Abstract
An integral equation of the Kirkwood type can be derived for the pair correlation function between two ions situated in a planar electric double layer by charging one of the ions. The use of this function in a modified Poisson-Boltzmann equation for the double layer potential is discussed. The correlation function should be symmetrical in the two ions when these are equidistant from the interface. This symmetry is lost when a closure procedure is introduced to solve the integral equation, which implies linear superposition of the self-atmospheres of the two ions. Two methods of restoring this symmetry are proposed. The relevance of the pair-correlation function to the discreteness-of-charge effect for adsorbed ions in the Stern inner region is explained. For two oppositely-charged species on the adsorption plane, the ion-pairing theory of Bjerrum and Fuoss, as extended by Poirier and DeLap, is applied in determining the discreteness-of- charge potential.
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