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 _formate_ and _acetate_ can be obtained in the form of neutral salts
by the action of the acids on the hydroxide; by double decomposition,
amorphous precipitates of basic salts are obtained. With _tartaric acid_
stable complex compounds are formed, as shown by the fact that alkalies
will not precipitate the hydroxide from a solution in presence of that
reagent, and by the elevation of the specific rotatory power. Many
_complex salts_ are known, the simplest having the composition
ThO(C₄H₄O₆R´)₂,8H₂O, where R´ = K,Na,NH₄; these are obtained by
dissolving thorium hydroxide in concentrated solutions of alkali
hydrogen tartrates. _Thorium acetylacetone_, Th(C₅H₇O₂)₄, is
precipitated by addition of ammonia to an aqueous solution of the
nitrate mixed with acetylacetone dissolved in ammonia; the solid is
recrystallised from alcohol, and melts at 171°.
~Atomic Weight of Thorium.~--The value adopted by the International
Committee (1914) is 232·4, but most of the determinations carried out
within the last thirty years show considerable discrepancies. The
earlier work of Berzelius (1829) and Chydenius (1861) led to very widely
varying results, and for the same reason little reliance can be placed
on the results of Delafontaine (1863) and Hermann (1864). In 1874 Cleve
determined the constant by ignition of the sulphate, obtaining the mean
values 234·03 and 233·97; the figure 234 based on these results was for
many years accepted as the true atomic weight. A series of
determinations carried out by Nilson in 1882 led to much lower results.
He employed the sulphate ennea- and octohydrates, first dehydrating
these, and then igniting to oxide, and showed that Cleve’s value must be
too high on account chiefly of the hygroscopic nature of the ignited
oxide, which increases in weight when kept; but his own values show
considerable discrepancies. The ratio Th(SO₄)₂,9H₂O-ThO₂ : ThO₂
(enneahydrate converted to oxide) gave the figure (corrected to vacuo)
232·51, whilst the ratio ThO₂ : 2SO₃ (anhydrous sulphate to oxide) gave
232·16; the ratio Th(SO₄)₂ : 9H₂O (hydrate to anhydrous salt) gave,
however, 233·75. The value obtained for the ratio ThO₂ : 2SO₃ for
anhydrous sulphate prepared from the octohydrate was 232·49 (corrected
to vacuo). Five years later, Krüss and Nilson prepared the anhydrous
sulphate from the pure octohydrate, and ignited this to the oxide. The
ratio ThO₂ : 2SO₃ gave as a mean of very concordant results the figure
232·49.
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