Concept of Reversible Cleavage in Surface Tension of Solids¹

V. A. Marichev

Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7

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Received June 4, 2009

Abstract — “Wholly plastic (as in cleavage)" surface area changing is the widely accepted concept formally allowing the application of Gibbs thermodynamics to surface tension of solids considered as a reversible process of partly plastic and partly elastic deformation as recommended by the IUPAC. However, this concept contains some internal contradictions that are serious enough to raise doubts about its correctness and, conseuently in validity of the thermodynamic analysis of surface tension of solid electrodes based on this concept.  This analysis leads to the generalized Lippmann equation and eventually approves using the classical Lippman equation for solids. The latter is shown to be erroneous since it is based on the misleading concept of “reversible cleavage” and contradicts all available in situ experimental data.