The equilibrium constant, K c , of the reaction 3Ti 2+ = 2Ti 3+ + Ti was studied in the molten binary mixtures of LiCl. The accurate values of K c were calculated by the best-fitting method under consideration of the TiOCl(s) dissolution at temperature of 973 K, 1023K and 1073 K, respectively. The fitted concentration of O 2- was verified by emf method with yttria-stabilized zirconia electrode (YSZE). The influence of the cation radius of electrolyte on the equilibrium constant was studied in molten binary mixtures of LiCl at 1023K on the basis of the reliable method for obtaining accurate value of K c . It was found that the K c values decreased from 0.59 to 0.27 with the concentration of LiCl increasing at 1023 K. More importantly, results disclosed that the values of K c correspond with polarizing power no matter in CsCl-LiCl or KCl-LiCl system.
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