Lanthanides

Concept

Along the bottom of the periodic table of elements, separated from the main body of the chart, are two rows, the first of which represents the lanthanides. Composed of lanthanum and the 14 elements of the lanthanide series, the lanthanides were once called the “rare earth” metals. In fact, they are not particularly rare: many of them appear in as much abundance as more familiar elements such as mercury. They are, however, difficult to extract, a characteristic that defines them as much as their silvery color; sometimes high levels of reactivity; and sensitivity to contamination. Though some lanthanides have limited uses, members of this group are found in everything from cigarette lighters to TV screens, and from colored glass to control rods in nuclear reactors.

How it works

Defining the Lanthanides

The lanthanide series consists of the 14 elements, with atomic numbers 58 through 71, that follow lanthanum on the periodic table of elements. These 14, along with the actinides—atomic numbers 90 through 103—are set aside from the periodic table due to similarities in properties that define each group.
Specifically, the lanthanides and actinides are the only elements that fill the f-orbitals. The lanthanides and actinides are actually “branches” of the larger family known as transition metals. The latter appear in groups 3 through 12 on the IUPAC version of the periodic table, though they are not numbered on the North American version.
The lanthanide series is usually combined with lanthanum, which has an atomic number of 57, under the general heading of lanthanides. As their name indicates, members of the lanthanide series share certain characteristics with lanthanum; hence the collective term “lanthanides.” These 15 elements, along with their chemical symbols, are:
• Lanthanum (La)
• Cerium (Ce)
• Praseodymium (Pr)
• Neodymium (Nd)
• Promethium (Pm)
• Samarium (Sm)
• Europium (Eu)
• Gadolinium (Gd)
• Terbium (Tb)
• Dysprosium (Dy)
• Holmium (Ho)
• Erbium (Er)
• Thulium (Tm)
• Ytterbium (Yb)
• Lutetium (Lu)
Most of these are discussed individually in this essay.


Properties of lanthanides

Bright and silvery in appearance, many of the lanthanides—though they are metals—are so soft they can be cut with a knife. Lanthanum, cerium, praseodymium, neodymium, and europium are highly reactive. When exposed to oxygen, they form an oxide coating. (An oxide is a compound formed by metal with an oxygen.) To prevent this result, which tarnishes the
Misch metal, which includes cerium, is often used in cigarette lighters.
Misch metal, which includes cerium, is often used in cigarette lighters.
metal, these five lanthanides are kept stored in mineral oil.
The reactive tendencies of the other lanthanides vary: for instance, gadolinium and lutetium do not oxidize until they have been exposed to air for a very long time. Nonetheless, lanthanides tend to be rather “temperamental” as a class. If contaminated with other metals, such as calcium, they corrode easily, and if contaminated with nonmetals, such as nitrogen or oxygen, they become brittle. Contamination also alters their boiling points, which range from 1,506.2°F (819°C) for ytterbium to 3,025.4°F (1,663°C) for lutetium.
Lanthanides react rapidly with hot water, or more slowly with cold water, to form hydrogen gas. As noted earlier, they also are quite reactive with oxygen, and they experience combustion readily in air. When a lanthanide reacts with another element to form a compound, it usually loses three of its outer electrons to form what are called tripositive ions, or atoms with an electric charge of +3. This is the most stable ion for lanthanides, which sometimes develop less stable +2 or +4 ions. Lanthanides tend to form ionic compounds, or compounds containing either positive or negative ions, with other substances—in particular, fluorine.

Are They Really “Rare”?

