Series Approach to Modeling Ion Size Effects for Asymmetric Electrolytes in the Diffuse Double Layer

Abstract

The theory of the diffuse layer for asymmetric electrolytes is reconsidered with emphasis on the effects of ion size on the diffuse layer potential drop and differential capacity. For asymmetric 2:1 and 1:2 electrolytes, this potential drop is expressed in terms of a polynomial with a linear, quadratic, and cubic term in the corresponding estimate in the Gouy-Chapman theory. Optimal polynomial coefficients and model validation for 2:1 electrolytes are provided by least-squares regression of Monte Carlo data obtained for a restricted electrolyte in a primitive solvent. These coefficients are then expressed as simple functions of the parameters commonly associated with the mean spherical approximation. The series approach accurately describes potential drops and differential capacities of the diffuse layer for 2:1 and 1:2 electrolytes for the chosen assumptions.