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 methods of the second class, which are processes of fractional
crystallisation, depend on the differences in solubility which are
observed in analogous compounds in passing from one member of the group
to another. The value of these methods, as opposed to the methods
depending on differences in basic strength, was clearly shown by Auer
von Welsbach, who in 1885 succeeded in resolving Mosander’s ‘Didymium’
into two new elements, praseodymium and neodymium, by fractional
crystallisation of the ammonium double nitrates; since that date, much
attention has been devoted to the task of finding rare earth compounds
which will lend themselves to such processes. The method is extremely
laborious, and may involve several thousand recrystallisations, in
consequence of the generally very slight differences of solubility, and
the ease with which the rare earth compounds, being almost always
isomorphous with one another, form mixed crystals.
Whilst the method of fractional crystallisation has come into general
use for the separation of one element from another only within the last
thirty years, processes for the separation of the cerium group from the
yttrium elements, depending on differences of solubility, have long been
known and used. The most important of these, the double sulphate method,
depends on the fact that the potassium double sulphates of the cerium
metals are almost insoluble, whilst those of the terbium group are
sparingly, and of the yttrium group readily soluble in a concentrated
solution of potassium sulphate. The cerium elements may be thus
completely removed from a solution of mixed salts by addition of a crust
of potassium sulphate crystals, or of an hot concentrated solution of
the same reagent. In other cases, _e.g._ in the double carbonate and
double oxalate processes, separation is effected by taking advantage of
the greater tendency to the formation of double salts possessed by the
yttrium metals.
In effecting a separation of closely related bodies by fractional
processes, in which a large number of repetitions of the same operation
are necessary, only the most careful and systematic procedure can avoid
much waste of valuable material; in these processes, the object of the
chemist is to obtain pure end fractions, whilst keeping the middle
fractions as small as possible. One method of procedure generally
adopted is illustrated in Fig. 7, which represents a fractional
crystallisation of a mixture of four or five substances, α, β, ... φ;
the separations being usually conducted in such a way that subgroups of
three, four or five elements are first obtained, these being then
further fractionated to obtain the pure elements. In the diagram, crops
of crystals are represented by crosses, the mother-liquors by circles;
for the sake of illustration, the process is made to appear as simple
as possible.
[Illustration: FIG. 7]
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