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 their chemical relations, the rare earth elements may be placed
between the metals of the alkaline earths, and the trivalent metals
iron, aluminium, and chromium. With the exceptions of cerium in the
ceric salts, and of samarium and europium in the recently discovered
dichlorides, they are uniformly trivalent, but the oxides are very
strong bases, and the salts very slightly hydrolysed in dilute
solutions; generally, therefore, they resemble the calcium family rather
than the aluminium group. Among the common salts, the oxalates,
phosphates, chromates, iodates, fluorides, carbonates, tartrates, and
borates are almost insoluble; the sulphates are only sparingly soluble
at ordinary temperatures. Among the double salts, the alkali double
sulphates are of great importance from their employment for separations;
the tendency to the formation of complex salts is greater among the
yttrium than among the cerium elements, increasing with the atomic
weight, and with the decrease in basic strength of the oxides.
The great similarity in chemical behaviour of the rare earth elements is
apparent not only in the similarity in composition, solubility and
chemical properties of the salts--which is so great that the general
account of the compounds which follows applies almost in its entirety to
each member of the group--but also in the crystallographic relations
between corresponding compounds. Many of the salt hydrates form
isomorphous series; the sulphate octohydrates, for example, appear to be
isomorphous throughout the whole group, and probably the relation would
be found to apply even more completely than is generally accepted, if
the necessary data were forthcoming. Of great interest and practical
importance is the isomorphism between the nitrates and double nitrates
of the cerium elements and bismuth, which has been utilised with such
valuable results in the processes of fractional crystallisation.
~The Metals.~--The earlier attempts to reduce compounds of the rare
earth elements to the metallic condition, by means of metallic sodium or
potassium, did not yield pure products; nor did the use of aluminium or
magnesium lead to results of practical importance. The metals were first
obtained in a coherent physical condition by Hillebrand and Norton,[147]
by electrolysis of the fused chlorides. These investigators obtained
cerium, lanthanum, and the so-called didymium, and measured their
specific heats; their results confirmed the atomic weights assigned to
the elements by Mendelejeff, except in the case of lanthanum. Their
method has since been elaborated by Muthmann, Hofer and Weiss,[148] who
have prepared large quantities of the cerium elements in the pure
state. More recently, Hirsch has prepared metallic cerium in large
quantities,[149] and has studied its properties.
[147] _Pogg. Ann._ 1875, ~155~, 631; ~156~, 466.
[148] _Annalen_, 1902, ~320~, 231; see also Muthmann and Weiss,
_ibid._ 1904, 331, 1.
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