CERIUM GROUP (_continued_)
LANTHANUM, PRASEODYMIUM, NEODYMIUM, AND SAMARIUM
In his examination of the ceria earths in 1839, Mosander discovered a
new constituent, which he called Lanthana; the new oxide was removed in
solution when the ignited mixture was extracted with dilute nitric acid,
which leaves cerium dioxide undissolved. On examination, the new oxide
was found to be heterogeneous; by fractional precipitation with ammonia,
and subsequent recrystallisation of the sulphates, he obtained two
oxides, which he called respectively Lanthana (λανθανειν, to be hidden),
from the absence of colour and specific reactions, and Didymia,
(διδυμοι, twins) from their similarity and the occurrence of the two
together.
Samaria was isolated by Lecoq de Boisbaudran, in 1879, from a specimen
of didymia extracted from the mineral samarskite. Two years previously,
Delafontaine had shown that the didymia separated from this mineral was
not spectroscopically identical with the oxide obtained from other
sources, and in 1878 had isolated an oxide which he called Decipia; this
was shown later, however, to be a mixture of which samaria was one
component. The samaria obtained by de Boisbaudran was by no means pure,
being associated with terbia earths; several investigators claimed to
have separated from it new oxides, most of these being proved afterwards
to have been more or less impure specimens of Europia.
In 1885, Auer von Welsbach[238] employed for the first time the method
which has now become of paramount importance for the separation of the
cerium group, viz. the fractional crystallisation of the double
nitrates. By this method he succeeded in resolving Mosander’s didymia
into two new oxides, for which he proposed the names Praseodidymia
(πρασινος, leek-green), from the colour of the salts, and Neodidymia
respectively; the shorter names praseodymia and neodymia are, however,
now generally adopted.
[238] _Monats._ 1885, ~6~, 477; _Sitzungsber. kaiserl. Akad. Wiss.
Wien_, 1885, ~92~, II, 317.
[Illustration: ~GROUP A~
MIXED DOUBLE NITRATES.
2R(NO₃)₃,3Mg(NO₃)₂,24H₂O.
|||
+--------------------------------+||
| +---------------+|+---------------+
| | | |
~1~ ~2~ ~3~ ~4~
La, Pr Pr, Nd Crude Nd Mother-liquors.
Compounds. Compounds. Compounds.
Fractionate as Fractionate as Continue the Sa, Eu, Gd, etc.
R(NO₃)₃,2NH₄NO₃, 2R(NO₃)₃, Separation. Crystallise with
4H₂O. 3Mn(NO₃)₂,24H₂O. | Bismuth magnesium
| | | nitrate.
| | +-------+ | | | | |
+-------------+ +---------+-------------+| | Terbium
| | | || | elements.
| | | || |
| | | || +---+
| | | || |
~5~ ~6~ ~7~ ~8~ ~9~
Pure ~La~ Pr with La. Impure Pr Pure ~Nd~ Pure ~Sa~
Compound. Compound. Compound. Compound.
Refine by Continue. Continue. Refine by
Sulphate | | Sulphate
crystallisa- | | crystallisa-
tion. | | tion.
| |
+--------+-----+ +----+
| | |
Mixture of ~Pr.~
Pr, La. Refine by Sulphate
crystallisation.
FIG. 8.--SEPARATION OF THE CERIUM ELEMENTS]
SEPARATION
The modern methods for the separation of these elements are based almost
entirely on the differences in solubility of the various double
nitrates.[239] The mixed double sulphates separated by saturation of a
solution of the chlorides with sodium sulphate, which contain the cerium
and most of the terbium elements, are transformed into nitrates, and the
neutral solution boiled with potassium bromate, in presence of powdered
marble, till all the cerium is precipitated as basic ceric nitrate. From
the filtered solution the other elements are thrown down as oxalates,
transformed into the magnesium double nitrates (A in Fig. 8), and
fractionated from nitric acid solution[240] until a rough separation has
been effected (fractions 1, 2, 3, and 4). The separation, which is
somewhat long and tedious, is followed by means of the absorption
spectra, and by the colour changes of the fractions. Fraction 1,
containing lanthanum and some praseodymium, should be faint green to
colourless; fraction 2 is colourless by the complementary action of the
coloured salts of neodymium and praseodymium; fraction 3, which should
contain the crude neodymium salt, is amethyst; and fraction 4, the
mother-liquor, is yellow from the presence of the samarium compound.
