The Rare Earths: Their Occurrence, Chemistry, and TechnologyLevy, Stanley Isaac
Science
The Rare Earths: Their Occurrence, Chemistry, and Technology
Levy, Stanley Isaac
Rare earths
_Thorium dioxide_, ThO₂, is obtained by the ignition of the hydroxide or
of suitable salts as a white powder, of which the properties and
appearance depend largely on the method and temperature used in its
formation. Whilst the residue obtained by ignition of the nitrate is an
extraordinarily voluminous and light flaky mass, the sulphate yields a
dense thick powder; the nitrate was therefore always preferred in the
manufacture of incandescent mantles (_q.v._), as it was thought that the
oxide obtained from it was the most suitable for illumination. In the
crystalline form the oxide has been obtained in the laboratory by fusion
with borax and with potassium phosphate. The first method gives
tetragonal crystals, probably isomorphous with those of rutile and
cassiterite; the phosphate fusion is said to give cubic crystals (see p.
74). The oxide is insoluble in acids, but can be transformed into the
sulphate by evaporation with concentrated sulphuric acid, or fusion with
alkali bisulphate. It does not liberate carbon dioxide when fused with
alkali carbonates.
By repeated evaporation with small quantities of acids, thoria can be
transformed into a gel soluble in water (thorium meta-oxide). The sol is
an opalescent fluid, orange-red by transmitted light, and contains small
quantities of the acid employed. The hydroxide may also be obtained in
this form by carefully washing it, and boiling with small quantities of
acids, or with thorium or other salts, or even by long continued washing
with pure water; similarly, continued dialysis of thorium salts
eventually yields such gels. The colloid is positively charged, and
resembles the zirconium oxide gel in its relation to negatively charged
colloids. The gel is easily precipitated by electrolytes.
Ignited thorium oxide has found considerable application in recent years
a catalyst in the preparation of ketones by the contact method of
Sabatier and Senderens.[478] By passing mixtures of the vapours of
appropriate acids over the catalyst heated to the necessary temperature,
good yields of the required ketones are obtained.[479]
[478] Cf. Senderens, _Ann. Chim. Phys._ 1913 [viii.], ~28~, 143.
[479] Cf. Pickard and Kenyon, _Trans. Chem. Soc._ 1913, ~103~, 1923.
The _sulphide_, ThS₂, is obtained, together with the oxysulphide, ThOS,
according to Duboin,[480] by passing a current of sulphuretted hydrogen
over a mixture of thorium chloride with excess of sodium chloride, at a
red heat. The former forms large brown crystals, from which the small
orange-yellow crystals of the oxysulphide may be separated by means of a
sieve; the latter is purified by treatment with warm nitric acid, which
dissolves the sulphide very readily. The oxysulphide is also obtained
when the anhydrous sulphate is heated in sulphuretted hydrogen.[481]
[480] _Compt. rend._ 1908, ~146~, 815.
[481] Hauser, _Zeitsch. anorg. Chem._ 1907, ~53~, 74.
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