THE CALORIC EFFECT OF ADSORPTION AT THE ELECTRIFIED METAL ELECTROLYTEINTERFACE

A thermodynamic treatment of the polarizable metal/electrolyte interfa ce is presented and generalizes the classical electro-capillary equati on, which interrelates variations in interfacial tension, cell potenti al, and solution composition, to include temperature changes. The resu lt can be used in investigations of the structure of electrified inter faces; for example, in the calculation of entropy changes which occur in the solvent layer adjacent to the metal surface (inner or Stern lay er) and, in particular, in the study of phase transitions in insoluble organic monolayers adsorbed at an electrochemical interface. (C) 1995 American Institute of Physics.