The c h l o r i d e s, s u l f a t e s, a n d

n i t r a t e s of the trivalentlanthanides
are soluble in water and in most cases
crystallize as crystalline hydrates
of variabie composition. The
solubility of the sulfates Lnz(SO43.
8Hz0
decreases sharply a s the temperature
is increased from 0 to looo
(Figure 131).
The f l u o r i d e s and o x a l a t e s
are sparingly soluble in water and
dilute inorganic acids. The fluorides
are precipitated either a s the
crystalline hydrates LnF, -0.5HzO
(La, Ce, etc. ) o r anhydrous salts (e.
g.,
of Pr and Nd). The most common
composition of the oxalates is

-
Lnz(CZO,), 1OHzO. The oxalates
of the lanthanides of the yttrium
subgroup
a r e more soluble in water than are
the oxalates of the cerium subgroup
(Figure 132). When heated to 500 to
600" the oxalates decompose yielding
oxides of the LnzQtype.
The lanthanide p h o s ph a t e s, c a r
b o n a t e s, and f e r r i c y a n i d e s
a r e also sparingly soluble in water.
Most of the simple lanthanide salts
have a tendency towards the forma
tion of double o r complex salts with
ammonium and alkali metal salts and
with a number of salts of bivalent
elements. The most important of these
are: the d o u b 1e n i t r a t e s of the
lanthanides with ammonium nitrate
Ln(N03),. 2NH4N03*4Hzo and
magnesium nitrate 3Mg(N03)z.
24H20, whose solubilities increase in
the transition from lanthanum to
gadolinium; the double lanthanide
potassium (or sodium) sulfates
(e. g., Lnz(S04)3.MeS04.nH20where
n is 1 o r 2). From the standpoint
of their solubility in water, double
lanthanide sulfates can be subdivided
into three groups: sparingly soluble
(La, Ce, P r , Nd, Sm), of medium
solubility (Eu, Gd, Tb, Dy) and
readily soluble (Ho, Er, Tu, Yb, Lu,
u). This
is extensively used for the advance
separation of the lanthanides into the
cerium and yttrium subgroups.
The lanthanides form complex
compounds with many organic
substances.
The most important a r e the
complexes with citric acid and with a
number
of aminopolyacetic acids: n i t r i l o t
r i a c e t i c acid (NTA), e t h y l e n e
d i a m i n e t e t r a a c e t i c acid
(EDTA) and some other so-called
"complexones" (see p. 356). In most
cases the stability of the organic
acid complexes of the lanthanides
increases from La to Lu, which is the
principle of some methods of
separation of the lanthanides. The
lanthanide
compounds are characterized by the
fact that their absorption spectra are
composed of sharp bands and lines.
The rslative intensities of the bands
in the wavelength range f5om 2000 to
7000 A a r e shown in Figure 133. In
the visible (3900 to 7700 A ), the
Ce3+, Gd", La3', Lu3+, and Yb3+ions
are
colorless. The remaining lanthanide
ions display characteristic colors.
Uses of rare-earth metals f 4f
The lanthanides are used a s metals,
alloys, and chemical compounds
in various branches of technology:
ferrous and nonferrous metallurgy,
production of glass and ceramics, the
chemical industry, medicine, and
agriculture. They still have other
potential uses, the number of which
increases a s the properties of
lanthanides, their alloys, and
compounds
become known.
267

Ferrous and nonferrous metallurgy.

The lanthanides find extensive use
as additives in the production of steel,
pig iron, and nonferrous metal
alloys. They are used mainly as
ferrocerium or mischmetall (a
lanthanide
alloy in which the main components
are cerium or cerium and lanthanum).
Lanthanide oxides a r e also used as
additiviesl51.
The addition of lanthanides improves
the quality of stainless and high
speed steels, high-silicon steels used
in electrical technology, and re
fractory steels; they increase the
mechanical strength (and especially
the
impact strength), corrosion resistance,
and refractoriness, improve the
workability of the steels, the surface
of castings, and increase the re
crystallization (grain growth)
temperature of steel. From 0.9 to 2.25
kg
of mischmetall is usually added per
ton of steel. The addition of cerium
or mischmetall causes deoxidation,
desulfurization, and probably denitridi
zation of the steel.
The lanthanide metals also improve
the quality of pig iron (casting
properties, hot ductility, resistance to
oxidation, and strength).
The addition of 0.3570 mischmetall to
nichrome prolongs its service
life at 1000" by a factor of 10.
Ferrous alloys with a high
concentration of cerium group metals
(70 to
7570lanthanides and 25 to 3070Fe)
are pyrophoric and find extensive use
in the production of flints (for
lighters) and are used in artillery for
tracer
compositions. Mischmetalls or a
mischmetall alloy with tin and
magnesium
may also be used for similar purposes.
The addition of lanthanide metals to
various aluminum and magnesium
alloys increases their high-
temperature strength. Aluminum-
copper and
aluminum-copper-silicon alloys
containing 0.05 to 0.3570 cerium are
used
for the production of various aircraft
engine parts. The introduction of
mischmetall increases the creep
strength of the high-strength fine-
grained
magnesium alloys (with zinc and
zirconium) used in aviation. These
magnesium alloys contain 0.5 to 4%
Zn, 0.6 to 0.770 Zr, and 1.25 to
2.7570
lanthanides.
The production of glass and
ceramics. The glass industry is one of
the major consumers of lanthanides.
The introduction of lanthanides in the
composition of glass produces
glasses which absorb ultraviolet and
infrared light. Glass containing
2 to 4% Ce2Qis used for the
production of protective goggles for
glass
blowing and welding works.
Praseodymium and neodymium have
a similar
effect.
Cerium-containing glass is resistant
(does not fog) under the effect of
radioactive radiation. It is' used in
nuclear technology.
Some lanthanide oxides are used in
the production of optical glass.
Thus, La203is one of the components
of silicon-free glass for photo
graphic lenses and periscopes.
NdzO3together with V20, are added
to
optical glass for photometers, Nicol
prisms and other instruments.
Lanthanide oxides have been used for
a long time as decolorizers and
colorants of glass. Thus, the addition
of a small amount of C e Q de
colorizes glass while the addition of
up to 1%of cerium oxide makes the
glass yellow while the addition of
larger amounts makes it brown.
Neodymium oxide colors the glass
bright red, praseodymium oxide
green,
and a mixture of both produces a blue
color.