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Lanthanides - Real-life applications

The Historical Approach


In studying the lanthanides, one can simply move along the periodic table, from lanthanum
all the way to lutetium. However, in light of the difficulties involved in extracting the
lanthanides, one from another, an approach along historical lines aids in understanding the
unique place each lanthanide occupies in the overall family.

S AMARIUM IS USED IN NUCLEAR POWER PLANT CONTROL RODS , SUCH AS


THE ONE SHOWN HERE .
(Tim Wright/Corbis
. Reproduced by permission.)
The terms "lanthanide series" or even "lanthanides" did not emerge for some timein other
words, scientists did not immediately know that they were dealing with a whole group of
metals. As is often the case with scientific discovery, the isolation of lanthanides followed an
irregular pattern, and they did not emerge in order of atomic number.
Cerium was in fact discovered long before lanthanum itself, in the latter half of the eighteenth
century. There followed, a few decades later, the discovery of a mineral called ytterite, named
after the town of Ytterby, Sweden, near which it was found in 1787. During the next century,
most of the remaining lanthanides were extracted from ytterite, and the man most responsible
for this was Swedish chemist Carl Gustav Mosander (1797-1858).
Because Mosander had more to do with the identification of the lanthanides than any one
individual, the middle portion of this historical overview is devoted to his findings. The
recognition and isolation of lanthanides did not stop with Mosander, however; therefore
another group of minerals is discussed in the context of the latter period of lanthanide
discovery.

Early Lanthanides
CERIUM.
In 1751, Swedish chemist Axel Crnstedt (1722-1765) described what he thought was a new
form of tungsten, which he had found at the Bastns Mine near Riddarhyttan, Sweden. Later,
German chemist Martin Heinrich Klaproth (1743-1817) and Swedish chemist Wilhelm
Hisinger (1766-1852) independently analyzed the material Crnstedt had discovered, and
both concluded that this must be a new element. It was named cerium in honor of Ceres,
an asteroid between Mars and Jupiter discovered in 1801. Not until 1875 was cerium actually
extracted from an ore.
Among the applications for cerium is an alloy called misch metal, prepared by fusing the
chlorides of cerium, lanthanum, neodymium, and praseodymium. The resulting alloy ignites
at or below room temperature, and is often used as the "flint" in a cigarette lighter, because it
sparks when friction from a metal wheel is applied.
Cerium is also used in jet engine parts, as a catalyst in making ammonia, and as an anti-knock
agent in gasolinethat is, a chemical that reduces the "knocking" sounds sometimes
produced in an engine by inferior grades of fuel. In cerium (IV) oxide, or CeO 2 , it is used to
extract the color from formerly colored glass, and is also applied in enamel and ceramic
coatings.
GADOLINIUM.
In 1794, seven years after the discovery of ytterite, Finnish chemist Johan Gadolin (1760-
1852) concluded that ytterite contained a new element, which was later named gadolinite in
his honor. A very similar name would be applied to an element extracted from ytterite, and
the years between Gadolin's discovery and the identification of this element spanned the
period of the most fruitful activity in lanthanide identification.
During the next century, all the other lanthanides were discovered within the composition of
gadolinite; then, in 1880, Swiss chemist Jean-Charles Galissard de Marignac (1817-1894)
found yet another element hiding in it. French chemist Paul Emile Lecoq de
Boisbaudran (1838-1912) rediscovered the same element six years later, and proposed that it
be called gadolinium.
Silvery in color, but with a sometimes yellowish cast, gadolinium has a high tendency to
oxidize in dry air. Because it is highly efficient for capturing neutrons, it could be useful in
nuclear power reactors. However, two of its seven isotopes are in such low abundance that it
has had little nuclear application. Used in phosphors for color television sets, among other
things, gadolinium shows some promise for ultra hightech applications: at very low
temperatures it becomes highly magnetic, and may function as a superconductor.

Mosander's Lanthanides
LANTHANUM.
Between 1839 and 1848, Mosander was consumed with extracting various lanthanides from
ytterite, which by then had come to be known as gadolinite. When he first succeeded in
extracting an element, he named it lanthana, meaning "hidden." The material, eventually
referred to as lanthanum, was not prepared in pure form until 1923.
Like a number of other lanthanides, lanthanum is very softso soft it can be cut with a
knifeand silvery-white in color. Among the most reactive of the lanthanides, it decomposes
rapidly in hot water, but more slowly in cold water. Lanthanum also reacts readily with
oxygen, and corrodes quickly in moist air.
As with cerium, lanthanum is used in misch metal. Because lanthanum compounds bring
about special optical qualities in glass, it also used for the manufacture of specialized lenses.
In addition, compounds of lanthanum with fluorine or oxygen are used in making carbon-arc
lamps for the motion picture industry.
SAMARIUM.
While analyzing an oxide formed from lanthanide in 1841, Mosander decided that he had a
new element on his hands, which he called didymium. Four decades later, Boisbaudran took
another look at didynium, and concluded that it was not an element; rather, it contained an
element, which he named samarium after the mineral samarskite, in which it is found. Still
later, Marignac was studying samarskite when he discovered what came to be known as
gadolinium. But the story did not end there: even later, in 1901, French chemist Eugne-
Anatole Demaray (1852-1903) found yet another element, europium, in samarskite.
Samarium is applied today in nuclear power plant control rods, in carbon-arc lamps, and in
optical masers and lasers. In alloys with cobalt, it is used in manufacturing the most
permanent electromagnets available. Samarium is also utilized in the manufacture of optical
glass, and as a catalyst in the production of ethyl alcohol.
ERBIUM AND TERBIUM.
To return to Mosander, he was examining ytterite in 1843 when he identified three different
"earths," all of which he also named after Ytterby: yttria, erbia, and terbia. Erbium was the
first to be extracted. A pure sample of its oxide was prepared in 1905 by French chemist
Georges Urbain (1872-1938) and American chemist Charles James (1880-1928), but the pure
metal itself was only extracted in 1934.
Soft and malleable, with a lustrous silvery color, erbium produces salts (which are usually
combinations of a metal with a nonmetal) that are pink and rose, making it useful as a tinting
agent. One of its oxides is utilized, for instance, to tint glass and porcelain with a pinkish cast.
It is also applied, to a limited extent, in the nuclear power industry.
Mosander also identified another element, terbium, in ytterite in 1839, and Marignac isolated
it in a purer form nearly half a century later, in 1886. To repeat a common theme, it is silvery-
gray and soft enough to be cut with a knife. When hit by an electron beam, a compound
containing terbium emits a greenish color, and thus it is used as a phosphor in color television
sets.

