Electrochemistry of Active Chromium: Part 1—Anomalous Corrosion and Products of Chromium Dissolution in Deaerated Sulfuric Acid

Chromium corroding in deaerated aqueous solution of sulfuric acid (H2SO4; pH 1 to 3) produces Cr(II) and Cr(III) ions simultaneously in the ratio 7:1, as well as H2. The corrosion potentials of electrochemically activated chromium are determined by the electrochemical processes as expected according to the Wagner-Traud model. However, the real rates of chromium corrosion determined by collecting evolved hydrogen, spectrophotometric determination of the accumulated Cr ions in the solution, or by weight-loss measurements are higher than the electrochemical dissolution rate by up to 12 times for pH 1.0. The effect is smaller for higher pH. This was due to the simultaneous “anomalous” (or chemical) dissolution process of the direct chemical reaction of Cr with H2O molecules, as proposed some time ago by Kolotyrkin and coworkers. Since “anomalous” dissolution cannot be detected by electrochemical means, it has been pointed out that in the presence of “anomalous” dissolution processes during metal corrosion, electrochemical corrosion rate measurements should be taken only as approximate, while the level of approximation should be determined by some other direct corrosion rate measurement method.