Palladium(II)-catalyzed oxidation of alpha-hydroxy acids with sodium N-chlorobenzenesulfonamide in perchloric acid solution: A kinetic and mechanistic study

Revathi, S. K. and Ananda, S. and Mohana, K. N. and Rangaswamy (2004) Palladium(II)-catalyzed oxidation of alpha-hydroxy acids with sodium N-chlorobenzenesulfonamide in perchloric acid solution: A kinetic and mechanistic study. COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 69 (8). pp. 1577-1589. ISSN 0010-0765

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Official URL: https://doi.org/10.1135/cccc20041577

Abstract

Kinetics of oxidation of glycolic acid (GA), lactic acid (LA) and 2-hydroxybutanoic acid (BA) with Chloramines B (CAB) catalyzed by Pd(II) in a HClO4 solution has been studied at 30 degreesC. The reaction rate shows first-order dependence each on CAB], hydroxy acid] and Pd( II)] and a fractional-order dependence on H+]. Additions of chloride ions, perchlorate ions and the reduction product of CAB, benzenesulfonamide (BSA), have no effect on the reaction rate. Variations of ionic strength and dielectric permittivity of the medium have no effect on the rate. Activation parameters have been evaluated. A mechanism consistent with kinetic data is proposed. A Taft linear free-energy relationship is observed for the reaction with rho(*) = - 3.593, indicating an increase in the rate with the presence of electron-donating substituents. An isokinetic relationship is observed with = 376 K, indicating the effect of enthalpy factors on the rate.

Item Type: Article
Uncontrolled Keywords: chloramine B; alpha-hydroxy acids; kinetics; oxidation; palladium(II); mechanism; substituent effects
Subjects: C Chemical Science > Chemistry
Divisions: Department of > Chemistry
Depositing User: lpa venkatesh user
Date Deposited: 22 Aug 2019 10:35
Last Modified: 22 Aug 2019 10:35
URI: http://eprints.uni-mysore.ac.in/id/eprint/6627

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