Separation
In the separation of the yttrium elements, methods based on differences in electropositive character are of much greater importance than in the separation of the cerium and terbium groups, and the method of nitrate fusion has been very largely employed even in comparatively recent work. This method, which was introduced by Berlin in 1860, has been of great value in the separation of yttrium and the ytterbium elements from the erbium group; it was employed in the isolation of ytterbium by Marignac, and of scandium by Nilson.
If a concentrated solution of the nitrates be evaporated down, and the syrupy residue subjected to gradually increasing temperature, the nitrates of the ytterbium elements and scandium are converted first into the basic nitrates; at somewhat higher temperatures the erbium salts are decomposed, whilst yttrium nitrate and the nitrates of any cerium elements present are the last to break up. If the mixture of basic and neutral nitrates be dissolved in boiling water, the former, being less soluble, crystallise out on cooling, and may be separated by this means, the process being repeated with the filtrate containing the unchanged nitrates. In this way, the weakly basic scandia and ytterbia quickly collect in the first fractions, whilst the oxides of the erbia group are easily separated from the more strongly basic yttria. The presence of the intermediate terbium group renders the process much less easily workable.
The process may be modified by raising the temperature to such an extent that the soluble basic nitrates are converted into insoluble superbasic nitrates, the temperatures at which this change occurs increasing from element to element as the positive character becomes more marked; the mixture of basic and superbasic salts is then extracted with dilute nitric acid which leaves that latter undissolved and removes the more positive elements in solution.
Fractional precipitation of the hydroxides by means of ammonia, alkalies, or alkaline earths has also been frequently employed. A modification of this process is the precipitation with aniline, carried out by Kruss;[358] in this method, the solution of the chloride in warm dilute alcohol is treated with an alcoholic solution of the organic base. Another modification is the ‘Oxide process’ employed by Auer von Welsbach[359] for the separation of the cerium elements, and by Drossbach[360] in the yttrium group. The concentrated solution of the mixed salts is thoroughly digested with the oxides obtained by precipitating a fraction of the earths; the more strongly basic oxides tend to displace the less basic, so that these accumulate in the insoluble part. The solution is filtered from the undissolved oxides, another fraction precipitated, and the oxides obtained from the precipitate digested with the concentrated solution as before.
[358] Zeitsch. anorg. Chem. 1893, 3, 108, 353.
[359] Monats. 1883, 4, 630.
[360] Ber. 1902, 35, 2826.
GROUP B
Yttrium Double Suplhates.
