Abstract
The kinetics of oxidation of diphenylsulfoxide (DPSO) by N-sodio-N-bromobenzenesulfonamide also known as bromamine-B (BAB) has been studied in HCl solution at 30°C. In the absence of Ru(III), the rate shows a first-order dependence on [BAB] and fractional-order dependence each on [DPSO] and [H+]. In the presence of Ru(III), the rate is first-order with respect to [BAB] and fractional-order each on [DPSO], [H+] and [Ru(III)] at low acid concentration. At high acid concentration the reaction rate shows a first-order dependence each on [oxidant], [DPSO] and [H+] and fractional-order on [Ru(III)]. The variation of the ionic strength, dielectric constant of the medium and addition of chloride ion and the reaction product of BAB (benzenesulfonamide) do not have any significant effect on the reaction rate. The activation parameters have been evaluated. The value of the protonation constant of monobromamine-B, 84.7 at 303 K, is evaluated from the proposed mechanism. Mechanisms consistent with the observed kinetic data have been proposed.
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