On energy transfer and generation of an electric current in the vicinity of an electrode dipped in an electrolyte and strongly heated by a current passing through it

Processes occurring when a metal electrode dipped in an electrolyte is heated by intense evaporation of the electrolyte are considered in terms of a physically rigorous model. Based on the Onsager principle of least energy dissipation rate in nonequilibrium processes, the fractions of thermal energy that are spent on heating and evaporating the electrolyte and on heating the vapor are found. The energy is released within the vapor-gas sheath when an electric current flows between the electrode and electrolyte surface. It is found that the electrolyte vapor temperature exceeds 1300 K. Analytical expressions are derived for the vapor-gas sheath thickness, the electrolyte vapor pressure, and the velocity of the vapor escaping the discharge zone. It is shown that field evaporation of thermally activated negative ions from the electrolyte surface cannot provide an electric current with densities found in experiments but is responsible for the generation of free electrons near the electrolyte surface. These electrons arise when the ions decay via collisions with excited molecules.