Electrode Reactions on Demetalized Surfaces

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Abstract
Many electrode reactions occurring nominally on metals proceed in fact on a demetalized surface produced by formation of a semiconducting surface reaction film on the electrode. A viewpoint is presented that in these cases of electrode reactions, the electrode kinetic behavior should be interpreted in terms of solid‐state surface properties (especially the bandgap and thence semiconduetivity and solid‐state cohesion) of the surface film rather than the electronic properties of the underlying metal. Equations are formulated to take this into account and the considerations developed provide a basis to interpret a large amount of literature data on the following subjects: oxygen reduction reaction; oxygen evolution reaction; anodic dissolution of metals in anhydrous hydrogen fluoride and in sulfamic acid‐formamide solutions; reaction on platinum, oxide films, and oxides; and possibly the open‐circuit corrosion potentials of some common metals

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