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Zirconium Chloride, ZrCl4

Zirconium Chloride, ZrCl4, is formed in a variety of ways, which are characteristic of the manner of formation of non-metallic rather than metallic chlorides. Thus it is produced (i) by the action of chlorine on a red-hot mixture of zircon or zirconia and charcoal; in the former case zirconium tetrachloride is mixed with silicon tetrachloride derived from the silica of the mineral; (ii) by the action of chlorine or hydrogen- chloride gas on the heated metal, when the chloride is obtained as a white, crystalline sublimate; (iii) by the action of chlorine on the carbide, ZrC, at 300° C.; (iv) by heating the oxide with phosphorus pentachloride in a sealed tube at 190°; (v) by heating the oxychloride, ZrOCl2, to 110° C. in a stream of hydrogen chloride. According to Lely and Hamburger, however, zirconium chloride is best prepared by the action of chlorine and carbon tetrachloride on the oxide at 800° C.; and Bourion has found that the pure chloride is rapidly obtained by passing the vapour of sulphur monochloride over heated thoria.

Zirconium chloride is a white, crystalline solid which fumes in moist air and reacts vigorously with water, forming the oxychloride ZrOCl2 which remains in solution. Zirconium chloride forms no crystallohydrate with water, but sublimes when heated, yielding a vapour whose density at 440° C. is 8.15 (air = 1) or 117.4 (H = 1) (theory for ZrCl4 requires 116.2); it may apparently be recrystallised from hydrochloric acid, but the product probably contains some oxychloride.

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