Solution

Discovery and early history

Rare earth elements became known to the world with the discovery of the black mineral "ytterbite" (renamed to gadolinite in 1800) by Lieutenant Carl Axel Arrhenius in 1787, at a quarry in the village of Ytterby, Sweden.[5]

Arrhenius' "ytterbite" reached Johan Gadolin, a Royal Academy of Turku professor, and his analysis yielded an unknown oxide (earth) which he called Ytteria. Anders Gustav Ekeberg isolated beryllium from the gadolinite but failed to recognize other elements which the ore contained. After this discovery in 1794 a mineral from Bastn?s near Riddarhyttan, Sweden, which was believed to be an iron-tungsten mineral, was re-examined by J?ns Jacob Berzelius and Wilhelm Hisinger. In 1803 they obtained a white oxide and called it ceria. Martin Heinrich Klaproth independently discovered the same oxide and called it ochroia.

Thus by 1803 there were two known rare earth elements, yttrium and cerium, although it took another 30 years for researchers to determine that other elements were contained in the two ores ceria and ytteria (the similarity of the rare earth metals' chemical properties made their separation difficult).

In 1839 Carl Gustav Mosander, an assistant of Berzelius, separated ceria by heating the nitrate and dissolving the product in nitric acid. He called the oxide of the soluble salt lanthana. It took him three more years to separate the lanthana further into didymia and pure lanthana. Didymia, although not further separable by Mosander's techniques was a mixture of oxides.

In 1842 Mosander also separated the ytteria into three oxides: pure ytteria, terbia and erbia (all the names are derived from the town name "Ytterby"). The earth giving pink salts he called terbium; the one which yielded yellow peroxide he called erbium.

So in 1842 the number of rare earth elements had reached six: yttrium, cerium, lanthanum, didymium, erbium and terbium.

Nils Johan Berlin and Marc Delafontaine tried also to separate the crude ytteria and found the same substances that Mosander obtained, but Berlin named (1860) the substance giving pink salts erbium and Delafontaine named the substance with the yellow peroxide terbium. This confusion led to several false claims of new elements, such as the mosandrium of J. Lawrence Smith, or the philippium and decipium of Delafontaine.

Spectroscopy
There were no further discoveries for 30 years, and the element didymium was listed in the periodic table of elements with a molecular mass of 138. In 1879 Delafontaine used the new physical process of optical-flame spectroscopy, and he found several new spectral lines in didymia. Also in 1879, the new element samarium was isolated by Paul émile Lecoq de Boisbaudran from the mineral samarskite.

The samaria earth was further separated by Lecoq de Boisbaudran in 1886 and a similar result was obtained by Jean Charles Galissard de Marignac by direct isolation from samarskite. They named the element gadolinium after Johan Gadolin, and its oxide was named "gadolinia".

Further spectroscopic analysis between 1886 and 1901 of samaria, ytteria, and samarskite by William Crookes, Lecoq de Boisbaudran and Eugène-Anatole Demar?ay yielded several new spectroscopic lines that indicated the existence of an unknown element. The fractional crystallization of the oxides then yielded europium in 1901.

In 1839 the third source for rare earths became available. This is a mineral similar to gadolinite, uranotantalum (now called "samarskite"). This mineral from Miass in the southern Ural Mountains was documented by Gustave Rose. The Russian chemist R. Harmann proposed that a new element he called "ilmenium" should be present in this mineral, but later, Christian Wilhelm Blomstrand, Galissard de Marignac, and Heinrich Rose found only tantalum and niobium (columbium) in it.

The exact number of rare earth elements that existed was highly unclear, and a maximum number of 25 was estimated. The use of X-ray spectra (obtained by X-ray crystallography) by Henry Gwyn Jeffreys Moseley made it possible to assign atomic numbers to the elements. Moseley found that the exact number of lanthanides had to be 15 and that element 61 had yet to be discovered.

Using these facts about atomic numbers from X-ray crystallography, Moseley also showed that hafnium (element 72) would not be a rare earth element. Moseley was killed in World War I in 1915, years before hafnium was discovered. Hence, the claim of Georges Urbain that he had discovered element 72 was untrue. Hafnium is an element that lies in the periodic table immediately below zirconium, and hafnium and zirconium are very similar in their chemical and physical properties.

During the 1940s, Frank Spedding and others in the United States (during the Manhattan Project) developed the chemical ion exchange procedures for separating and purifying the rare earth elements. This method was first applied to the actinides for separating plutonium-239 and neptunium, from uranium, thorium, actinium, and the other actinide rare earths in the materials produced in nuclear reactors. The plutonium-239 was very desirable because it is a fissile material.

The principal sources of rare earth elements are the minerals bastn?site, monazite, and loparite and the lateritic ion-adsorption clays. Despite their high relative abundance, rare earth minerals are more difficult to mine and extract than equivalent sources of transition metals (due in part to their similar chemical properties), making the rare earth elements relatively expensive. Their industrial use was very limited until efficient separation techniques were developed, such as ion exchange, fractional crystallization and liquid-liquid extraction during the late 1950s and early 1960s.

Rare earth elements are heavier than iron and thus are produced by supernova nucleosynthesis or the s-process in asymptotic giant branch stars. In nature, spontaneous fission of uranium-238 produces trace amounts of radioactive promethium, but most promethium is synthetically produced in nuclear reactors.

Global rare earth production
Global production 1950–2000
Until 1948, most of the world's rare earths were sourced from placer sand deposits in India and Brazil. Through the 1950s, South Africa took the status as the world's rare earth source, after large veins of rare earth bearing monazite were discovered there. Through the 1960s until the 1980s, the Mountain Pass rare earth mine in California was the leading producer. Today, the Indian and South African deposits still produce some rare earth concentrates, but they are dwarfed by the scale of Chinese production. China now produces over 97% of the world's rare earth supply, mostly in Inner Mongolia,[10][11] even though it has only 37% of proven reserves.[12] All of the world's heavy rare earths (such as dysprosium) come from Chinese rare earth sources such as the polymetallic Bayan Obo deposit. In 2010, the USGS released a study which found that the United States had 13 million metric tons of rare earth elements.

New demand has recently strained supply, and there is growing concern that the world may soon face a shortage of the rare earths. In several years from 2009 worldwide demand for rare earth elements is expected to exceed supply by 40,000 tonnes annually unless major new sources are developed.