Influence of the dielectrophoretic force in mixed electrical double layers.

The equilibrium properties of a charged plane immersed in an aqueous electrolyte solution are examined using a generalized Poisson-Boltzmann equation that takes into account the finite ion size by modeling the solution as a suspension of polarizable insulating spheres in water. This formalism is applied to a general solution composed of two or more counterion species with different valences, sizes, and effective permittivity values. It is shown that, due to the dependence of the dielectrophoretic force on the ion size and effective permittivity value, the concentration of the smaller counterion strongly increases while that of the larger one decreases in the immediate vicinity of the charged surface. As a result the surface potential value strongly increases as compared to the usual modified Poisson-Boltzmann theory that only includes steric interactions among ions. This effect is particularly important in the case of mixtures of univalent and divalent counterions, being significant even for relatively low surface charge values.