Electrochemical instabilities due to pitting corrosion of iron

Electrochemical instabilities induced by chlorides and bromides due to pitting corrosion of iron in sulfuric acid solutions are investigated. Analysis of the electrochemical instabilities as a function of the applied potential and the nature and concentration of the aggressive chemical species shows that the system exhibits a transition from aperiodic bursting of large-amplitude to small-amplitude chaotic oscillations at a critical potential (bifurcation potential, E _bif). The E _bif is determined by the halide concentration inside the pits and coincides with the repassivation potential defined in corrosion studies to explain pit repassivation due to changes in pit chemistry. Surface observations show that, at E < E _bif, an active-passive state dissolution (etching) occurs, while at E > E _bif, a polishing state dissolution is reached. Spatial interactions between early initiated pits and the adjacent electrode surface, oxide film alteration, aggressive species accumulation around active pits, and formation of ferrous salt layers in front of the Fe electrode are all considered to be associated with electrochemical instabilities emerging during pitting corrosion of iron under different dissolution states. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 535–550. The text was submitted by the authors in English.