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Kinetics of oxidation of uranium(IV) by permanganate ion in aqueous perchlorate media

The kinetics of oxidation of uranium(IV) by permanganate ion in 1.0 mol dm–3 perchloric acid solution has been investigated using a stopped-flow spectrophotometer. The reaction was found to be second order overall and first order in the concentrations of both reactants. The catalytic effect of the perchlorates of Hg2+, Cu2+, and Fe3+ on the reaction rate has been investigated. The activation parameters were evaluated and found to be ΔS‡= 30.52 ± 1.22 J K–1 mol–1, ΔH‡= 62.89 ± 1.87 kJ mol–1, and ΔG‡= 53.79 ± 1.44 kJ mol–1. A tentative mechanism consistent with the kinetics is discussed.