Cathodic contact glow discharge electrolysis: its origin and non-faradaic chemical effects

Normal electrolysis (NE), at sufficiently high voltages, breaks down and undergoes a transition to a phenomenon called contact glow discharge electrolysis (CGDE) in which a sheath of glow discharge plasma encapsulates one of the electrodes, the anode or the cathode. The chemical effects of CGDE are highly non-faradaic e.g. a mixture of H-2 and H2O2 plus O-2 each in excess of the Faraday law value is liberated at the glow discharge plasma electrode from an aqueous electrolyte solution. Studies of cathodic CGDE, particularly its origin and chemical effects, in comparison to those of anodic CGDE have received significantly less attention and have not been studied in detail. The present paper is an attempt towards elucidation of the mechanisms of the growth of cathodic CGDE during NE and its non-faradaic chemical effects. The findings of the study have led to the inference that emission of secondary electrons from the metal cathode with sufficient kinetic energies, vaporization of the electrolyte solvent in the vicinity of the cathode surface induced by Joule heating and the onset of hydrodynamic instabilities in local vaporization contribute to the generation of the plasma at the cathode during NE. The findings have further shown that non-faradaic yields of CGDE at the cathode originate from energy transfer processes in two reaction zones: a plasma phase reaction zone around the cathode which accounts for similar to 75% of the yields, and a liquid phase reaction zone near the plasma-catholyte solution interface accounting for the remaining similar to 25% of the yields.