Poisson–Boltzmann Description of the Electrical Double Layer Including Ion Size Effects

Abstract

The electrical double layer is examined using a generalized Poisson-Boltzmann equation that takes into account the finite ion size by modeling the aqueous electrolyte solution as a suspension of polarizable insulating spheres in water. We find that this model greatly amplifies the steric effects predicted by the usual modified Poisson-Boltzmann equation, which imposes only a restriction on the ability of ions to approach one another. This amplification should allow for an interpretation of the experimental results using reasonable effective ionic radii (close to their well-known hydrated values).