KF is employed as a source of fluoride ions added to the melt to disclose the influence of fluoride on the disproportionation reactions of titanium ions, 3Ti2+ = 2Ti3+ + Ti, and 4Ti3+ = 3Ti4+ + Ti. The results reveal that the equilibrium transferred to the right direction for the first reaction and the apparent equilibrium constant increased sharply, mainly because of the formation of coordination compounds: TiFi3-i. The accurate values of the equilibrium constants referring to the formation reactions of Ti3+ + iF- = TiFi3-i (i = 1-6) in NaCl-KCl melt at 1023 K were evaluated with a best fit least squares method. It is also revealed that the stable states of the coordination compounds are TiF2+, TiF2+, TiF4- and TiF63-. Moreover, the Gibbs free energies for complex formation were estimated. Ti2+ was undetectable when the concentration of fluoride ion was high enough. The equilibrium constant for the formation reaction, Ti4- + 6F- = TiF62-, was evaluated. The equilibrium constant, Kc2, for the disproportionation reaction 4Ti3+ = 3Ti4+ + Ti, in chloride melt was determined as 0.015.
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