Cerium

Cerium is a chemical element; it has symbol Ce and atomic number 58. It is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the oxidation state of +3 characteristic of the series, it also has a stable +4 state that does not oxidize water. It is considered one of the rare-earth elements. Cerium has no known biological role in humans but is not particularly toxic, except with intense or continued exposure.

Despite always occurring in combination with the other rare-earth elements in minerals such as those of the monazite and bastnäsite groups, cerium is easy to extract from its ores, as it can be distinguished among the lanthanides by its unique ability to be oxidized to the +4 state in aqueous solution. It is the most common of the lanthanides, followed by neodymium, lanthanum, and praseodymium. Its estimated abundance in the Earth's crust is 68 ppm.

Cerium was the first of the lanthanides to be discovered, in Bastnäs, Sweden. It was discovered by Jöns Jakob Berzelius and Wilhelm Hisinger in 1803, and independently by Martin Heinrich Klaproth in Germany in the same year. In 1839 Carl Gustaf Mosander separated cerium(III) oxide from other rare earths, and in 1875 William Francis Hillebrand became the first to isolate the metal. Today, cerium and its compounds have a variety of uses: for example, cerium(IV) oxide is used to polish glass and is an important part of catalytic converters. Cerium metal is used in ferrocerium lighters for its pyrophoric properties. Cerium-doped YAG phosphor is used in conjunction with blue light-emitting diodes to produce white light in most commercial white LED light sources.

Cerium is the second element of the lanthanide series. In the periodic table, it appears between the lanthanides lanthanum to its left and praseodymium to its right, and above the actinide thorium. It is a ductile metal with a hardness similar to that of silver. Its 58 electrons are arranged in the configuration [Xe]4f¹5d¹6s², of which the four outer electrons are valence electrons. The 4f, 5d, and 6s energy levels are very close to each other, and the transfer of one electron to the 5d shell is due to strong interelectronic repulsion in the compact 4f shell. This effect is overwhelmed when the atom is positively ionised; thus Ce²⁺ on its own has instead the regular configuration [Xe]4f², although in some solid solutions it may be [Xe]4f¹5d¹. Most lanthanides can use only three electrons as valence electrons, as afterwards the remaining 4f electrons are too strongly bound: cerium is an exception because of the stability of the empty f-shell in Ce⁴⁺ and the fact that it comes very early in the lanthanide series, where the nuclear charge is still low enough until neodymium to allow the removal of the fourth valence electron by chemical means.

Cerium has a variable electronic structure. The energy of the 4f electron is nearly the same as that of the outer 5d and 6s electrons that are delocalized in the metallic state, and only a small amount of energy is required to change the relative occupancy of these electronic levels. This gives rise to dual valence states. For example, a volume change of about 10% occurs when cerium is subjected to high pressures or low temperatures. In its high pressure phase (α-Cerium), the 4f electrons are also delocalized and itinerate, as opposed to localized 4f electrons in low pressure phase (γ-Cerium). It appears that the valence changes from about 3 to 4 when it is cooled or compressed.

Like the other lanthanides, cerium metal is a good reducing agent, having standard reduction potential of E^⦵ = −2.34 V for the Ce³⁺/Ce couple. It tarnishes in air, forming a passivating oxide layer like iron rust. A centimeter-sized sample of cerium metal corrodes completely in about a year. More dramatically, metallic cerium can be highly pyrophoric:

Being highly electropositive, cerium reacts with water. The reaction is slow with cold water but speeds up with increasing temperature, producing cerium(III) hydroxide and hydrogen gas:

Four allotropic forms of cerium are known to exist at standard pressure and are given the common labels of α to δ: