Abstract
The passive oxide film on metals in aqueous solutions is stable (corrosion-resistive) to the extent that the Fermi level at the film/solution interface remains within the electronic energy band gap of the film (in the state of electronic band edge level pinning). Transpassivation that leads to a potential-dependent dissolution of the passive film occurs in the range of electrode potential in which the Fermi level is pinned in the electronic valence band level at the film/aqueous solution interface. Chloride adsorption introduces the surface state of electronic acceptor levels on the passive oxide film. When the Fermi level of passive metal anodes is pinned at the chloride-induced surface state, the localized transpassive dissolution of the passive film proceeds at the chloride adsorption sites to cause a local film breakdown. The critical potential for the local film breakdown appears less anodic (more negative) than the general transpassivation potential.
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