Kinetic study of the oxidation of water by CeIV ions mediated by activated ruthenium dioxide hydrate

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Abstract
The results of a kinetic study of the oxidation of water to oxygen by CeIVions, mediated by thermally activated ruthenium dioxide hydrate (RuO2·yH2O*), are reported. At low [Ce4+], i.e. ca. 3.45 × 10–5 mol dm–3, the rate of reduction of CeIV ions (R) was diffusion controlled and depended directly upon [Ce4+]. and [redox catalyst], but was virtually independent of [Ce3+]. At higher [Ce4+], i.e. 3.45 × 10–3 mol dm–3, the kinetics were more complex, with R decreasing with increasing [Ce3+] and decreasing [Ce4+] and [redox catalyst]. The observed kinetics can be successfully described using an electrochemical model in which the catalyst particles are considered to act as microelectrodes which mediate the transfer of electrons between a Nernstian reaction (the reduction of CeIV ions) and an irreversible reaction (the oxidation of water). Using this model it proved possible to obtain from any [Ce4+]vs. time decay trace a Tafel plot of the variation of current as a function of potential for the oxidation of water on the surface of the particles of RuO2·yH2O*. In addition to providing valuable mechanistic information concerning this reaction, it also allowed the original kinetic traces to be reconstructed and decay curves simulated for a wide range of conditions. From the variation in Tafel plot data as a function of temperature, an activation energy for water oxidation of 52 ± 8 kj mol–1 was obtained.

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