Poisson–Nernst–Planck model with Chang-Jaffe, diffusion, and ohmic boundary conditions

Abstract

Using the linear Poisson–Nernst–Planck impedance-response continuum model, we investigate the possible equivalences of three different types of boundary conditions previously proposed to model the electrode behavior of an electrolytic cell in the shape of a slab. We show analytically that the boundary conditions proposed long ago by Chang-Jaffe are fully equivalent to the ohmic boundary conditions only if the positive and negative ions have the same mobility, or when only ions of a single polarity are mobile. In the case where the ions have different and non-zero mobilities, we fit exact impedance spectra created for ohmic boundary conditions by using the Chang-Jaffe Poisson–Nernst–Planck response model, one that is dominated by diffusion effects. These fits yield conditions for essentially exact or approximate numerical correspondence for the complex impedance between the two models even in the unequal mobility case. Finally, diffusion type boundary conditions are shown to be fully equivalent to the ohmic one. Some limiting cases of the model parameters are investigated.