Kinetics and mechanism of chromium electrodeposition from formate and oxalate solutions of Cr(III) compounds

Kinetics of multistep reaction of Cr(III) ions discharge to metal was studied on a stationary electrode and on a rotating disk electrode from the solutions containing formic acid or oxalic acid. The electroreduction of Cr(III) complex ions in aqueous solutions is shown to proceed via the formation of relatively stable intermediates-Cr(II) compounds which are partially removed into bulk solution. The effect of pH, organic ligand concentration and disk rotation velocity on the partial current density of chromium electroplating was demonstrated. The kinetic equations of the studied process were derived and compared with the experimental data. Kinetic parameters for the discharge of Cr(II) ions were calculated. The mechanism of chromium electrodeposition reaction was proposed. The electrodeposition of chromium from formate bath is suggested to proceed with the participation of hydroxocomplexes of bivalent chromium. The oxalate complexes of bivalent chromium directly discharge in the electrolytes containing oxalic acid. The partial polarization curves of chromium electrodeposition exhibit a current peak which may be caused by blocking the electrode surface with poorly soluble Cr(III) hydroxide. (C) 2009 Elsevier Ltd. All rights reserved.