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 which can be adopted in attempting a separation are of two
kinds. The first includes those processes which take advantage of the
gradual variation in basic strength of the hydroxides as the atomic
weight changes; the most important of these are fractional precipitation
of the hydroxides, and fractional decomposition of the nitrates.
Fractional precipitation of the hydroxides is generally effected by
gradual addition of ammonia, soda, magnesia, or other base, to a
solution of the mixed salts; such a solution may also be digested with
the oxides obtained by ignition of another fraction of the rare earth
compounds. If the digestion be sufficiently complete, the precipitate in
each case will be richer in the less basic hydroxides, whilst the
solution will be richer in the salts of the more electropositive
elements.
The fractional decomposition of the nitrates is based on the fact that
when a mixture of the salts is heated gradually, the nitrate of the
least positive element begins to decompose first. The temperature is
maintained for some time at the point at which decomposition begins;
when nitrous fumes cease to be evolved the mixture is cooled, and
extracted with water or dilute acids. The insoluble portion--basic or
superbasic nitrate (see p. 128)--will then be richer in the less
electropositive elements; the solution is evaporated, and the solid so
obtained subjected to a somewhat higher temperature, and the process
repeated several times. In this way, a series of fractions is obtained,
in which the elements tend to distribute themselves in order of
electropositive character. By a sufficient number of systematic
repetitions of such steps, the elements may eventually be obtained in
the form of compounds of approximate purity, which may then be refined
by one of the methods of the second kind described below. Experience has
shown, however, that a quicker and more complete separation may
generally be effected by combining two or more methods of separation;
one method will give the best separation up to certain limits, but then
becomes much less valuable; the separation at this point is therefore
taken up by another process. A process depending on differences of basic
strength of the hydroxides is generally supplemented by a method of the
second class, i.e. a process of fractional crystallisation; where the
basicity method is not used (as, for example, in most of the recent
processes for separation of the cerium elements), two or more different
methods of fractional crystallisation will supplement one another.
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