Decoupling of the Nernst-Planck and Poisson equations. Application to a membrane system at overlimiting currents

This paper deals with one-dimensional stationary Nernst-Planck and Poisson (NPP) equations describing ion electrodiffusion in multicomponent solution/electrode or ion-conductive membrane systems. A general method for resolving ordinary and singularly perturbed problems with these equations is developed. This method is based on the decoupling of NPP equations that results in deduction of an equation containing only the terms with different powers of the electrical field and its derivatives. Then, the solution of this equation, analytical in several cases or numerical, is substituted into the Nernst-Planck equations for calculating the concentration profile for each ion present in the system. Different ionic species are grouped in valency classes that allows one to reduce the dimension of the original set of equations and leads to a relatively easy treatment of multi-ion systems. When applying the method developed, the main attention is paid to ion transfer at limiting and overlimiting currents, where a significant deviation from local electroneutrality occurs. The boundary conditions and different approximations are examined: the local electroneutrality (LEN) assumption and the original assumption of quasi-uniform distribution of the space charge density (QCD). The relations between the ion fluxes at limiting and overlimiting currents are discussed. In particular, attention is paid to the "exaltation" of counterion transfer toward an ion-exchange membrane by co-ion flux leaking through the membrane or generated at the membrane/solution interface. The structure of the multi-ion concentration field in a depleted diffusion boundary layer (DBL) near an ion-exchange membrane at overlimiting currents is analyzed. The presence of salt ions and hydrogen and hydroxyl ions generated in the course of the water "splitting" reaction is considered. The thickness of the DBL and its different zones, as functions of applied current density, are found by fitting experimental current-voltage curves.