Theoretical Prediction of the Scan Rate Dependencies of the Pitting Potential and the Probability Distribution in the Induction Time

The point defect model (PDM) has been used to derive the dependence of the pitting potential on the voltage scan rate. Relationships derived from the PDM predict that the observed pitting potential is a linear function of the square root of voltage scan rate at low scan rates, which agrees with experimental data reported in the literature. Furthermore, the critical concentration of condensed cation vacancies that give rise to passivity breakdown, as estimated from the sweep rate dependence of the pitting potential, is found to be in good agreement with that estimated from structural considerations. The PDM is also used to predict the probability distribution function in the induction time for pitting (tind), that is, the survival probability, by assuming that the maximum diffusivity of the cation vacancy in a population of specimens is log‐normally distributed. This calculated "external" distribution in the induction time is found to be in reasonable agreement with experimental induction time data for passivity breakdown on multiple specimens of single crystal (100) Ni and polycrystalline nickel buffered chloride solutions.