[239] The following scheme is largely from James, ‘The Separation of
the Rare Earths,’ _J. Amer. Chem. Soc._ 1912, ~34~, 757.
[240] See Demarçay, _Compt. rend._ 1900, ~130~, 1019 and 1186; also
Drossbach, _Ber._ 1902, ~35~, 2826, and Muthmann and Weiss, _Annalen_,
1904, ~331~, 1.
Fraction 1 is now converted to the double ammonium nitrates, which allow
of a readier separation at this stage; two fractions are obtained, of
which the less soluble, fraction 5, is the fairly pure lanthanum
compound, whilst the more soluble, fraction 6, contains the praseodymium
with a little lanthanum. The lanthanum ammonium nitrate, fraction 5, is
converted into the anhydrous sulphate, which is dissolved in ice-water;
when the solution is gradually warmed, the enneahydrate, La₂(SO₄)₃,9H₂O,
separates, and may be obtained perfectly pure by recrystallisation. It
is of interest that the radioactive element actinium is chemically very
similar to lanthanum, and follows it closely through the process of
separation.
The mixed praseodymium and neodymium magnesium nitrates which constitute
fraction 2 are transformed into the double manganese nitrates, and the
crystallisation from nitric acid continued.[241] The less soluble part,
fraction 7, is fairly free from neodymium, and the separation is
continued with that of fraction 6, until both lanthanum and neodymium
have been completely removed. The more soluble part, fraction 8, yields
the pure neodymium compound, as does also the crude neodymium magnesium
nitrate which constitutes fraction 3, if the crystallisation be
continued.
[241] Cf. Lacombe, _Bull. Soc. Chim._ 1904, [iii.], ~31~, 570.
The mother-liquors, fraction 4, are treated with bismuth magnesium
nitrate,[242] which is intermediate in solubility between the analogous
compounds of samarium and europium, and the crystallisation continued.
The less soluble fraction contains the samarium compound, in which
bismuth is the only impurity; this is easily removed by treatment with
sulphuretted hydrogen. The remaining fractions are used as a source of
the terbium elements (see p. 186).
[242] See Urbain and Lacombe, _Compt. rend._ 1903, ~137~, 792; _ibid._
1904, ~138~, 84 and 1136.
The double carbonate method[243] is very suitable for the preparation of
pure lanthanum compounds after the removal of cerium. The mixture of
salts is added to a warm 50% solution of potassium carbonate, and to the
clear liquid, water is added gradually, with constant stirring. The
double carbonates of the most positive elements are the least soluble,
and are first thrown down, so that the precipitate is rich in lanthanum;
it is collected and washed with a 25% potassium carbonate solution, and
the process repeated. A few repetitions suffice to separate lanthanum
completely from the other members of the group. The method may also be
used for the purification of praseodymium salts.
[243] Meyer, _Zeitsch. anorg. Chem._ 1904, ~41~, 94.
~Lanthanum~, La = 139·0
As the most electropositive element of the rare earth group, lanthanum
is the most similar in its chemical properties to the metals of the
alkaline earths. The _metal_ itself (see p. 115) oxidises even in dry
air, and in moist air rapidly becomes coated with a white layer of
hydroxide; it attacks water, and burns vigorously when heated in the
air. An alloy with aluminium, of the formula LaAl₄, has been prepared by
Muthmann and Beck[244]; it forms lustrous white crystals, very stable in
the air and very resistant towards acids.
[244] _Annalen_, 1904, ~331~, 46.
The _hydroxide_ is of interest from the fact that, if precipitated under
suitable conditions, it has the power of taking up solid iodine to form
a deep blue adsorption compound[245]; colloidal solutions of basic
lanthanum acetate are also coloured blue by addition of a few drops of
iodine solution. If precipitation with alkali be carried out in presence
of hydrogen peroxide, an hydrated _peroxide_ of the composition
La₂O₅,_n_H₂O is obtained.[246] This compound partially decomposes with
evolution of oxygen at ordinary temperatures; towards carbon dioxide and
acids it acts as a true peroxide, with formation of hydrogen peroxide.
