Chemistry and physics of the ‘‘liquid’’/solid interface: A surface science perspective

Abstract

Through experimental simulation of the electrochemicaldouble layer under conditions of ultrahigh vacuum, surface science experiments can provide detailed and definitive information about the metal/electrolyte interface. The relevance of this somewhat nontraditional approach to the liquid/solid interface might appear questionable, but thermodynamic considerations, along with an ever expanding list of gas/solid to liquid/solid analogies, attests to its merit. In this article, thermodynamic arguments for the direct relationship between vacuum and electrochemical experiments are presented and supporting experimental results in the areas of solvent adsorption, surface solvation, hydrophilic and hydrophobic interactions, specific and nonspecific adsorption, adlayer solution theory of HF and H2O coadsorbed on Ag(110), and electrochemical charge transfer reactions in vacuum are reviewed. On the basis of these results a new, three‐dimensional model of the metal/electrolyte interface is proposed.