Rigorous analysis of reversible faradaic depolarization processes in the electrokinetics of the metal/electrolyte solution interface

The bipolar faradaic depolarization of the interface metal/solution is examined for the situation in which the transversal electron transfer is limited by mass transfer of the components of a reversible redox couple. Transversal diffusion of the electroactive species to and from the surface and lateral convective mass transport, resulting from a pressure gradient applied along the surface, are taken into account. The analysis first focuses on the case in which the lateral electric field required for bipolar behavior is externally applied through the solution. Numerical analysis of the intrinsic nonlinear coupling between the convective-diffusion equation and the Poisson equation for finite currents allows derivation of the spatial distribution of the potential and the concentration profiles of the electroactive species. The corresponding distribution of the local faradaic current density along the metallic surface and the ensuing overall bipolar current are obtained. Characteristics of the conductivity curves, bipolar current versus applied field, are given for different sets of electric and hydrodynamic parameters. Then, on the basis of these results, the analysis of bipolar faradaic depolarization process is extended to electrokinetic phenomena, in particular streaming potential.