Current state and problems in the surface tension of solids

Derivation of the Shuttleworth equation is considered in connection with some aspects of thermodynamic formalism. The dual concept of surface energy formally allows application of Gibbs thermodynamics to the surface tension of solids (considered as a reversible process of partly plastic and partly elastic deformation). However, internal contradictions of this concept raise fundamental questions regarding its correctness and the following thermodynamic analysis of surface tension of solid electrodes. This analysis leads to the generalized Lippmann equation, and finally to using the classical Lippmann equation for solids that is shown to be incorrect. Experimental data on the charge transfer during halide and hydroxide ions adsorption on the gold and platinum electrodes obtained by five different in situ physical methods have been compared with those obtained by thermodynamic analysis. A good agreement has been found between all experimental data, but they contradict the results of thermodynamic analysis. This shows the incorrectness of the generalized Lippman equation and the impossibility of using the classical Lippman equation for solid electrodes.