The interaction of electric field and hydrostatic pressure in an electrical double layer: A simple 'first principle' model that accounts for the finite sizes of counterions

摘要

A simple model describing the influence of ion size in the electrical double layer (EDL) near a highly charged plane is proposed here. This model is based on the Poisson-Boltzmann equation with a single additional term representing the mechanical response of bulky ions to hydrostatic pressure. This pressure is produced by Coulomb forces, and increases to several kilobars in the vicinity of a highly charged plane. Numerical simulations demonstrate close packing as a limit for counterion concentrations. Differential capacity reaches maximum at 0.1-0.3 V and remains reasonably small in wide range of potentials. (C) 2015 Elsevier Inc. All rights reserved.