[245] Damour, _Compt. rend._ 1857, ~43~, 976; see also Biltz, _Ber._
1904, ~37~, 719
[246] Melikoff and Pissarjewski, _Zeitsch. anorg. Chem._ 1899, ~21~,
70.
The _oxide_ is colourless, and forms colourless salts with those acids
in which the anion is not coloured. The oxide is distinguished from the
other rare earth oxides in that it turns moistened litmus paper blue; it
resembles lime, in hissing when slaked, absorbing carbon dioxide from
the air, and liberating ammonia from ammonium salts. By fusion with
alkali carbonates, and by digestion with concentrated alkali hydroxides,
Baskerville and Catlett[247] claim to have obtained lanthanates and
metalanthanates, but their work has not yet been confirmed.
[247] _J. Amer. Chem. Soc._ 1904, ~26~, 75.
The _sulphate_, La₂(SO₄)₃,9H₂O, is the least soluble of all the rare
earth sulphates. The enneahydrate is the only form stable at ordinary
temperatures,[248] though under special conditions, hydrates with 6 and
with 16 molecules of water of crystallisation have been obtained. It
separates in needles belonging to the hexagonal system; 100 parts of
water dissolve at 0°, 3·01, and at 100°, 0·69 parts of the salt. The
_acetylacetone compound_ melts at 185°.
[248] Muthmann and Rölig, _Ber._ 1898, ~31~, 1718.
A large number of other lanthanum compounds have been prepared, but
these are so typical of the rare earth salts generally that no detailed
treatment is required; for a full account of them, the reader is
referred to Abegg’s classical handbook.
~Atomic Weight.~--A large number of determinations of this constant have
been made, but the results even of recent investigations do not agree so
closely as might be desired. The value adopted by the International
Committee, 139·0, is based on the work of Brauner and Pavliček,[249]
carried out in 1902. These authors give an account of all the
determinations made up to that date, with critical discussion of the
methods employed and the possible sources of error. The more important
investigations have been based on the ratio La₂O₃ : La₂(SO₄)₃, for the
determination of which the most stringent precautions must be taken. The
synthetic method has generally been employed, on account of the tenacity
with which the oxide clings to traces of sulphuric anhydride. In this
method, the total decomposition of the acid sulphate, and the protection
of the very hygroscopic sulphate, La₂(SO₄)₃, from atmospheric moisture,
constitute the chief difficulties. By this method, H. C. Jones[250] in
1902 obtained a result (138·76) considerably lower than the value found
by Brauner and Pavliček (_loc. cit._) A later research by Brill,[251]
who carried out a synthetic sulphate determination on a minute scale,
using a Nernst microbalance, gave the value 139·5, which, whilst
considerably higher than either of the other figures, shows that Brauner
and Pavliček’s number can hardly be too high.
[249] _Trans. Chem. Soc._ 1902, ~81~, 1243.
[250] _Amer. Chem. J._ 1902, ~28~, 23.
[251] _Zeitsch. anorg. Chem._ 1906, ~47~, 464.
~Detection.~--Pure lanthanum compounds show no absorption in the
visible region, and the pure oxide gives no cathode luminescence. The
emission spectra show very characteristic lines in the violet and
ultraviolet. The chief lines are:
3949·27
3988·69
4238·55
4333·98
6250·14
6262·52
6394·46
For arc spectra see Exner and Haschek; Eder and Valenta.[252]
[252] _Sitzungsber. kaiserl. Akad. Wiss. Wien_, 1910, ~119~, IIa, 39.
~Praseodymium~, Pr = 140·6
This element occurs only in small quantities in the commoner rare earth
minerals, and its separation in the pure state is in consequence a
matter of very great difficulty. The salts and their solutions have a
characteristic green colour. The salts are derived from the sesquioxide,
Pr₂O₃, but a dioxide, PrO₂, and an intermediate oxide of uncertain
composition are known. The absorption spectrum has five absorption
bands, one of which coincides with a band in the absorption spectrum of
neodymium; this fact has been interpreted as an indication of the
non-elementary nature of both metals.[253] Difference in the absorption
spectra have been put forward by several workers as indicating the
complex nature of praseodymium, but an exhaustive examination by
Stahl[254] in 1909 showed that there is no reason to doubt that the
metal is really an element.
