Abstract
The oxidation of MnII by S2O82− to MnVII in phosphoric acid medium proceeds via a stable MnIII and MnIV species. The reaction is catalysed by Ag+ and exhibits first order dependence on [S2O82−], [Ag+] and, is independent of [MnII]. The [H+] has no significant effect on the reaction. It is observed that the PO43− ion stabilises the transient manganese(III) and manganese(IV) species by forming a stable and soluble phosphato-complexes. The activation parameters for the two stages of oxidation, namely MnII →MnIV and MnIV→MnVII at 25° C are Ea=52 ±4 kJ mole−1, ΔS*=−57±2 JK−1 mole−1 and Ea =56±4 kJ mole−1, ΔS*=−44±2 JK−1 mole−1, respectively. A mechanism consistent with the experimental observations is proposed.
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