Cerium

Cerium is a chemical element; it has symbol Ce and atomic number 58, and 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.…

Cerium is a chemical element; it has symbol Ce and atomic number 58, and 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.

Chemical properties of the element

Like the other lanthanides, cerium metal is a good reducing agent, having standard reduction potential of E  = −2.34 V for the 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:

Halides

Cerium forms all four trihalides (X = F, Cl, Br, I) usually by reaction of the oxides with the hydrogen halides. The anhydrous halides are pale-colored, paramagnetic, hygroscopic solids. Upon hydration, the trihalides convert to complexes containing aquo complexes . Unlike most lanthanides, Ce forms a tetrafluoride, a white solid. It also forms a bronze-colored diiodide, which has metallic properties. Aside from the binary halide phases, a number of anionic halide complexes are known. The fluoride gives the Ce(IV) derivatives and . The chloride gives the orange .

Oxides and chalcogenides

Cerium(IV) oxide ("ceria") has the fluorite structure, similarly to the dioxides of praseodymium and terbium. Ceria is a nonstoichiometric compound, meaning that the real formula is , where x is about 0.2. Thus, the material is not perfectly described as Ce(IV). Ceria reduces to cerium(III) oxide with hydrogen gas. Many nonstoichiometric chalcogenides are also known, along with the trivalent (Z = S, Se, Te). The monochalcogenides CeZ conduct electricity and would better be formulated as . While are known, they are polychalcogenides with cerium(III): cerium(IV) derivatives of S, Se, and Te are unknown.

Cerium(IV) complexes

The compound ceric ammonium nitrate (CAN) is the most common cerium compound encountered in the laboratory. The six nitrate ligands bind as bidentate ligands. The complex is 12-coordinate, a high coordination number which emphasizes the large size of the ion. CAN is a popular oxidant in organic synthesis, both as a stoichiometric reagent and as a catalyst. It is inexpensive, stable in air, easily handled, and of low toxicity. It operates by one-electron redox. Cerium nitrates also form 4:3 and 1:1 complexes with 18-crown-6 (the ratio referring to that between the nitrate and the crown ether). Classically, CAN is a primary standard for quantitative analysis. Cerium(IV) salts, especially cerium(IV) sulfate, are often used as standard reagents for volumetric analysis in cerimetric titrations. Due to ligand-to-metal charge transfer, aqueous cerium(IV) ions are orange-yellow. Aqueous cerium(IV) is metastable in water and is a strong oxidizing agent that oxidizes hydrochloric acid to give chlorine gas. In the Belousov–Zhabotinsky reaction, cerium oscillates between the +4 and +3 oxidation states to catalyze the reaction.

Organocerium compounds

Organocerium chemistry is similar to that of the other lanthanides, often involving complexes of cyclopentadienyl and cyclooctatetraenyl ligands. Cerocene adopts the uranocene molecular structure. The 4f electron in cerocene is poised ambiguously between being localized and delocalized and this compound is considered intermediate-valent. Alkyl, alkynyl, and alkenyl organocerium derivatives are prepared from the transmetallation of the respective organolithium or Grignard reagents, and are more nucleophilic but less basic than their precursors. and asteroid Ceres, after which cerium is named|alt=The dwarf planet Ceres.]] Cerium was discovered in Bastnäs in Sweden by Jöns Jakob Berzelius and Wilhelm Hisinger, and independently in Germany by Martin Heinrich Klaproth, both in 1803. Cerium was named by Berzelius after the asteroid Ceres, formally 1 Ceres, discovered two years earlier. Ceres was initially considered to be a planet at the time. The asteroid is itself named after the Roman goddess Ceres, goddess of agriculture, grain crops, fertility and motherly relationships. Cerium was originally isolated in the form of its oxide, which was named ceria, a term that is still used. The metal itself was too electropositive to be isolated by then-current smelting technology, a characteristic of rare-earth metals in general. After the development of electrochemistry by Humphry Davy five years later, the earths soon yielded the metals they contained. Ceria, as isolated in 1803, contained all of the lanthanides present in the cerite ore from Bastnäs, Sweden, and thus only contained about 45% of what is now known to be pure ceria. It was not until Carl Gustaf Mosander succeeded in removing lanthana and "didymia" in the late 1830s that ceria was obtained pure. Wilhelm Hisinger was a wealthy mine-owner and amateur scientist, and sponsor of Berzelius. He owned and controlled the mine at Bastnäs, and had been trying for years to find out the composition of the abundant heavy gangue rock (the "Tungsten of Bastnäs", which despite its name contained no tungsten), now known as cerite, that he had in his mine. Mosander and his family lived for many years in the same house as Berzelius, and Mosander was undoubtedly persuaded by Berzelius to investigate ceria further. The element played a role in the Manhattan Project, where cerium compounds were investigated in the Berkeley site as materials for crucibles for uranium and plutonium casting. For this reason, new methods for the preparation and casting of cerium were developed within the scope of the Ames daughter project (now the Ames Laboratory). Production of extremely pure cerium in Ames commenced in mid-1944 and continued until August 1945.

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