Abstract
The kinetics of the osmium(VIII)-catalysed oxidation of selenium(IV) by alkaline ferricyanide has been studied for 0·1M-perchlorate solutions. The reaction shows first-order dependence to the concentrations of SeIV, Fe(CN)63–, OH– and OsVIII. Increase in ionic strength of the medium has an accelerating effect on the reaction rate, while an addition of ferrocyanide ions retards the rate. The mechanism indicates that the reaction occurs by the interaction between HSeO43– and Fe(CN)63– ions forming an unstable HSeO42– intermediate which is then attacked by OsVIII to give the oxidised product HSeO4– and the reduced form of osmium rapidly reacts with another molecule of ferricyanide to regenerate the OsVIII. The rate law expression has been obtained.
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