Electrochemistry of molten LiCl–KCl–CrCl3 and LiCl–KCl–CrCl2 mixtures

Abstract

Chemical reactions during dissolution of CrCl3 or CrCl2 in molten LiCl–KCL eutectic have been demonstrated to occur, but the nature of the reactions is not yet well understood. Reduction of CrCl3 to chromium metal occurs through two well-characterized electrochemical steps, at approximately +0.1 and –0.9 V vs Ag/AgCl. Each step was studied in the 0.025–0.085 molar CrCl3 concentration range, at various temperatures between 375 and 550 °C. The Cr(iii)/Cr(ii) electron transfer step exhibited reversible behaviour under all the experimental conditions studied. In contrast, the Cr(ii)/Cr(0) step could involve Cr(ii) adsorbed species and initial chromium electrocrystallization phenomena, mainly depending on the nature of the substrate.