Abstract
Uncatalysed and OsVIII-catalysed oxidation of dimethyl sulphoxide (DMSO) by potassium ferrate [FeVI] has been studied in alkaline medium in the 9.8–11.9 pH range, in the presence of IO 4 − as a stabilizing agent. The order in [FeVI] and [DMSO] was found to be unity for the uncatalysed reaction and zero and fractional respectively for the catalysed reaction. The [OsVIII] order was unity in the catalysed reaction. The rate of oxidation decreased with increase in pH and the order in [H+] was fractional for the uncatalysed oxidation. However in the catalysed oxidation, the rate at first decreased and then increased with increase in pH. The effect of changing [IO 4 − ] and [buffer] on the oxidation rate was negligible in both cases. Suitable mechanisms consistent with the observed kinetics have been proposed.
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