Though they were once known as the rare earth metals, lanthanides were so termed because, as we shall see, they are difficult to extract from compounds containing other substances— including other lanthanides. As for rarity, the scarcest of the lanthanides, thulium, is more abundant than either arsenic or mercury, and certainly no one thinks of those as rare substances. In terms of parts per million (ppm), thulium has a presence in Earth’s crust equivalent to 0.2 ppm. The most plentiful of the lanthanides, cerium, has an abundance of 46 ppm, greater than that of tin.
If, on the other hand, rarity is understood not in terms of scarcity, but with regard to difficulty in obtaining an element in its pure form, then indeed the lanthanides are rare. Because their properties are so similar, and because they are inclined to congregate in the same substances, the original isolation and identification of the lanthanides was an arduous task that took well over a century. The progress followed a common pattern.
First, a chemist identified a new lanthanide; then a few years later, another scientist came along and extracted another lanthanide from the sample that the first chemist had believed to be a single element. In this way, the lanthanides emerged over time, each from the one before it, rather like Russian matryoshka or “nesting” dolls.

Extracting lanthanides

Though most of the lanthanides were first isolated in Scandinavia, today they are found in considerably warmer latitudes: Brazil, India, Australia, South Africa, and the United States. The principal source of lanthanides is monazite, a heavy, dark sand from which about 50% of the lanthanide mass available to science and industry has been extracted.
In order to separate lanthanides from other elements, they are actually combined with other substances—substances having a low solubility, or tendency to dissolve. Oxalates and fluorides are low-solubility substances favored for this purpose. Once they are separated from non-lanthanide elements, ion exchange is used to separate one lanthanide element from another.
There is a pronounced decrease in the radii of lanthanide atoms as they increase in atomic number: in other words, the higher the atomic number, the smaller the radius. This decrease, known as the lanthanide contraction, aids in the process of separation by ion exchange. The lanthanides are mixed in an ionic solution, then passed down a long column containing a resin. Various lanthanide ions bond more or less tightly, depending on their relative size, with the resin.
After this step, the lanthanides are washed out of the ion exchange column and into various solutions. One by one, they become fully separated, and are then mixed with acid and heated to form an oxide. The oxide is then converted to a fluoride or chloride, which can then be reduced to metallic form with the aid of calcium.

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.
Samarium is used in nuclear power plant control rods, such as the one shown here.
Samarium is used in nuclear power plant control rods, such as the one shown here.
The terms “lanthanide series” or even “lanthanides” did not emerge for some time—in 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 Cronstedt (1722-1765) described what he thought was a new form of tungsten, which he had found at the Bastnas Mine near Riddarhyt-tan, Sweden. Later, German chemist Martin Heinrich Klaproth (1743-1817) and Swedish chemist Wilhelm Hisinger (1766-1852) independently analyzed the material Cronstedt 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 antiknock agent in gasoline—that is, a chemical that reduces the “knocking” sounds sometimes produced in an engine by inferior grades of fuel. In cerium (IV) oxide, or CeO2, 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 lan-thanides 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 (18381912) 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 soft—so soft it can be cut with a knife—and 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 Eugene-Anatole Demarcay (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 (18801928), 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 Isolation of 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 lan-thanides other than Mosander. As for ytterbium, it is highly malleable, like other lanthanides, but does not have any significant applications in industry.

Key Terms

Alloy: A mixture of two or more metals.
Atomic number: The number of protons in the nucleus of an atom. Since this number is different for each element, elements are listed on the periodic table of elements in order of atomic number.
Ion: An atom or atoms that has lost or gained one or more electrons, and thus has a net electrical charge.
Lanthanide contraction: A progressive decrease in the radius of lanthanide atoms as they increase in atomic number.
Lanthanide series: A group of 14 elements, with atomic numbers 58 through 71, that follow lanthanum on the periodic table of elements.
Lanthanides: The lanthanide series, along with lanthanum.
Oxide: A compound formed by the chemical bonding of a metal with oxygen.
Periodic table of elements: A chart showing the elements arranged in order of atomic number, grouping them according to common characteristics.
Rare earth metals: An old name for the lanthanides, reflecting the difficulty of separating them from compounds containing other lanthanides or other substances.
Transition metals: Groups 3 through 12 on the IUPAC or European version of the periodic table of elements. The lanthanides and actinides, which appear at the bottom of the periodic table, are “branches” of this family.
Swedish chemist Per Teodor Cleve (18401905) 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 lan-thanides, thulium is highly malleable—and 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 31—not 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,Demarcay 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.

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