A new correlation effect in the Helmholtz and surface potentials of the electrical double layer

The restricted primitive model of an electrical double layer around a spherical macroparticle was discussed. The theoretical curves for the Helmholtz and surface potentials versus the macroparticle charge showed an unexpected positive curvature when the ionic size of uni- and divalent electrolyte species was increased. The concept of compactness of the electrical double layer was introduced. Analysis shows that the interplay between electrostatic and ionic size correlation effects was responsible for the singularity.

Adsorption; Colloids; Computer simulation; Electrolysis; Electrolytes; Integral equations; Monte Carlo methods; Surface properties; Theorem proving; Thermodynamics; Electrical double layers; Electrolyte species; Macroparticles; Electrodynamics

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