The influence of fluoride ions on the equilibrium between titanium ions and titanium metal in fused alkali chloride melts.

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, 3Ti(2+) = 2Ti(3+) + Ti, and 4Ti(3+) = 3Ti(4+) + 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: TiFi(3-i). The accurate values of the equilibrium constants referring to the formation reactions of Ti(3+) + iF(-) = TiFi(3-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 TiF(2+), TiF2(+), TiF4(-) and TiF6(3-). Moreover, the Gibbs free energies for complex formation were estimated. Ti(2+) was undetectable when the concentration of fluoride ion was high enough. The equilibrium constant for the formation reaction, Ti(4-) + 6F(-) = TiF6(2-), was evaluated. The equilibrium constant, Kc2, for the disproportionation reaction 4Ti(3+) = 3Ti(4+) + Ti, in chloride melt was determined as 0.015.