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 _sulphites_ of the rare earth elements are sparingly soluble
crystalline salts, of the general formula R₂(SO₃)₃,_x_H₂O. They are
obtained by passing sulphur dioxide into a suspension of the hydroxides
in water, or by double decomposition of soluble salts with alkali
sulphite. They dissolve in excess of sulphurous acid, and on evaporation
of the solution are deposited unchanged. They are distinguished from
thorium sulphite by the fact that they form no alkali double salts. The
strongly electropositive character of the rare earth metals is shown by
the fact that they form normal and not basic sulphites.
The _thiosulphates_ are readily soluble, crystalline bodies. With the
exception of the ceric and scandium salts, they are not hydrolysed in
boiling solution, a fact which allows of a complete separation from the
readily hydrolysed thiosulphates of zirconium and thorium.
_Dithionates_ of the commoner rare earth elements, of the general
formula R₂(S₂O₆)₃,_x_H₂O, have been prepared by double decomposition of
the sulphates with barium dithionate. They are readily soluble,
crystalline salts.
The _selenates_ are soluble, crystalline salts, which separate from
aqueous solutions in various hydrated forms. They resemble the sulphates
in being less soluble in hot than in cold water, and numerous cases of
isomorphism have been observed among the corresponding sulphate and
selenate hydrates. Several alkali double selenates have been described;
they show a close resemblance to the analogous double sulphates.
The _selenites_ are amorphous, insoluble compounds, obtained by the
action of selenious acid on the carbonates, or on solutions of neutral
salts. Basic and acid selenites are also known.
~Nitrates.~--The nitrates are crystalline, deliquescent compounds,
readily soluble in water and alcohol, but less easily in nitric acid, a
fact which has been of considerable importance for purposes of
separation. The solubility is greatest in the case of lanthanum nitrate,
diminishing through the cerium group to a minimum in gadolinium nitrate,
and then increasing again. They separate from aqueous solution in the
form of crystalline hydrates; in the cerium group, these have commonly
the formula R(NO₃)₃,6H₂O, whilst the nitrates of the yttrium elements
usually crystallise with 3 or 5 molecules of water. By carefully heating
the hydrated salts, basic nitrates may be obtained, which in the yttrium
group are soluble in water, and may be obtained crystalline; in the
cerium group, the basic nitrates are insoluble. By further heating,
insoluble ‘superbasic salts,’ and finally the oxides, are obtained in
all cases. The temperatures at which these basic and superbasic
compounds are formed vary with the electropositive character of the
element; this fact affords a method of separation which has been very
frequently employed.
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