[253] Auer von Welsbach, _Sitzungsber. kaiserl. Akad. Wiss. Wien_,
1903, ~112~, II_a_, July; also Urbain, _Ann. Chim. Phys._ 1900, [vii],
~19~, 184.
[254] _Le Radium_, 1909, ~6~, 215.
The _metal_ is prepared by electrolysis of the fused chloride; in order
to attain the temperature required to fuse the element, a very thin
cathode is employed; if too powerful a current be used, the dioxide is
formed. The metal is purified by remelting it in crucibles of magnesia,
under a layer of anhydrous barium chloride. It has a yellowish shade,
and is more stable in the air than lanthanum and cerium. For physical
properties, see p. 115. No alloys have been prepared.
The _hydroxide_ is thrown down by alkalies as a gelatinous green
precipitate; in the presence of hydrogen peroxide, an hydrated peroxide,
which closely resembles the corresponding lanthanum compound, is thrown
down.
The _Oxides_.--By ignition of salts of volatile acids, Auer von
Welsbach[255] obtained an oxide to which he assigned the formula Pr₄O₇.
More recent work[256] has shown that the composition of the oxide
obtained depends upon the conditions under which the various salts are
decomposed. By fusing the nitrate in presence of potassium nitrate at
400-450°C., Meyer obtained the dioxide, PrO₂; at higher temperatures
this decomposes, giving the intermediate oxides. The formation
of the dioxide is greatly influenced by the presence of other
oxides,[257]--ceric oxide, acting as an oxygen carrier, favouring
whilst the other oxides hinder. The pure dioxide is a brownish-black
powder, which resembles manganese dioxide, but is less stable. It
liberates halogens from the halogen acids, and oxidises manganese salts
to permanganates, but does not completely oxidise ferrous or stannous
salts, losing instead a part of its oxygen in the gaseous form. The
dioxide cannot be obtained in the wet way.
[255] _Monats._ 1885, ~6~, 477.
[256] See, _e.g._ Meyer, _Zeitsch. anorg. Chem._ 1904, ~41~, 94.
[257] Brauner, _Monats._ 1882, ~3~, 1; Marc, _Ber._ 1902, ~35~, 2370;
Meyer and Koss, _ibid._ 3470.
When heated in a stream of hydrogen, the dioxide yields the
_sesquioxide_, Pr₂O₃, as a greenish-yellow powder,which readily absorbs
oxygen from the air, becoming brown, with formation of the intermediate
oxide.
The _chloride_, PrCl₃,7H₂O, forms large green prisms, very readily
soluble in water; 100 parts of the solvent at 13° take up 334·2 parts of
the hydrated salt, the solution having the specific gravity 1·687. The
anhydrous chloride is a pale green deliquescent powder, which melts at a
red heat to a clear green liquid; ebullioscopic measurements show that
in alcoholic solution it has the simple molecular formula PrCl₃.
The _Bromate_, Pr(BrO₃)₃,9H₂O, has been obtained by James and
Langelier[258] by dissolving the oxide in aqueous bromic acid, and also
by double decomposition. It forms greenish hexagonal prisms, melting at
56·5°, and is readily soluble; 100 parts of water dissolve 190 parts of
this salt at 25°. At 100° it loses five molecules of water, forming the
tetrahydrate Pr(BrO₃)₃,4H₂O, which loses all its water at 130°. The
anhydrous salt begins to decompose at 150°.
[258] _J. Amer. Chem. Soc._ 1909, ~31~, 913.
The _sulphate_ crystallises with 8 molecules of water of crystallisation
at ordinary temperatures, but hydrates with 15¹⁄₂, 12, and 5 molecules
of water respectively have been described. The octohydrate is
considerably more soluble than lanthanum sulphate enneahydrate. The
anhydrous salt is a bright green powder.
_Praseodymium acetylacetone_ melts at 146°.
