The dissipated energy of electrode surfaces: Temperature jumps from coupled transport processes

Nonequilibrium thermodynamics for surfaces has been applied to the electrode surfaces of an electrochemical cell. It is shown that the temperature of the surface differs from that of the adjacent electrolyte and electrode, and that a temperature jump exists across the surface. Mathematical expressions are derived for the temperature profiles of two cells at steady-state conditions. Methods for estimating transport coefficients for the coupled transport processes at the electrode surface are discussed. Possible numerical results for the temperature profile, the overpotential, and the dissipated energy are reported. The results reflect the relative importance of heat conductivities, electric conductivities, and the Peltier coefficients for the electrode surface phenomena in combination with bulk properties. Significant temperature jumps may occur at normal electrolysis conditions 10(3) to 10(4) A m(-2), and for temperature jump coefficients which are smaller than 10(3) J s(-1) K-2 m(-2). The overpotential may have contributions from the Peltier coefficients for the surface larger than the ohmic contribution. The method of analysis gives new information useful for heat control of electrochemical cells, electrode kinetic studies, and interpretation of overpotentials.