Structure-mechanical approach to surface tension of solids

Some problems of applying the Lippmann equation to adsorption studies on solid electrodes are shortly reviewed. A novel nonthermodynamic approach to consider the role of elastic and plastic deformation of electrode surfaces during adsorption is proposed. The extremely thin electrode surface layers affected electrically and mechanically by adsorbate are supposed to be free of dislocations because of volume discrepancy. The nearest structure-mechanical analogs of such layers are the whisker crystals whose side surface could have one- and two-dimensional defects, but have no active dislocations. Like whiskers, surface metal layers should possess a high ultimate strength close to the theoretical one and a purely elastic deformation. Affected only by adsorbate, the 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 the solid metal surface.