The Rare Earths: Their Occurrence, Chemistry, and TechnologyLevy, Stanley Isaac
Science
The Rare Earths: Their Occurrence, Chemistry, and Technology
Levy, Stanley Isaac
Rare earths
[105] _Phil Mag._ 1831, [ii.], ~10~, 139.
[106] _Amer. J. Sci._ 1837, ~32~, 162.
[107] _Pogg. Ann._ 1840, ~49~, 223.
The question of the manner in which the thorium is combined in monazite
is of considerable importance, in view of the fact that it is to this
element that the mineral owes its commercial value. The amount present
varies from traces up to over 20 per cent., but the usual value is
between 5 and 7 per cent. The first explanation of its presence was
advanced by Dunnington[108] who suggested, on the result of only one
analysis, that orangite (ThSiO₄) was present mechanically mixed with the
monazite. Penfield[109] supported this suggestion, and stated that in
three analyses of pure material he found the ratio of rare earths to
phosphorus pentoxide and that of thoria to silica exactly equal to
unity, though the actual amounts of thoria varied considerably. He also
quotes an analysis made by Rammelsberg in 1877, in which no thoria was
found, to show that it is not an essential constituent. In a microscopic
examination he found dark resinous particles scattered throughout the
section; after moistening with hydrochloric acid, warming, and washing,
these dark spots became white, and could be stained with fuchsine, the
monazite remaining unaffected throughout. He concluded that these
particles were thorite or orangite.
[108] _Amer. Chem. J._ 1882, ~4~, 138.
[109] _Amer. J. Sci._ 1882, [iii.], ~24~, 250; 1888, ~36~, 322.
Blomstrand[110] disputed Penfield’s conclusions. In twelve analyses of
monazite from various parts of Scandinavia he never once found either
thoria or silica absent. Of these twelve analyses, two give the ratio of
thoria to silica, ThO₂ : SiO₂, exactly unity, in seven cases the ratio
is not greater than 1·25, in five cases it varies considerably. He
summed up his results in three statements:
(_a_) Silica is never absent; its amount depends not on the amount of
thoria, but on the amount of phosphorus pentoxide present.
(_b_) The thoria which is always present is combined partly with
silica, partly with phosphorus pentoxide.
(_c_) In most cases, the rare earths alone are insufficient to satisfy
the ratio R₂O₃ : P₂O₅ = 1.
[110] _J. pr. Chem._ 1890, ~41~, 266.
An exhaustive examination of the question has been made more recently by
Kress and Metzger.[111] They made in all over fifty analyses, using
thirty different specimens of monazite; they estimated silica both as
quartz and as silicate silica, and determined thorium by the fumarate
method--the other investigators had used the thiosulphate method of
Hermann (_vide_ p. 286). Their results may be summarised as follows:
(i.) Silica is always present.
(ii.) The amount of silica usually increases with the thoria, but not
regularly.
(iii.) By far the majority of cases showed insufficient total silica
to combine with the thoria present.
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