Zirconyl oxalate, ZrO,C₂O₄, is obtained in the hydrated form when oxalic acid is added to a zirconium salt in the presence of hydrochloric or acetic acid. It is a white powder, soluble in oxalic acid, and easily hydrolysed by water. If an aqueous solution of oxalic acid be saturated with zirconium hydroxide, an acid oxalate, ZrOH(HC₂O₄)₃,7H₂O, is obtained on evaporation. Double oxalates are readily obtained by dissolving zirconium hydroxide in solutions of alkali hydrogen oxalates, the general form being Zr(C₂O₄R´)₄,xH₂O. The tartrate precipitated when tartaric acid is added to a zirconium salt in solution probably has the cyclic structure,
as shown by the great rise in the specific rotatory power of solutions of alkali oxalates on addition of zirconium compounds. The precipitate dissolves readily in alkalies, and various double alkali tartrates have been prepared; the potassium salt, ZrO(C₄H₄O₆K)₂,3H₂O, is analogous to the thorium alkali tartrates. The solubility in alkalies is of great importance for the separation of iron and zirconium.
Atomic Weight of Zirconium.
—The value of this constant is not very accurately known. The International Committee has adopted the value 90·6, but there is some uncertainty as to the value of the decimal fraction. Berzelius in 1825 employed the analytical sulphate method, and found Zr = 88·47. The numbers of Hermann (1844), obtained by the analysis of the oxychloride, 2ZrOCl₂,9H₂O,[471] were very discordant, the mean giving the value 89·56. Marignac in 1860 analysed the potassium salt, K₂ZrF₆; this he heated with strong sulphuric acid, the residue being ignited until all the zirconium sulphate was transformed to oxide; the weighed mixture was then freed from potassium sulphate, and the residual oxide dried and weighed. From the three ratios K₂ZrF₆ : ZrO₂, K₂ZrF₆ : H₂SO₄, and K₂SO₄ : ZrO₂, he obtained the mean values 90·02, 91·55, and 90·68 respectively. Weibull in 1881-1882 determined the ratios Zr(SO₄)₂ : ZrO₂ and Zr(SeO₄)₂ : ZrO₂ by ignition of the sulphate and selenate respectively; he obtained the values 89·55 and 90·81.
[471] Chauvenet (loc. cit.) could not confirm the existence of this hydrate.
Bailey carried out a series of analytical sulphate determinations in 1890, obtaining the mean value 90·656. Brauner criticises the method on the ground that the preparation of the pure neutral anhydrous sulphate is almost impossible; the sulphate heated to 400° is not yet anhydrous, so that Bailey’s result, on this ground, is probably too low. Venable in 1898 analysed the oxychloride; he claimed to have obtained the compound ZrOCl₂,3H₂O, by heating the crystallised salt at 100°-125° in hydrogen chloride, a method which Chauvenet (loc. cit.) has found to lead to the dihydrate, ZrOCl₂,2H₂O. His value was 90·803.
Detection and Estimation.
—The following reactions may be employed to distinguish zirconium:
(1) The oxalate precipitated from neutral or faintly acid solution dissolves readily in excess of oxalic acid; the oxalates of thorium and of the rare earth elements are practically insoluble under these conditions. The fluoride also dissolves in excess of hydrofluoric acid or of alkali fluoride, behaviour characteristic of this element alone among the group.