—The oxalates of the rare earth elements are of the greatest importance, on account of the fact that they are not only insoluble in water, but are also very sparingly soluble in dilute mineral acids, and in excess of oxalic acid. They can be completely precipitated even from strongly acid solutions by addition of sufficient excess of oxalic acid, or alkali oxalate, and thus afford a means of easily and completely separating the rare earth group from the commoner elements.
They are thrown down by addition of oxalic acid, or alkali oxalate, as amorphous precipitates, which rapidly become crystalline, especially if the solution is warmed. From water at normal temperatures they usually separate as the decahydrates, R₂(C₂O₄)₃,10H₂O, but hydrates with 7, 9, and 11 molecules of water of crystallisation are also known. From strongly acid solutions, mixed oxalo-salts of the general formula R(C₂O₄)X, where X = Cl, NO₃, HSO₄, etc., may be obtained. These mixed salts may also be prepared by dissolving the oxalates in concentrated solutions of the chlorides, nitrates, etc., whilst nitro-sulphates, R(SO₄)NO₃, have been obtained by recrystallising the sulphates from strong nitric acid. The tendency to form salts with mixed acid radicles appears to be general.[166]
[166] See Meyer and Marckwald, Ber. 1900, 33, 1003; also Matignon, Ann. Chim. Phys. 1906, [viii.], 8, 243.
The solubilities of the oxalates in mineral acids of various concentrations have been examined by Hauser and Wirth.[167] Whilst the solubilities in water are exceedingly slight, and increase with increasing atomic weight of the elements, i.e. from the cerium to the yttrium group, in mineral acids of concentration 3-4N the solubility becomes noticeable, and is greatest for the oxalates of the most positive elements. The solubility is greatly lessened, however, if considerable excess of oxalic acid be present.
[167] Zeitsch. anal. Chem. 1908, 47, 389.
Double oxalates with the alkali oxalates can be obtained with the salts of the yttrium elements only, the oxalates of the cerium elements being almost insoluble in excess of alkali oxalate in the cold. Of the alkali double oxalates, the potassium compounds are the most soluble, but the ammonium compounds show the greatest differences in solubility; von Welsbach has employed the method of fractional crystallisation of these salts from a saturated solution of ammonium oxalate for separations in the yttrium group. The sodium double oxalates are the least soluble of these double salts.
Since the rare earth elements are almost always separated in the form of the oxalates, the methods for transforming these into soluble compounds become important. They may be ignited to oxides, and these dissolved in nitric acid; if the content of ceria is very high, the oxide mixture may become insoluble, but this difficulty may be overcome by addition of a reducing agent—hydrogen peroxide is very convenient for this purpose. The oxalates may also be dissolved directly in fuming nitric acid, care being taken to avoid loss; if the mixture contains cerium, the oxidation is hastened, ceric salts having the property of acting as oxygen carriers. By boiling for a short time with potash, the oxalates may be easily transformed into the hydroxides, which can be dissolved in dilute acids.
Formates.
—On account of the considerable differences in solubility by which they are characterised, these salts have been employed for separations. The formates of the cerium group are considerably less soluble than those of the yttrium group. They may be partly precipitated from solutions of rare earth salts by addition of alkali formate—formic acid itself causes precipitation only with salts of weak acids, e.g. the acetates—but are best prepared by dissolving the oxides in formic acid; on concentration of the solution, the formates of the cerium and terbium elements successively separate, the salts of the yttrium group remaining in solution. The separation of the terbium earths by this method was attempted by Delafontaine; his ‘new’ element, Philippium, obtained from the mother-liquors, was in reality a mixture of the terbium and yttrium elements, which cannot be completely separated by the formate method.[168]
[168] See Urbain, Ann. Chim. Phys. 1900, [vii.], 19, 184.