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Thermodynamics for the situation where there is a discontinuous change of the electrode condition with potential due to the formation of a two dimensional condensed phase - diffuse layer effects

Lookup NU author(s): Professor Ronald Armstrong, Dr Ben Horrocks

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Abstract

The thermodynamics for the situation where there is a discontinuous change of the electrode condition with potential due to the formation of a two dimensional condensed liquid-like phase are examined, with particular reference to the effect of the presence of a diffuse layer. The existence of a diffuse layer does not fundamentally change the nature of the transition. However the potential at which the discontinuity is found is very sensitive to the concentration of support electrolyte, although the charge on the electrode is relatively insensitive. It is shown that transitions from gas-like adsorption to liquid-like adsorption are always irreversible (in a theoretical sense) because of the positive edge free energy associated with patches of the liquid-like state. (C) 1999 Elsevier Science S.A. All rights reserved.

Publication metadata

Author(s): Armstrong RD, Horrocks BR

Publication type: Article

Publication status: Published

Journal: Journal of Electroanalytical Chemistry

Year: 1999

Volume: 463

Issue: 1

Pages: 9-15

Print publication date: 01/03/1999

ISSN (print): 1572-6657

ISSN (electronic): 1873-2569

Publisher: Elsevier SA

URL: http://dx.doi.org/10.1016/S0022-0728(98)00426-4

DOI: 10.1016/S0022-0728(98)00426-4

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