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 _acetates_ are readily soluble in water, the yttrium salts being
rather less easily soluble than those of the cerium group. They are
therefore obtained by dissolving the oxides in acetic acid; addition of
alkali acetate to a solution of a rare earth salt gives no precipitate,
even on boiling, behaviour which is in marked contrast to the ease with
which the salts of other trivalent metals are hydrolysed under these
conditions. In this respect the rare earth elements differ also from the
tetravalent elements zirconium and thorium (and from cerium in the
tetravalent state); soluble salts of the latter, on boiling with sodium
acetate, give insoluble basic acetates. Even sparingly soluble compounds
of the rare earth elements are as a rule taken into solution by
digestion with ammonium acetate.
_Tartrates._--Addition of ammonium tartrate to a neutral solution of
rare earth salts throws down an amorphous precipitate, which dissolves
easily in acids, and in excess of the precipitant. In the presence of
tartaric acid, precipitation of the earths by addition of sodium
hydroxide is completely inhibited. Potassium hydroxide under these
conditions gives a precipitate in the case of the yttrium elements,
though only on boiling; ammonia gives a crystalline precipitate even in
the cold with this group. These precipitates are alkali double tartrates
of the yttrium metals; the cerium elements give no precipitate at all.
In all cases, therefore, the precipitation of the hydroxides is
inhibited by the presence of tartaric acid.
A very large number of organic salts of the rare earth elements has been
prepared and examined during the past two decades, in the endeavour to
find some class of compounds which will allow of an easy separation of
the group. The _benzoates_, _succinates_, _hippurates_, _citrates_ and
similar relatively simple salts first received attention, but less
common acids, as _e.g._ the hydroxynaphthalenesulphonic acids, have also
been employed.[169] The use of various organic acids for the separation
and estimation of thorium in presence of the rare earths is outlined in
that connection (see p. 288). More recently, the glycollates and
cacodylates have been prepared. The _glycollates_[170] of the cerium
elements have the general formula R(C₂H₃O₃)₃, and crystallise in crusts;
they are more soluble than the yttrium compounds, which have the formula
R(C₂H₃O₃)₃,2H₂O, and crystallise in needles. The _cacodylates_,[171]
R₂[As(CH₃)₂O₂]₆, crystallise with 16 or 18 molecules of water, and have
similar solubility relations.
[169] Erdmann and Wirth, _Annalen_, 1908, ~361~, 190; see also Pratt
and James, _J. Amer. Chem. Soc._ 1911, ~33~, 1330; Baskerville and
Turrentine, _ibid._, 1904, ~26~, 46; James, Hoben and Robinson,
_ibid._, 1912, ~34~, 276, etc.
[170] Jantsch and Grünkraut, _Zeitsch. anorg. Chem._ 1913, ~79~, 305.
[171] Whittlemore and James, J. _Amer. Chem. Soc._ 1913, ~35~, 627.
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