Lanthanum Traditional Cache

Lanthanum is a chemical element with the symbol La and atomic number 57. Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and other rare earth elements. Lanthanum is a malleable, ductile, and soft metal that oxidizes rapidly when exposed to air. It is produced from the minerals monazite and bastnäsite using a complex multistage extraction process. Lanthanum compounds have numerous applications as catalysts, additives in glass, carbon lighting for studio lighting and projection, ignition elements in lighters and torches, electron cathodes, scintillators, and others. Lanthanum carbonate (La₂(CO₃)₃) was approved as a medication against renal failure.

Lanthanum is a soft, malleable, silvery white metal which has hexagonal crystal structure at room temperature. At 310 °C, lanthanum changes to a face-centered cubic structure, and at 865 °C into a body-centered cubic structure. Lanthanum easily oxidizes (a centimeter-sized sample will completely oxidize within a year) and is therefore used as in elemental form only for research purposes. For example, single La atoms have been isolated by implanting them into fullerene molecules. If carbon nanotubes are filled with those lanthanum-encapsulated fullerenes and annealed, metallic nanochains of lanthanum are produced inside carbon nanotubes.

The word lanthanum comes from the Greek lanthano = to lie hidden. Lanthanum was discovered in 1839 by Swedish chemist Carl Gustav Mosander, when he partially decomposed a sample of cerium nitrate by heating and treating the resulting salt with dilute nitric acid. From the resulting solution, he isolated a new rare earth he called lantana. Lanthanum was isolated in relatively pure form in 1923. Lanthanum is the most strongly basic of all the trivalent lanthanides, and this property is what allowed Mosander to isolate and purify the salts of this element. Basicity separation as operated commercially involved the fractional precipitation of the weaker bases (such as didymium) from nitrate solution by the addition of magnesium oxide or dilute ammonia gas. Purified lanthanum remained in solution. (The basicity methods were only suitable for lanthanum purification; didymium could not be efficiently further separated in this manner.) The alternative technique of fractional crystallization was invented by Dmitri Mendeleev, in the form of the double ammonium nitrate tetrahydrate, which he used to separate the less-soluble lanthanum from the more-soluble didymium in the 1870s. This system was used commercially in lanthanum purification until the development of practical solvent extraction methods that started in the late 1950s. (A detailed process using the double ammonium nitrates to provide 99.99% pure lanthanum, neodymium concentrates and praseodymium concentrates is presented in Callow 1967, at a time when the process was just becoming obsolete.) As operated for lanthanum purification, the double ammonium nitrates were recrystallized from water. When later adapted by Carl Auer von Welsbach for the splitting of didymium, nitric acid was used as a solvent to lower the solubility of the system. Lanthanum is relatively easy to purify, since it has only one adjacent lanthanide, cerium, which itself is very readily removed due to its potential tetravalency. The fractional crystallization purification of lanthanum as the double ammonium nitrate was sufficiently rapid and efficient, that lanthanum purified in this manner was not expensive. The Lindsay Chemical Division of American Potash and Chemical Corporation, for a while the largest producer of rare earths in the world, in a price list dated October 1, 1958 priced 99.9% lanthanum ammonium nitrate (oxide content of 29%) at $3.15 per pound, or $1.93 per pound in 50-pound quantities. The corresponding oxide (slightly purer at 99.99%) was priced at $11.70 or $7.15 per pound for the two quantity ranges. The price for their purest grade of oxide (99.997%) was $21.60 and $13.20, respectively.

Although lanthanum belongs to the element group called rare earth metals, it is not rare at all. Lanthanum is available in relatively large quantities (32 ppm in Earth’s crust). "Rare earths" got their name because they were indeed rare as compared to the "common" earths such as lime or magnesia, and historically only a few deposits were known. Monazite (Ce, La, Th, Nd, Y)PO₄, and bastnäsite (Ce, La, Y)CO₃F, are the principal ores in which lanthanum occurs, in percentages of up to 25 to 38 percent of the total lanthanide content. In general, there is more lanthanum in bastnäsite than in monazite. Until 1949, bastnäsite was a rare and obscure mineral, not even remotely contemplated as a potential commercial source for lanthanides. In that year, the large deposit at the Mountain Pass rare earth mine in California was discovered. This discovery alerted geologists to the existence of a new class of rare earth deposit, the rare-earth bearing carbonatite, other examples of which soon surfaced, particularly in Africa and China.