~Atomic Weight.~--The value 140·6, adopted by the International
Committee, is based on the work of Jones, v. Scheele, Auer von
Welsbach, and Feit and Przibylla; the work of Brauner, however, points
consistently to a higher atomic weight. Most of these investigators have
used the sulphate method. The first determinations of von Welsbach for
the newly discovered element[259] gave the value 140·8 (see p. 179);
another series of determinations published in 1903[260] gave the mean
value 140·57. Jones[261] obtained the sesquioxide for the synthetic
sulphate operation by reduction of the peroxide in a current of
hydrogen; according to Brauner, this method gives an oxide which is not
perfectly pure, probably by absorption of water vapour and carbon
dioxide from the air. Jones’ mean value was 140·466. v. Scheele[262]
used the same method, as well as a combined oxalate-sulphate method; his
figures vary considerably, the mean value being 140·55. Feit and
Przibylla,[263] using their volumetric method, obtained the value
140·54.
[259] _Monats._ 1885, ~6~, 477.
[260] _Sitzungsber. kaiserl. Akad. Wiss. Wien_, 1903, ~112~, 1037.
[261] _Amer. Chem. J._ 1898, ~20~, 345.
[262] _Zeitsch. anorg. Chem._ 1898, ~17~, 310.
[263] _Zeitsch. anorg. Chem._ 1906, ~50~, 249.
Brauner’s earlier work,[264] carried out in 1898, gave the value 140·95.
In 1901 this author[265] carried out an extensive research on the atomic
weight of praseodymium, employing four different methods with
spectroscopically pure material; the mean value of his very concordant
results was 140·97, almost the value he obtained in 1901. A further
investigation into the value of this constant appears desirable.
[264] _Proc. Chem. Soc._ 1898, ~14~, 70.
[265] _Ibid._ 1901, ~17~, 65; see also Abegg, III, i. 263.
~Detection.~--The maxima of the absorption bands are given by
Rech[266] as follows:
[266] _Zeitsch. wiss. Photochem._ 1906, ~3~, 411.
Yellow 596·4 and 588·2, weak.
Blue 481·3 very intense.
468·3 coincident with a neodymium band.
Violet 444·2
The arc spectrum is very rich in lines.[267] The most intense, which
may be used also for identification, are the following:
[267] Exner and Haschek; Bertram, _Zeitsch. wiss. Photochem._ 1906,
~3~, 16; Eder and Valenta, _Sitzungsber. kaiserl. Akad. Wiss. Wien_,
1910, ~119~, II_a_, 65.
4008·90
4100·91
4118·70
4143·33
4179·60
4189·70
4206·88
4223·18
4225·50
4241·20
4305·99
4429·38
4496·60
4510·32
~Neodymium~, Nd = 144·3.
Neodymium is, after cerium, the commonest constituent of the cerium
group in the more important rare earth minerals, and its separation is
therefore by no means so difficult as that of praseodymium. The
compounds of the element obtained by von Welsbach in 1885 were not pure,
being admixed with samarium compounds which had not been completely
separated. Neodymium salts were first prepared free from samarium by
Demarçay[268] in 1898; they are of a violet-rose colour, and show in
solution a well-marked and characteristic absorption spectrum, the bands
being very numerous and sharply defined, and extending over the whole
optical region. In chemical as well as in physical and crystallographic
properties, they show an extremely close resemblance to the compounds of
praseodymium.
[268] _Compt. rend._ 1898, ~126~, 1039.
On account of the high melting-point, the preparation of the _metal_
presents the same difficulties as that of praseodymium. A current of
90-100 ampères is employed at a potential difference of 15-22 volts;
this suffices to raise the thin carbon cathode to a bright white heat,
and to fuse the liberated metal. For the properties of the element, see
p. 115.
The _sesquioxide_, Nd₂O₃, when perfectly pure, has a light blue or lilac
colour, with a faint reddish fluorescence; the shade varies somewhat
according to the method of and temperature employed for the preparation.
A bluish or violet-red fluorescence is highly characteristic of the
salts, and is particularly noticeable if the powdered recrystallised
oxalate be viewed in a good light. The greyish or brownish colour of the
oxide observed by some authors is probably due to traces of
impurity.[269] The existence of higher oxides of the formulæ Nd₂O₄ and
Nd₂O₅ respectively, which Brauner[270] put forward, has been disputed
by other writers, though it is found[271] that in the presence of ceria
and praseodymia, the sesquioxide can take up more oxygen. Waegner[272]
claimed to have obtained the compound Nd₄O₇ by heating the oxalate in a
stream of oxygen, though his material, as well as that of Brauner,
contained praseodymia. More recently, Joye and Garnier[273] have shown
that the spectrum attributed by Waegner to the hypothetical Nd₄O₇ was in
reality that of an hydrated oxide, 2Nd₂O₃,2H₂O; these authors have also
prepared a second hydrated oxide of the formula 2Nd₂O₃,3H₂O.
