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 amorphous impure metal is a dark grey powder, of specific gravity
11·3; the hammered and strongly heated leaf has the density 12·16. It
burns readily in air with great brilliance, and when finely powdered
ignites if crushed or rubbed. When heated in the electric furnace, it
melts, according to von Bolton,[476] at about 1450°; von Wartenburg[477]
found the melting-point to be about 1700°; the fused beads resemble
platinum in physical properties. It is somewhat resistant to acids,
dissolving easily only in aqua regia, and more slowly in fuming
hydrochloric acid. It combines directly when heated in sulphur or
halogens, and in nitrogen and hydrogen.
[476] v. Bolton, _Zeitsch. Elektrochem._ 1908, ~14~, 768.
[477] _Ibid._ 1909, ~15~, 866.
The _hydride_, ThH₄, is best obtained by heating the metal in hydrogen,
an energetic reaction taking place at a red heat. Winkler observed that
a mixture of the dioxide with magnesium absorbs hydrogen readily when
heated. The hydride is a stable greyish-black powder, not attacked by
water, but dissolving readily in hydrochloric acid, with evolution of
hydrogen. The _nitride_, Th₃N₄, is prepared by heating the metal in the
gas, or the carbide in a stream of ammonia. It is a brown powder,
decomposed by water with evolution of ammonia and formation of the
dioxide. The _azide_ has been used for purposes of detection and
estimation, since in boiling solution it is hydrolysed with separation
of the hydroxide; zirconium and ceric salts also show this reaction, but
the rare earth salts give no precipitate.
The _hydroxide_, Th(OH)₄,_x_H₂O, is precipitated from solutions of
thorium salts by alkalies or ammonia, as a gelatinous white precipitate,
insoluble in excess. It dissolves readily in mineral acids or in alkali
carbonates. Hydrogen peroxide and ammonia throw down an hydrated
_peroxide_, Th₂O₇; from neutral solutions hydrogen peroxide alone throws
down _peroxy-salts_, which contain acid groups. This peroxide may also
be obtained by the action of sodium hypochlorite or hydrogen peroxide on
the hydroxide, as in the case of the zirconium compound. It readily
gives up oxygen, passing into the more stable peroxide, ThO₃. Since in
neutral or faintly acid solutions zirconium and the rare earths give no
precipitate with hydrogen peroxide, the reaction is extremely useful in
the detection and estimation of thorium.
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