Mathematical Modeling of the Influence of Equilibrium Coefficient Variation on the Steady-State Transport of a Binary Electrolyte in the Cross-Section of a Desalination Channel

This paper presents the first theoretical investigation of the effect of a variable equilibrium coefficient on the steady-state transport of a binary electrolyte in a desalination channel cross-section of the electrodialyzer. To address this problem, we developed a new mathematical model in the form of a boundary value problem for an extended system of stationary Nernst–Planck–Poisson equations. We obtained a numerical solution to this problem using the finite element method. Analysis of this solution revealed that the channel cross-section has a complex structure: it is divided into seven regions dominated by different processes, and, consequently, the solution to the boundary value problem behaves differently in each of them. Existing models of the diffusion layer or channel cross-section typically assume a constant equilibrium coefficient. In this paper, we demonstrated that in the channel cross-section, the velocity change corresponding to the equilibrium constant is related not only to the field strength but also to the magnitude of the space charge. In the space-charge region, in the boundary layers near the ion-exchange membranes, intense dissociation of water molecules occurs, and the higher the equilibrium coefficient, the more intense this dissociation is. We have shown that an internal boundary layer (recombination region) arises deep within the solution, associated with the recombination reaction of H+ and OH− ions. In this study, we found that with increasing equilibrium coefficient, fluxes increase, while with increasing fluxes, the electric field strength decreases proportionally, and equilibrium is reached. We demonstrate that by calibrating a single fitting parameter in the model, the simulation results can be matched to experimental data with high accuracy. Thus, our proposed model and its numerical solution provide a completely new understanding of the ion transport process in electromembrane systems, taking into account the influence of the dissociation/recombination reaction of water molecules.