Surface charging parameters of charged particles in symmetrical electrolyte solutions

Abstract

Surface electric charge of dispersed particles is an essential determinant of physicochemical properties, coagulation and flocculation processes, and stability of colloidal solutions. Size-dependence of surface potential, charge density, and total surface charge of suspended charged particles has recently received attention in the literature. Despite the clear significance of understanding such dependence, very few studies have been devoted to this problem, with contradictory results of the relationship type. Currently, there is no analytical formula to represent explicit relationships between surface charging parameters and particle size. This research work is directed at development of accurate physics-based formulas for quantification of curvature-dependence of surface potential, surface charge density, and total surface charge for cylindrical and spherical charged particles immersed in a symmetrical electrolyte solution. First, a non-dimensional approach is adopted to simplify the problems, overcoming the difficulty of dealing with multiple influential variables. Then, to reduce the degrees of freedom of the problems under consideration, Gauss's law is combined with the condition of electro-neutrality in an electrical double layer (EDL). Next, the resulting complex integral equations are solved to construct characteristic curves and to express the dimensionless surface charging parameters explicitly as a function of the dimensionless particle radius. The new theoretical expressions are founded on approximate analytical and numerical solutions of the nonlinear Poisson–Boltzmann (PB) equation in cylindrical and spherical geometries. Afterwards, the solutions of the non-dimensionalized problems are dimensionalized to derive accurate explicit closed-form expressions, describing how surface charging parameters are related to the radius of a charged particle, properties of the solution, and thermodynamic conditions. These analytical formulas enable researchers to properly determine surface potential, surface charge density, total surface charge, and radius of dispersed particles by characterizing only one of them. Finally, the validity of the commonly-held hypothesis that surface charge density is independent of particle size is examined at the end of this study.