile and absence of free radical was proved. Amyl aldehyde has been identified as a product of oxidation. The rate of the reaction has been conducted at four different temperatures and activation parameters were calculated. From the observed kinetic results, a suitable mechanism with rate law has been proposed.

Author(s): M. Vellaisamy and R. Santhi

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