Abstract
Two-dimensional concentrations of adsorbed ions in double-layers at charged interfaces, especially when appreciable specific adsorption obtains, are equivalent to quite substantial (1–4 M ) three-dimensional concentrations in regular electrolyte solutions. Under such conditions, ion-specific Gurney co-sphere overlap interactions give an important contribution to the non-ideal free energy of electrolytes in solution. It is proposed that similar interaction effects arise two-dimensionally in double-layers, giving rise to a contribution to the lateral interaction energy in monolayer arrays of ions. Three types of calculations are described by which these interaction effects can be evaluated. One is applied to some recent data on tetrapropylammonium ion adsorption at Hg, where hydrophobic interactions arise. Related problems concerned with solvent dipole orientation in the inner layer, when appreciable surface concentrations of hydrated ions are present, are referred to. The probable role of field-gradient/quadrupole interactions is noted.
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