Later Isolationof Lanthanides


YTTERBIUM, HOLMIUM, AND THULIUM.
For many years after Mosander, there was little progress in the discovery of lanthanides, and
when it came, it was in the form of a third element, named after the town where so many of
the lanthanides were discovered. In 1878, while analyzing what Mosander had called erbia,
Marignac realized that it contained one or possibly two elements.
A year later, Swedish chemist Lars Frederik Nilson (1840-1899) concluded that it did indeed
contain two elements, which were named ytterbium and scandium. (Scandium, with an
atomic number of 21, is not part of the lanthanide series.) Urbain is sometimes credited for
discovering ytterbium: in 1907, he showed that the materials Nilson had studied were actually
a mixture of two oxides. In any case, Urbain said that the credit should be given to Marignac,
who is the most important figure in the history of lanthanides other than Mosander. As for
ytterbium, it is highly malleable, like other lanthanides, but does not have any significant
applications in industry.
Swedish chemist Per Teodor Cleve (1840-1905) found in 1879 that erbia contained two more
elements, which he named holmium and thulium. Thulium refers to the ancient name for
Scandinavia, Thule. Rarest of all the lanthanides, thulium is highly malleableand also
highly expensive. Hence it has few commercial applications.
DYSPROSIUM.
Named for the Greek word dysprositos , or "hard to get at," dysprosium was discovered by
Boisbaudran. Separating ytterite in 1886, he found gallium (atomic number 31not a
lanthanide); samarium (discussed above); and dysprosium. Yet again, a mineral extracted
from ytterite had been named after a previously discovered element, and, yet again, it turned
out to contain several elements. The substance in question this time was holmium, which, as
Boisbaudran discovered, was actually a complex mixture of terbium, erbium, holmium, and
the element he had identified as dysprosium. A pure sample was not obtained until 1950.
Because dysprosium has a high affinity for neutrons, it is sometimes used in control rods for
nuclear reactors, "soaking up" neutrons rather as a sponge soaks up water. Soft, with a
lustrous silver color like other lanthanides, dysprosium is also applied in lasers, but otherwise
it has few uses.
EUROPIUM AND LUTETIUM.
Whereas many other lanthanides are named for regions in northern Europe, the name for
europium refers to the European continent as a whole, and that of lutetium is a reference to
the old Roman name for Paris. As mentioned earlier, Demaray found europium in
samarskite, a discovery he made in 1901. Actually, Boisbaudran had noticed what appeared
to be a new element about a decade previously, but he did not pursue it, and thus the credit
goes to his countryman.
Most reactive of the lanthanides, europium responds both to cold water and to air. In addition,
it is capable of catching fire spontaneously. Among the most efficient elements for the
capture of neutrons, it is applied in the control systems of nuclear reactors. In addition, its
compounds are utilized in the manufacture of phosphors for TV sets: one such compound, for
instance, emits a reddish glow. Yet another europium compound is added to the glue on
postage stamps, making possible the electronic scanning of stamps.
Urbain, who discovered lutetium, named it after his hometown. James also identified a form
of the lanthanide, but did not announce his discovery until much later. Except for some uses
at a catalyst in the production of petroleum, lutetium has few industrial applications.

WHERE TO LEARN MORE


Cotton, Simon. Lanthanides and Actinides. New York: Oxford University Press, 1991.
Heiserman, David L. Exploring Chemical Elements and Their Compounds. Blue Ridge
Summit, PA: Tab Books, 1992.
"Luminescent Lanthanides" (Web site). <http://orgwww.chem.uva.nl/lanthanides/> (May 16,
2001).
Snedden, Robert. Materials. Des Plaines, IL: Heinemann Library, 1999.
Oxlade, Chris. Metal. Chicago: Heinemann Library, 2001.
Stwertka, Albert. A Guide to the Elements. New York: Oxford University Press, 1996.
Whyman, Kathryn. Metals and Alloys. Illustrated by Louise Nevett and Simon Bishop. New
York: Gloucester Press, 1988.

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