SURFACE CONTRIBUTIONS TO EMF AND HALF CELL POTENTIALS OF NONISOTHERMAL ELECTRODE CONCENTRATION CELLS

Abstract

Nonequilibrium thermodynamics for surfaces is used to obtain general formulae for electrochemical cells. This theory gives boundary conditions for all thermodynamic variables at surfaces. enabling us to integrate the electric field across the electrode surface. Half cell potentials are obtained by integration half way through the celL The electrode surface is seen as a two-dimensional. polarized. electroneutral, and open thermodynamic system. The electric potential jump across the surface gives significant contributions to the cell emf compared to the electrolyte contribution to the cell emf. The theory reduces to the classical emf values for certain conditions. and imposes conditions on experimental designs and interpretations.