Abstract
The effect of capillary waves on the double layer capacitance of the interface between two immiscible electrolytes has been studied. We have found that a corrugation of the interface due to capillary waves leads to an increase in the capacitance, as compared with the Gouy–Chapman result for a flat interface. The theory offers a concept of a roughness function, R̃, which determines the deviation of capacitance from the Gouy–Chapman result. R̃ is a function of Debye lengths of the two immiscible electrolytes. Analytical expression for the roughness function has been derived which shows a strong dependence of R̃ on the interfacial tension and the dielectric constants of contacting solutions. Predictions amenable to experimental tests have been discussed.
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