Applicability of Gibbs adsorption equation and Maxwell relations to deformed solid surfaces

Abstract

Revisiting derivations of Gibbs adsorption equation show its applicability to solid surfaces without limiting requirement of constant state of strain. Some attempts to use such a restriction to prove the correctness of the Shuttleworth equation have failed. Also, we have shown that the mandatory conditions for the Maxwell's relations make its inapplicable for the description of capillary and electrocapillary phenomena on solid surfaces, as they lead, if used correctly, to trivial results - known Gibbs adsorbtion equation and Lippmann electrocapillary equation. Attempts to use Maxwell's relations for the case of solid electrodes available in the literature are based on mathematical defects and, consequently, yield erroneous results.