The dominance of small ions in the electric double layer of size- and charge-asymmetric electrolytes: a mean-field study on the charge reversal and surface charge amplification

The dominance of counterions in the electric double layer of size-asymmetric semi-punctual ions was proposed more than 30 years ago by Valleau and Torrie. According to their theoretical prescription, at large colloidal surface charges, the double layer properties of a fully asymmetric binary electrolyte become similar to those of a completely symmetric electrolyte if the properties of counterions are the same in both instances. In the same theoretical framework, we propose here that, for a fixed concentration of the smallest ionic species and weakly/moderate colloidal surface charges, the valence of small ions rules or mainly determines the structural and thermodynamic properties of the electric double layer regardless of the colloidal polarity. In other words, we show that the characteristics of the small ions dominate the double layer structure of non-highly charged colloids, independently if the small ions are coions or counterions. This is illustrated by a comprehensive analysis of the ionic and integrated charge profiles around a spherical macroion immersed in a fully size- and charge-asymmetric semi-punctual electrolyte. Charge reversal and surface charge amplification are observed in the regime of low/medium colloidal surface charge densities. The origin of these counterintuitive phenomena, and their corresponding localisation properties in the Helmholtz zone, are explained in terms of the electric double layer structure.