[269] See Waegner, _Zeitsch. anorg. Chem._ 1904, ~42~, 118; also
Baxter and Chapin, _J. Amer. Chem._ Soc. 1911, ~33~, 1.
[270] _Chem. News_, 1898, ~77~, 161; _ibid._ 1901, ~83~, 197.
[271] See Meyer and Koss, _Ber._ 1902, ~35~, 3740; and Marc, _ibid._
2370.
[272] _Loc. cit._
[273] _Compt. rend._ 1912, ~154~, 510.
The _chloride_, NdCl₃,6H₂O, is obtained by crystallisation from aqueous
solutions; it is also precipitated by addition of water to an alcoholic
solution. It forms large deliquescent rose-coloured crystals; 100 parts
of water at 13° dissolve 246·2 parts of the salt, the saturated solution
having the density 1·741; at 100°, 511·6 parts are dissolved. The
solution resembles those of the other chlorides of the group in that it
readily dissolves the rare earth oxalates. When heated in a current of
hydrogen chloride of 130°, the hexahydrate yields a monohydrate,
NdCl₃,H₂O; at 160° the anhydrous chloride is obtained as a very
deliquescent rose-coloured powder, which melts at a red heat to a clear
red liquid. The anhydrous chloride forms an additive compound
NdCl₃,12NH₃, when exposed to the action of ammonia at low
temperatures;[274] by gradually heating this, a large number of other
additive compounds are formed, containing smaller quantities of ammonia.
[274] Matignon and Trannoy, _Compt. rend._ 1906, ~142~, 1042.
The anhydrous _iodide_, NdI₃, has been obtained[275] by passing hydrogen
iodide over the heated anhydrous chloride, and also by heating the
carbide in iodine vapour. It fuses to a black liquid, which at a higher
temperature suddenly becomes transparent.
[275] Matignon, _ibid._ 1905, ~140~, 1637.
The _bromate_, Nd(BrO₃)₃,9H₂O, which is exactly similar to the analogous
compound of praseodymium, forms rose-coloured hexagonal prisms, melting
at 66·7°.
The _sulphate_, Nd₂(SO₄)₃,8H₂O, is isomorphous with the corresponding
salt of praseodymium, but is considerably less soluble. Only the one
hydrate is known.
The _nitrates_ show an interesting case of isomorphism with the
corresponding bismuth nitrate hydrates.[276] The stable form of the
neodymium salt is the hexahydrate, Nd(NO₃)₃,6H₂O, whilst the
pentahydrate, Nd(NO₃)₃,5H₂O, is labile. Of the bismuth salts, on the
other hand, the pentahydrate is stable whilst the hexahydrate is labile;
but mixed crystals of both pairs may be obtained, the stable neodymium
hexahydrate with the unstable bismuth compound, and the stable bismuth
pentahydrate with the labile neodymium salt.
[276] Bodman, _Ber._ 1898, ~31~, 1237.
Many _double carbonates_ are obtained by dissolving the normal carbonate
in excess of the precipitant. The absorption spectra of these solutions,
which have a blue colour, are abnormal and very intense, and have been
suggested as a basis of quantitative estimation.[277]
[277] Muthmann and Stutzel, _Ber._ 1899, ~32~, 2653.
The _acetylacetone derivative_ forms violet crystals, melting at
144°-145°.
A large number of _organic salts_ of neodymium have been prepared by
James, Hoben, and Robinson.[278]
[278] _J. Amer. Chem. Soc._ 1912, ~34~, 276.
~Atomic Weight.~--The earlier determinations of this constant were
carried out by the sulphate method, the synthetic process being usually
employed. Auer von Welsbach, at the time of the discovery of
praseodymium and neodymium,[279] gave the values 143·6 and 140·8
respectively for their atomic weights. Brauner, who carried out a
determination in 1898,[280] showed that these numbers should be
interchanged, and gave the value 143·63 for neodymium. Boudouard,[281]
employing the analytical sulphate method, obtained the value 143·05,
whilst in the same year Jones[282] gave the value 143·6. A second
determination by Brauner[283] gave the value 143·89. All these values
are undoubtedly too low, the material being probably contaminated with
other earths.
