Ruthenium(III) catalyzed kinetics of chloroacetic acids oxidation by sodium N‐bromobenzenesulfonamide in hydrochloric acid medium

Ananda, S. and Venkatesha, B.M. and Mahadevappa, D.S. and Gowda, N.M.M. (1993) Ruthenium(III) catalyzed kinetics of chloroacetic acids oxidation by sodium N‐bromobenzenesulfonamide in hydrochloric acid medium. International Journal of Chemical Kinetics, 25 (9). pp. 755-770.

Full text not available from this repository. (Request a copy)
Official URL: https://doi.org/10.1002/kin.550250906

Abstract

Kinetics of uncatalyzed and Ru(III)-catalyzed oxidations of mono-, di-, and tri-chloroacetic acids by the title compound (bromamine-B or BAB) in HCl medium has been studied at 40-degrees-C. The uncatalyzed reaction shows a first-order dependence of the rate on BAB], and fractional and zero orders in acid] at low and high HCl] ranges, respectively. The Ru(III)-catalyzed reaction, on the other hand, shows a first-order behavior on each of BAB] and substrate], second-order dependence on Ru(III)], and inverse fractional and inverse first orders in acid] at low and high HCl] ranges. Addition of halide ions and the reduction product of BAB, benzenesulfonamide, has no effect on the reaction rate. Variation of ionic strength of the medium has no influence on the reaction. Solvent isotope effect was studied using D2O. Activation parameters have been evaluated from the Arrhenius plots. Mechanisms consistent with the above kinetic data have been proposed. The protonation constant of monobromamine-B evaluated from the uncatalyzed reaction is 12.4 while that evaluated from Ru(III) catalyzed reaction is 12.7. A Taft linear free-energy relationship is noted for the catalyzed reaction with rho* = 1.2 and 0.07 indicating that electron withdrawing groups enhance the rate. An isokinetic relation is observed with beta = 338 K indicating that enthalpy factors control the reaction rate. (C) 1993 John Wiley & Sons, Inc.

Item Type: Article
Subjects: C Chemical Science > Chemistry
Divisions: Department of > Chemistry
Depositing User: lpa venkatesh user
Date Deposited: 07 May 2021 08:02
Last Modified: 07 May 2021 08:02
URI: http://eprints.uni-mysore.ac.in/id/eprint/16290

Actions (login required)

View Item View Item