Nonequilibrium Thermodynamics for the Stability Study of Contact Glow Discharge Electrolysis

Beyond a critical voltage in a two-electrode configuration, the conventional electrolysis is no longer sustained when a thin gaseous envelope covers the working electrode, and the emission of visible light is observed. The system is examined as a process far from thermodynamic equilibrium, with the identification and computation of conjugated thermodynamic fluxes and forces generating the entropy production. The quadratic form of the entropy variational function is employed for the stability discussion, in the Lyapunov's sense of stability for steady state autonomous systems. Thermodynamic arguments, compared with experimental observations on the gas film dynamics, show that the stability of the phenomenon is mainly governed by thermal and electrochemical contributions of the electrochemical cell.

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