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Kinetics and Mechanism of Oxidation of Aromatic Acetals by Ceric Ammonium Nitrate in Acetonitrile Medium

Authors: P. CHOCKALINGAM; P. S. RAMAKRISHNAN; S. J. ARULRAJ; K. NAMBI;

Kinetics and Mechanism of Oxidation of Aromatic Acetals by Ceric Ammonium Nitrate in Acetonitrile Medium

Abstract

Department of Chemistry, Rajah Serfoji Government College, Thanjavur-613 005 Post-Graduate Department of Chemistry, The Autonomous St. Joseph's College. Tiruchirapalli-620 002 Manuscript received 25 July 1991, revised 23 March 1992, accepted 1 April 1992 Aromatic acetals of benzaldehyde and substituted benzaldehydes with n-butanol have been prepared and subjected to ceric ammonium nitrate oxidation in acetonitrile medium. The oxidation follows a total second order kinetics, first order each in (acetal) and [CeIV]. Variation in ionic strength of the medium and added nitrate ions have no influence on the rate. Decrease of dielectric constant of the medium decreases the rate. Activation parameters have been computed from Arrhenius plots. Activation enthalpy and entropy of the oxidation are linearly related. Both activation energy and frequency factor have been found to control the reaction. A probable mechanism has been proposed.

Keywords

Oxidation, Benzaldehyde

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