[279] _Loc. cit._
[280] _Proc. Chem. Soc._ 1898, ~14~, 70.
[281] _Compt. rend._ 1898, ~126~, 900.
[282] _Amer. Chem. J._ 1898, ~20~, 345.
[283] _Proc. Chem. Soc._ 1901, ~17~, 66.
In his second determination in 1908, Auer von Welsbach[284] gave the
value 144·54 as the mean of three determinations. Feit and
Przibylla,[285] using their volumetric method, gave the value 144·52,
whilst Holmberg,[286] using material which he considered to have been
the purest obtained up to that time, obtained the figure 144·11. More
recently, Baxter and Chapin[287] have made determinations by treating
the chloride with pure silver nitrate, and weighing the precipitated
silver chloride, as well as by titration. The mean value obtained by the
first method--ratio NdCl₃ : 3AgCl--was 144·272 (extremes 144·250 and
144·298), and by the second method--ratio NdCl₃ : 3Ag--was 144·268
(extremes 144·249 and 144·283), giving the mean value for the whole
series of 144·270.
[284] _Loc. cit._
[285] _Zeitsch. anorg. Chem._ 1905, ~43~, 202; _ibid._ 1906, ~50~,
249.
[286] _Ibid._ 1907, ~53~, 124.
[287] _Proc. Amer. Acad._ 1911, ~46~, 215.
The value adopted by the International Committee is 144·3.
~Detection.~--The absorption spectra of neodymium compounds have been
examined by Demarçay, Forsling, von Welsbach, Rech, Schäfers, and
Baxter and Chapin, with concordant results. The positions of the
absorption maxima as given by Holmberg[288] from the measurements of
Forsling are as follows, the weaker bands being omitted:
[288] _Zeitsch. anorg. Chem._ 1907, ~53~, 83.
677·5
621·7
578·5 } In concentrated solution
575·4 } these give the
573·5 } intense absorption
571·6 } region in the yellow.
532·3}
521·6} In concentrated
520·4} solution these
512·4} give one intense
508·7} band.
474·5
468·7
461·0
427·1
The arc spectrum is given by Exner and Haschek, Bertram,[289] and
Eder and Valenta.[290] The most intense lines are as follows:
[289] _Zeitsch. wiss. Photochem._ 1906, ~3~, 16.
[290] _Sitzungsber. kaiserl. Akad. Wiss. Wien_, 1910, ~119~, II_a_,
554.
3863·52
3951·32
4061·27
4156·30
4247·54
4282·67
4303·78
4325·87
4375·11
4385·81
4400·96
4446·51
4451·71
4463·09
4920·84
5923·35
5319·98
5594·58
5620·75
6310·69
6314·69
6385·32
~Samarium~, Sa = 150·4
The samarium of the earlier chemists (see p. 168) contained a large
proportion of the terbium elements, from which a fairly complete
separation was first effected by Demarçay in 1900.[291] By the
fractional crystallisation of the double magnesium nitrate in presence
of bismuth magnesium nitrate, Urbain and Lacombe[292] succeeded in
preparing samarium compounds, which were shown by spectroscopic
examination[293] to be free from other earths. The element is
intermediate in electropositive character and in the solubility
relations of its salts between neodymium and the terbium earths; its
salts are topaz-yellow in colour, and in concentrated solutions show
absorption in the blue and violet regions. The oxide is almost white in
colour, with only a faint yellow tinge. A systematic investigation of
samarium compounds was carried out by Cleve,[294] but his work was
vitiated by the fact that his material was very impure. More recently,
the pure salts have been examined by Matignon and his pupils.
[291] _Compt. rend._ 1900, ~130~, 1185.
[292] _Ibid._ 1904, ~138~, 84 _and_ 1166.
[293] Eberhard, _Zeitsch. anorg. Chem._ 1905, ~45~, 374.
