Steric Effects in Electrolytes: A Modified Poisson-Boltzmann Equation

The adsorption of large ions from solution to a charged surface is investigated theoretically. A generalized Poisson--Boltzmann equation, which takes into account the finite size of the ions is presented. We obtain analytical expressions for the electrostatic potential and ion concentrations at the surface, leading to a modified Grahame equation. At high surface charge densities the ionic concentration saturates to its maximum value. Our results are in agreement with recent experiments.