The Rare Earths: Their Occurrence, Chemistry, and TechnologyLevy, Stanley Isaac
Science
The Rare Earths: Their Occurrence, Chemistry, and Technology
Levy, Stanley Isaac
Rare earths
In the double sulphate separation of the yttrium and cerium groups, the
terbium elements divide themselves between the soluble and the insoluble
portions; if the separation is made as complete as possible by addition
of a large excess of alkali sulphate under suitable conditions, the
larger part of the compounds of the group will be precipitated with the
cerium elements. In the separation of the cerium elements the terbium
elements collect in the most soluble fractions, and the mother-liquors
of the double nitrate crystallisations therefore form a very convenient
source of these elements. A considerable proportion, however, will
usually remain in solution with the double sulphates of the yttrium
group; in the bromate separation of these (see p. 198), the terbium
elements collect in the least soluble fractions. By careful
fractionation under suitable conditions, the double sulphate method may
be used to separate the terbium group completely from the cerium and
yttrium elements. A very convenient method of separating the terbium
group from a rare earth mixture is the ethylsulphate process of Urbain.
By fractional crystallisation of these salts from alcohol or water, the
separation into three groups can be satisfactorily accomplished.
For the separation of the terbium elements from one another, the nitrate
and double nitrate methods are most suitable. Samarium can readily be
separated by crystallisation of the double magnesium nitrates in
presence of bismuth magnesium nitrate; by continuing the fractionation,
europium magnesium nitrate can be separated in a pure state, as there is
a considerable difference between the solubility of this salt and the
corresponding compound of gadolinium;[311] the process, however, is
somewhat long and tedious. For the separation of gadolinium and terbium,
the double nitrates are converted into the simple nitrates, and these
fractionated from nitric acid in presence of bismuth nitrate. The
gadolinium nitrate separates before the bismuth nitrate, and may be
obtained fairly pure in this way, though the process is extremely
tedious, and several thousand recrystallisations are required.[312]
Terbium nitrate has almost the same solubility as bismuth nitrate, and
the two separate together in the middle fractions. The more soluble
nitrates of the erbia earths collect in the mother-liquors.
[311] James (_J. Amer. Chem. Soc._ 1912, ~34~, 757) employs at this
stage the fractional crystallisation of the double nickel nitrates.
[312] See Urbain, _Compt. rend._ 1904, ~139~, 736.
~Europium~, Eu = 152·0
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