kinetics of oxidation of chloroacetic acids by sodium n-bromo-p-toluenesulphonamide (bromamine-t) in hcl medium and catalysis by ru(iii) ion

Venkatesha, B. M. and Sridhar, M. A. and Mahadevappa, D. S. (1994) kinetics of oxidation of chloroacetic acids by sodium n-bromo-p-toluenesulphonamide (bromamine-t) in hcl medium and catalysis by ru(iii) ion. INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY, 33 (2). pp. 128-135. ISSN 0376-4710

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Abstract

Kinetics of uncatalysed and Ru(m) catalysed oxidations of mono, di and trichloroacetic acids by bromamine-T (BAT) in acid medium has been studied at 40 degrees C. The rate laws for the two Paths are rate = k[BAT][H+](x) and rate = [BAT](t)[S](t)[Ru(III)(y)[H+](-z) where x, y and z are less than unity. Added halide ions and the reaction product, toluenesulphonamide have no effect on the rate. Variation in ionic strength of medium has no influence on the reaction. The solvent isotope effect has been studied in D2O medium. Activation parameters have been evaluated from the Arrhenius plots. Mechanisms consistent with the experimental rate laws have been proposed. The protonation constant of monobromamine-T to form CH3C6H4SO2NH(2)Br is evaluated from the uncatalysed reaction as 9.3 + 1.0 at 40 degrees C. The value for the same from Ru(III) catalysed reaction is 10.3 +/- 1.0. A Taft linear free-energy relation is noted for the catalysed reaction with rho*=1.22 and 0.067 indicating that electron withdrawing groups increase the rate. An isokinetic relation is observed with beta=457K showing that enthalpy factors control the rate of reaction.

Item Type: Article
Additional Information: Unmapped bibliographic data: DA - 1994/02// [EPrints field already has value set] LA - English [Field not mapped to EPrints]
Subjects: Physical Sciences > Chemistry
Divisions: PG Campuses > Manasagangotri, Mysore > Chemistry
Depositing User: Users 24 not found.
Date Deposited: 06 May 2013 07:01
Last Modified: 11 Nov 2015 07:09
URI: http://eprints.uni-mysore.ac.in/id/eprint/8323

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