SOME ASPECTS OF DISCRETENESS-OF-CHARGE AND ION-SIZE EFFECTS FOR IONS ADSORBED AT CHARGED METAL-AQUEOUS ELECTROLYTE INTERFACES

It is argued that the self-image potential of an ion adsorbed on a charged metal from an aqueous electrolyte is described in terms of multiple imaging and not single imaging in the metal as proposed by Bockris. The image potential of an isolated ion situated on the i.H.p. in the inner region with a continuously and smoothly varying dielectric profile is calculated. This is compared with the corresponding potential for an inner region model with a discontinuous dielectric profile. It is shown that when the position of the i.H.p. relative to the o.H.p. is changed, the two potentials will in general cross each other such that the discontinuous model has the more negative self-image potential when the i.H.p. approaches the o.H.p. The scaled-particle expression for the entropic contribution due to ion-size effects in the adsorption isotherm of an ion in the inner region is compared with the corresponding Flory-Huggins formula. It is demonstrated that the two theories can give very different results. In particular, when the adsorbed ions are considerably larger than the solvent molecules, it is possible that scaled-particle theory leads to a 'negative' ion-size entropy term, which decreases with increase in density of adsorbed ion. © 1979 Elsevier Sequoia S.A.