Redox Reactions of Platinum Elements: XV. Kinetics of Rhodium(III) Oxidation with Xenon Difluoride in Nitric Acid Solutions |
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| Authors: | Koltunov V. S. Khaperskaya A. V. Koltunov G. V. Renard E. V. |
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| Affiliation: | (1) Bochvar Russian Research Institute of Inorganic Materials, State Scientific Center of the Russian Federation, Moscow, Russia |
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| Abstract: | The rate of the reaction 2Rh(H2O)63+ + XeF2 = 2Rh(OH)3+ + Xe + 2HF + 4H+ + 6H2O is described by the second-order equation -d[Rh(III)]/dt = k1[Rh(III)][XeF2], where k1 = 15.4±0.8 l mol-1 min-1 at 17.8°C and the solution ionic strength  = 2. The activation energy of the reaction is E1 = 60.6±1.0 kJ mol-1. This reaction is complicated by the parallel hydrolysis reaction 2XeF2 + 2H2O = 2Xe + O2 + 4HF. The reaction mechanism includes a slow stage of H atom transfer from Rh(H2O)63+ to XeF2 molecule with formation of XeF. radical as an intermediate. The subsequent stages of Rh(H2O)5(OH)3+ hydrolysis and reduction of XeF· radical to Xe proceed rapidly. |
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