The Rare Earths: Their Occurrence, Chemistry, and TechnologyLevy, Stanley Isaac
Science
The Rare Earths: Their Occurrence, Chemistry, and Technology
Levy, Stanley Isaac
Rare earths
The modern methods for the separation of these elements are based almost
entirely on the differences in solubility of the various double
nitrates.[239] The mixed double sulphates separated by saturation of a
solution of the chlorides with sodium sulphate, which contain the cerium
and most of the terbium elements, are transformed into nitrates, and the
neutral solution boiled with potassium bromate, in presence of powdered
marble, till all the cerium is precipitated as basic ceric nitrate. From
the filtered solution the other elements are thrown down as oxalates,
transformed into the magnesium double nitrates (A in Fig. 8), and
fractionated from nitric acid solution[240] until a rough separation has
been effected (fractions 1, 2, 3, and 4). The separation, which is
somewhat long and tedious, is followed by means of the absorption
spectra, and by the colour changes of the fractions. Fraction 1,
containing lanthanum and some praseodymium, should be faint green to
colourless; fraction 2 is colourless by the complementary action of the
coloured salts of neodymium and praseodymium; fraction 3, which should
contain the crude neodymium salt, is amethyst; and fraction 4, the
mother-liquor, is yellow from the presence of the samarium compound.
[239] The following scheme is largely from James, ‘The Separation of
the Rare Earths,’ _J. Amer. Chem. Soc._ 1912, ~34~, 757.
[240] See Demarçay, _Compt. rend._ 1900, ~130~, 1019 and 1186; also
Drossbach, _Ber._ 1902, ~35~, 2826, and Muthmann and Weiss, _Annalen_,
1904, ~331~, 1.
Fraction 1 is now converted to the double ammonium nitrates, which allow
of a readier separation at this stage; two fractions are obtained, of
which the less soluble, fraction 5, is the fairly pure lanthanum
compound, whilst the more soluble, fraction 6, contains the praseodymium
with a little lanthanum. The lanthanum ammonium nitrate, fraction 5, is
converted into the anhydrous sulphate, which is dissolved in ice-water;
when the solution is gradually warmed, the enneahydrate, La₂(SO₄)₃,9H₂O,
separates, and may be obtained perfectly pure by recrystallisation. It
is of interest that the radioactive element actinium is chemically very
similar to lanthanum, and follows it closely through the process of
separation.
The mixed praseodymium and neodymium magnesium nitrates which constitute
fraction 2 are transformed into the double manganese nitrates, and the
crystallisation from nitric acid continued.[241] The less soluble part,
fraction 7, is fairly free from neodymium, and the separation is
continued with that of fraction 6, until both lanthanum and neodymium
have been completely removed. The more soluble part, fraction 8, yields
the pure neodymium compound, as does also the crude neodymium magnesium
nitrate which constitutes fraction 3, if the crystallisation be
continued.
[241] Cf. Lacombe, _Bull. Soc. Chim._ 1904, [iii.], ~31~, 570.
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