Oxidation of dimethylsulphoxide by sodium m-bromobenzene- sulphonamide: A kinetic and mechanistic study |
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| Authors: | DS Mahadevappa S Ananda ASA Murthy KS Rangappa |
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| Institution: | 1. Department of Chemistry, University of Saskatchewan, Saskatoon, Sask. Canada S7N OWO |
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| Abstract: | The kinetics of oxidation of dimethylsulphoxide (DMSO) by sodium N-bromobenzenesulphonamide or bromamine-B (BAB) has been studied in HClO4, HCl and NaOH media, at 35°C, with OsO4 as a catalyst in the latter medium. In acid medium, the rate shows a first order dependence on BAB] and second order in H+], but Is Independent of substrate concentration. Alkali retards the reaction (Inverse first order) and the rate is independent of oxidant concentration, but shows fractional order in DMSO] and depends on (0sO4]2. The solvent isotope effect was studied by using D2O. Activation parameters have also been determined. Mechanisms proposed and the derived rate laws are consistent with the observed kinetics. |
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