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Titanium Tetrafluoride, TiF4

Impure Titanium Tetrafluoride, TiF4, is formed when magnesium titanifluoride, Mg2TiF6, or the corresponding barium salt, BaTiF6, is decomposed by strong ignition; but it is best prepared by one of the three following methods: (i) the action of fluorine on titanium, (ii) the action of anhydrous hydrogen fluoride on titanium, (iii) the action of anhydrous hydrogen fluoride on titanium tetrachloride at 100°-120° C.; for, owing to the high volatility of hydrogen chloride compared with hydrogen fluoride, the reaction

4HF + TiCl ⇔ 4TiF4 + 4HCl

proceeds in one direction only.

Titanium tetrafluoride is a colourless mass having a density 2.798 at 20.5° C. It boils at 284° C. and at 444° C. has a vapour density of 64.5 (theory = 62.05). It is noteworthy that the boiling-point of the fluoride is above that of the tetrachloride, TiCl4 (136° C.); this probably indicates that the former is polymerised near its boiling-point. This difference between the tetrafluoride and tetrachloride is in marked contrast with that between the silicon halides, SiF4 and SiCl4, and the corresponding halides of other non-metals and metalloids, and relates titanium to the metals rather than the metalloids. The saline nature of the fluoride is further shown by the fact that it is hygroscopic, and forms a clear solution in water, which deposits the hydrate TiF4.2H2O on evaporation. With alcohol the compound TiF4.C2H5OH is formed, and with ammonia the compound TiF4.2NH3; but, singularly, it does not combine directly with hydrogen fluoride, although the salts M2TiF6 are so well known. Roasting with sulphuric acid converts titanium tetrafluoride into titanic oxide.

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