Development of a Generalized Version of the Poisson– Nernst–Planck Equations Using the Hybrid Mixture Theory: Presentation of 2D Numerical Examples

Abstract

A numerical scheme for the transient solution of a generalized version of the Poisson–Nernst–Planck (PNP) equations is presented. The finite element method is used to establish the coupled non-linear matrix system of equations capable of solving the present problem iteratively. The PNP equations represent a set of diffusion equations for charged species, i.e. dissolved ions, present in the pore solution of a rigid porous material in which the surface charge can be assumed neglectable. These equations are coupled to the ‘internally’ induced electrical field and to the velocity field of the fluid. The Nernst–Planck equations describing the diffusion of the ionic species and Gauss’ law in use are, however, coupled in both directions. The governing set of equations is derived from a simplified version of the so-called hybrid mixture theory (HMT). The simplifications used here mainly concerns ignoring the deformation and stresses in the porous material in which the ionic diffusion occurs. The HMT is a special version of the more ‘classical’ continuum mixture theories in the sense that it works with averaged equations at macroscale and that it includes the volume fractions of phases in its structure. The background to the PNP equations can by the HMT approach be described by using the postulates of mass conservation of constituents together with Gauss’ law used together with consistent constitutive laws. The HMT theory includes the constituent forms of the quasistatic version of Maxwell’s equations making it suitable for analyses of the kind addressed in this work. Within the framework of HTM, constitutive equations have been derived using the postulate of entropy inequality together with the technique of identifying properties by Lagrange multipliers. These results will be used in obtaining a closed set of equations for the present problem.