Abstract
We have calculated analytically the electrostatic Gibbs energy profile for transfer of an ion between two bulk dielectric phases separated by a planar boundary. The profile incorporates the finite ionic size and dielectric image interactions. There is no discontinuity as the ion traverses the boundary and the model is well represented by a simple point charge when the ionic centre is beyond about half an ionic radius from the boundary. The profile is in line with observations based on interfacial inner-layer capacitances that ions can partly penetrate the boundary between two immiscible liquids at equilibrium. It represents an inner-layer capacitance contribution when the distance of closest approach is different for cations and anions.
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