Lanthanides - How it works





D EFINING THE L ANTHANIDES

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. (Massimo Listri/Corbis. Reproduced by permission.)
M ISCH METAL , WHICH INCLUDES CERIUM , IS OFTEN USED IN CIGARETTE LIGHTERS .
(Massimo Listri/Corbis
. Reproduced by permission.)
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.

A RE T HEY R EALLY "R ARE "?

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.