[294] _Trans. Chem. Soc._ 1883, ~43~, 362; _Bull. Soc. Chim._ 1885,
[ii.], ~43~, 53; _Chem. News_, 1886, ~53~, 30, 45, 67, 80, 91, 100.
The melting-point of the _metal_ lies between 1300° and 1400°C., so that
its preparation by the electrolytic method is a matter of great
difficulty. A mixture of the chloride with one-third of its weight of
barium chloride is electrolysed by means of a current of 100 ampères,
using a cathode of only 2·5 mm. thickness; the metal so obtained is
greyish white in colour, and is the hardest of the cerium elements.
The _chloride_ separates from aqueous solution as the hexahydrate,
SaCl₃,H₂O, in large tabular yellow crystals. The anhydrous chloride is
white, but fuses to a chocolate-brown liquid; it forms a large number of
additive compounds with ammonia. When heated in an atmosphere of dry
hydrogen or ammonia, air and moisture being carefully excluded, it
yields the _subchloride_,[295] SaCl₂, as a dark brown crystalline solid,
insoluble in alcohol and all organic solvents. Samarous chloride
dissolves in water, forming a deep brownish-red solution, which rapidly
becomes colourless, with evolution of hydrogen, and precipitation of the
oxide and oxychloride. _Samarous iodide_, SaI₂, may be obtained by a
similar process, and closely resembles the chloride.
[295] Matignon and Cazes, _Compt. rend._ 1906, ~142~, 83.
The _bromate_, Sa(BrO₃)₃,9H₂O, melts at 75°, and closely resembles the
corresponding compounds of the didymium metals. The _sulphate_
crystallises with 8, and the _nitrate_ with 6 molecules of water. The
_carbonate_, Sa₂(CO₃)₃,3H₂O, can be obtained only by passing carbon
dioxide through an aqueous suspension of the hydroxide; addition of
alkali carbonate to a solution of a samarium salt precipitates hydrated
double carbonates.
The _acetylacetone compound_ melts at 146°-147°C.
Many organic salts have been prepared by James, Hoben, and Robinson
(_loc. cit._).
~Atomic Weight.~--The earlier determinations of this constant were
carried out with material not entirely free from europium. Demarçay[296]
carried out a synthetic sulphate operation with the material which he
obtained free from europium in 1900, and found values between the limits
147·2 and 148·0. The International Committee has adopted the value
150·4, which is based on the work of Urbain and Lacombe[297] in 1904.
These authors made determinations of three series of ratios, obtained by
(_a_) conversion of sulphate octohydrate to anhydrous sulphate, (_b_)
conversion of anhydrous sulphate to oxide, and (_c_) conversion of
sulphate octohydrate to oxide; these gave the values 150·314, 150·533,
and 150·484 respectively, from which the mean atomic weight is
150·44.[298]
[296] _Loc. cit._
[297] _Compt. rend._ 1904, ~138~, 1166.
[298] These numbers are calculated by Brauner (Abegg’s _Handbuch_,
III. i. p. 285) on the basis O = 16, S = 32·06, H = 1·0076, and are
somewhat higher than those given by Urbain and Lacombe, who used the
round numbers O = 16, S = 32, and H = 1.
~Detection.~--The absorption spectrum of samarium compounds is only
visible in fairly concentrated solutions, so that the element cannot
usually be detected in a mixture by this means. The position of the
maxima of the strongest bands (Demarçay, _loc. cit._) are:
476
463
417
402
These are all in the blue and violet regions; the first and second are
in the neighbourhood of neodymium and europium bands (_q.v._), and in
concentrated solutions the bands would partially coincide. Since these
are the two elements from which the separation is most difficult, and
are moreover the most constant in their occurrence with samarium, the
absorption spectrum is of very little use as a test.
The arc spectrum is very rich in lines,[299] of which the most intense
are:
3739·30
4152·38
4203·18
4225·48
4229·83
4236·88
4256·54
4319·12
4329·21
4334·32
4347·95
4391·03
4420·72
4421·32
4424·55
4434·07
4434·52
4452·92
4454·84
4458·70
4467·50
4519·80
4524·08
4544·12
4566·38
4577·88
4642·41
4674·79
[299] Exner and Haschek; Eder and Valenta; Rütten and Mersch,
_Zeitsch. wiss. Photochem._ 1905, ~3~, 181.