Surface tension of solids. Structure-mechanical approach |
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Authors: | V A Marichev |
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Affiliation: | (1) Department of Chemistry, University of Western Ontario, London, Ontario, Canada, N6A 5B7 |
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Abstract: | Problems of applying the classic and generalized Lippmann equations to adsorption studies on solid electrodes are shortly
reviewed. Long-time thermodynamic discussion results in no clear-cut decision. A new nonthermodynamic approach is proposed
considering the principal possibility and role of elastic and plastic deformations of the electrode surface during adsorption.
The extremely thin electrode surface layers affected electrically and mechanically by adsorbate are supposed to be free of
dislocations because of volume restriction. The nearest structure-mechanical analogs of such layers are the whisker crystals
whose side surface could have one-and two-dimensional defects, but no active dislocations. Like whiskers, surface metal layers
should possess a high ultimate strength close to the theoretical one and a purely elastic deformation. Special attention has
been paid to the concepts of “reversible wholly plastic deformation (as in cleavage)” used for derivation of the generalized
Lippmann equations for solids. This concept was shown to be an idealized one having no relation to the real plastic deformation
of metals. It is a case of mixed notions since “cleavage” is not a kind of deformation. It is a kind of irreversible fracture
mostly without the steps of plasticity. Affected only by adsorbate, the thin surface electrode layer should be considered
as absolutely elastic body, whose plastic deformation is impossible, i.e. the Lippmann equation and other equations containing
terms of plastic deformation cannot be used in thermodynamics of adsorption on the solid metals.
The text was submitted by authors in English. |
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