Mechanism of the transpassive dissolution and secondary passivation of chromium in sulphuric acid solutions

The transpassive dissolution and secondary passivation of Cr in 1...10 M H2SO4 solutions were studied by a combination of different electrochemical methods. The steady-state polarization curves for transpassive dissolution exhibited a Tafel behaviour with a slope being independent on the acid concentration. Lower dissolution rates were measured for higher acid concentrations. Ring-disk measurements showed a release of both soluble Cr(VI) and Cr(III) during transpassivity. Impedance spectra were qualitatively similar in all acid concentrations, comprising one capacitive and two inductive semicircles. A kinetic model comprising two parallel transpassive dissolution paths was consistent with the experimental results. Typical passivation diagrams were observed for Cr in 10 M H2SO4, and a secondary passive state was established at higher potentials. The formation of the secondary passive film was confirmed by contact electric resistance (CER) measurements. A renewed version of the surface charge approach was consistent with the experimental results in the region of the secondary passivation.