Reactions at the corroding nickel electrode in molten sodium carbonate under CO/CO2 atmosphere

Anodic reactions at the CO, CO₂|Ni electrode in molten sodium carbonate at 1000°C are examined in detail. Experimental polarization curves are fitted via a computer graphics procedure to a model employing five anodic reactions with activation, concentration and resistance polarization, and passivation. The resultant empirical parameters are interpreted in terms of absolute rate expressions describing possible anodic reactions. Three of the anodic reactions are found to be in accord with the findings at inert electrodes by previous investigators, i.e. oxidation of CO by two mechanisms and oxidation of carbonate, while the cathodic reaction is consistent with reduction of CO₂. The remaining two anodic reactions were associated with the oxidation of nickel to Ni²⁺ with formation of a NiO film above a passivation potential, and, at higher anodic overpotentials, oxidation of NiO to a higher oxide, e.g. Ni₂O₃. There is an indication of the formation of a third oxide at still higher anodic overpotentials.