A new model of the differential capacitance of the double layer

D. Price, J. W. Halley

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Abstract

We present a new model of the metal-electrolyte interface which takes explicit account of the mobility of electrons at a metallic interface. The model can be described as a simple modification of the classical Stern-Gouy-Chapman double layer theory, but it contains an essential new feature of fundamentally quantum mechanical origin. A basic prediction of the theory is that at high enough temperatures the inverse 1/Cc of the compact part of the differential capacitance Cc is linear in the charge σm per unit area for small σm if adsorption does not occur. We confirm this for Hg, In, Ag, Cd and (Pb) with NaF (KF) electrolyte. The slope of the 1/Cc vs. σm line is predicted in a simple model to be proportional to the inverse 1/ρ{variant}m of the metallic charge density ρ{variant}m and we predict the coefficient on the basis of two detailed models. The results are compared with experiment on a variety of metal electrolyte interfaces. The limitations of the theory are discussed.

Original languageEnglish (US)
Pages (from-to)347-353
Number of pages7
JournalJournal of Electroanalytical Chemistry
Volume150
Issue number1-2
DOIs
StatePublished - Jul 25 1983

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