Abstract
A review is given of previous theories of electrolytic rectification and it is shown that none of them are able to account for all of the phenomena observed. Experimental results are then presented which show that both the magnitude of the cathodic current at a given applied field, and the activation energies for cathodic current flow are controlled by the size of the cation in solution, and by specific adsorption under applied cathodic bias. The existence of a surface barrier, height about 1 volt, thickness about 250 Å, has been proven. The proposed band scheme for anodic oxide layers thus includes a steep surface barrier at the outer oxide interface, an ohmic contact at the valve metal/oxide interface, and traps in the oxide.
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