An electrode kinetic model for pit initiation has been described in te
rms of the charge on the oxide surface and the pH of zero charge param
eter. The model takes into account adsorption of chloride ions on the
oxide surface, penetration of chloride ions through the oxide him via
vacancy transport, and localized dissolution of aluminum at the metal/
oxide interface in three consecutive single electron transfer steps. M
athematical expressions are derived which agree with the experimentall
y determined variation in pitting potential with chloride ion concentr
ation al constant pH and with the variation in pitting potential with
pH at constant chloride ion concentration.