An interpretation framework is presented which provides a straightforward means to characterise the electrochemical reactivity of aqueous ions together with their various hydrolysed counterparts. Our novel approach bypasses the more laborious strategy of solving rigorously, for all relevant species, the complete set of Butler-Volmer equations coupled to diffusion differential equations. Specifically, we consider the spatial variable via a Koutecký-Koryta type of differentiation between nonlabile and labile zones adjacent to the electrode. The theory is illustrated by an assessment of the electrochemical reactivity of aqueous In(III) species based upon proper comparison between relevant time scales of the involved interfacial processes, i.e. diffusion, (de)protonation of inner-sphere water, dissociation/release of H2O and OH−, and electron transfer. The analysis reveals that whilst all In(III) species are labile on the experimental timescale with respect to (de)protonation and (de)hydration, there are large differences in the rates of electron transfer between In(H2O)63+ and the various hydroxy species. Specifically, in the case of In(H2O)63+, the rate of electron transfer is so slow that it replaces the traditional Eigen rate-limiting water release step in the overall passage from hydrated In3+ to its reduced metallic form; in contrast, the In(III) hydroxy species display electrochemically reversible behaviour.
- Electrochemical irreversibility
- Reaction layer