177-579: The rare-earth elements ( REE ), also called the rare-earth metals or rare earths , and sometimes the lanthanides or lanthanoids (although scandium and yttrium , which do not belong to this series, are usually included as rare earths), are a set of 17 nearly indistinguishable lustrous silvery-white soft heavy metals . Compounds containing rare earths have diverse applications in electrical and electronic components, lasers, glass, magnetic materials, and industrial processes. Scandium and yttrium are considered rare-earth elements because they tend to occur in
354-434: A body-centered cubic (bcc) crystal structure . As it cools further to 1394 °C, it changes to its γ-iron allotrope, a face-centered cubic (fcc) crystal structure, or austenite . At 912 °C and below, the crystal structure again becomes the bcc α-iron allotrope. The physical properties of iron at very high pressures and temperatures have also been studied extensively, because of their relevance to theories about
531-549: A fissile material . The principal sources of rare-earth elements are the minerals bastnäsite ( RCO 3 F , where R is a mixture of rare-earth elements), monazite ( XPO 4 , where X is a mixture of rare-earth elements and sometimes thorium), and loparite ( (Ce,Na,Ca)(Ti,Nb)O 3 ), 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
708-436: A negative ion . However, owing to widespread current use, lanthanide is still allowed. Primordial From decay Synthetic Border shows natural occurrence of the element The term "lanthanide" was introduced by Victor Goldschmidt in 1925. Despite their abundance, the technical term "lanthanides" is interpreted to reflect a sense of elusiveness on the part of these elements, as it comes from
885-430: A nuclear spin (− 1 ⁄ 2 ). The nuclide Fe theoretically can undergo double electron capture to Cr, but the process has never been observed and only a lower limit on the half-life of 4.4×10 years has been established. Fe is an extinct radionuclide of long half-life (2.6 million years). It is not found on Earth, but its ultimate decay product is its granddaughter, the stable nuclide Ni . Much of
1062-499: A supernova for their formation, involving rapid neutron capture by starting Fe nuclei. In the far future of the universe, assuming that proton decay does not occur, cold fusion occurring via quantum tunnelling would cause the light nuclei in ordinary matter to fuse into Fe nuclei. Fission and alpha-particle emission would then make heavy nuclei decay into iron, converting all stellar-mass objects to cold spheres of pure iron. Iron's abundance in rocky planets like Earth
1239-606: A CO 2 -rich primary magma, by fractional crystallization of an alkaline primary magma, or by separation of a CO 2 -rich immiscible liquid from. These liquids are most commonly forming in association with very deep Precambrian cratons , like the ones found in Africa and the Canadian Shield. Ferrocarbonatites are the most common type of carbonatite to be enriched in REE, and are often emplaced as late-stage, brecciated pipes at
1416-545: A NiAs type structure and can be formulated La (I )(e ) 2 . TmI is a true Tm(I) compound, however it is not isolated in a pure state. All of the lanthanides form sesquioxides, Ln 2 O 3 . The lighter/larger lanthanides adopt a hexagonal 7-coordinate structure while the heavier/smaller ones adopt a cubic 6-coordinate "C-M 2 O 3 " structure. All of the sesquioxides are basic, and absorb water and carbon dioxide from air to form carbonates, hydroxides and hydroxycarbonates. They dissolve in acids to form salts. Cerium forms
1593-491: A close packed structure like most of the lanthanides but has an unusual 9 layer repeat Gschneider and Daane (1988) attribute the trend in melting point which increases across the series, ( lanthanum (920 °C) – lutetium (1622 °C)) to the extent of hybridization of the 6s, 5d, and 4f orbitals. The hybridization is believed to be at its greatest for cerium, which has the lowest melting point of all, 795 °C. The lanthanide metals are soft; their hardness increases across
1770-528: A component of magnets in hybrid car motors." The global demand for rare-earth elements (REEs) is expected to increase more than fivefold by 2030. The REE geochemical classification is usually done on the basis of their atomic weight . One of the most common classifications divides REE into 3 groups: light rare earths (LREE - from 57 La to 60 Nd), intermediate (MREE - from 62 Sm to 67 Ho) and heavy (HREE - from 68 Er to 71 Lu). REE usually appear as trivalent ions, except for Ce and Eu which can take
1947-453: A deeper (4f) shell is progressively filled with electrons as the atomic number increases from 57 towards 71. For many years, mixtures of more than one rare earth were considered to be single elements, such as neodymium and praseodymium being thought to be the single element didymium. Very small differences in solubility are used in solvent and ion-exchange purification methods for these elements, which require repeated application to obtain
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#17328019642032124-454: A distorted sodium chloride structure. The binary ferrous and ferric halides are well-known. The ferrous halides typically arise from treating iron metal with the corresponding hydrohalic acid to give the corresponding hydrated salts. Iron reacts with fluorine, chlorine, and bromine to give the corresponding ferric halides, ferric chloride being the most common. Ferric iodide is an exception, being thermodynamically unstable due to
2301-541: A diverse range of coordination geometries , many of which are irregular, and also manifests itself in the highly fluxional nature of the complexes. As there is no energetic reason to be locked into a single geometry, rapid intramolecular and intermolecular ligand exchange will take place. This typically results in complexes that rapidly fluctuate between all possible configurations. Many of these features make lanthanide complexes effective catalysts . Hard Lewis acids are able to polarise bonds upon coordination and thus alter
2478-664: A few percent of yttrium). Uranium ores from Ontario have occasionally yielded yttrium as a byproduct. Well-known minerals containing cerium, and other LREE, include bastnäsite , monazite , allanite , loparite , ancylite , parisite , lanthanite , chevkinite, cerite , stillwellite , britholite, fluocerite , and cerianite. Monazite (marine sands from Brazil , India , or Australia ; rock from South Africa ), bastnäsite (from Mountain Pass rare earth mine , or several localities in China), and loparite ( Kola Peninsula , Russia ) have been
2655-614: A high probability of being found close to the nucleus and are thus strongly affected as the nuclear charge increases across the series ; this results in a corresponding decrease in ionic radii referred to as the lanthanide contraction . The low probability of the 4f electrons existing at the outer region of the atom or ion permits little effective overlap between the orbitals of a lanthanide ion and any binding ligand . Thus lanthanide complexes typically have little or no covalent character and are not influenced by orbital geometries. The lack of orbital interaction also means that varying
2832-553: A macroscopic piece of iron will have a nearly zero overall magnetic field. Application of an external magnetic field causes the domains that are magnetized in the same general direction to grow at the expense of adjacent ones that point in other directions, reinforcing the external field. This effect is exploited in devices that need to channel magnetic fields to fulfill design function, such as electrical transformers , magnetic recording heads, and electric motors . Impurities, lattice defects , or grain and particle boundaries can "pin"
3009-544: 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, but that element 61 had not yet been discovered. (This is promethium, a radioactive element whose most stable isotope has a half-life of just 18 years.) Using these facts about atomic numbers from X-ray crystallography, Moseley also showed that hafnium (element 72) would not be
3186-431: A melt phase if one is present. REE are chemically very similar and have always been difficult to separate, but the gradual decrease in ionic radius from light REE (LREE) to heavy REE (HREE), called the lanthanide contraction , can produce a broad separation between light and heavy REE. The larger ionic radii of LREE make them generally more incompatible than HREE in rock-forming minerals, and will partition more strongly into
3363-401: A melt phase, while HREE may prefer to remain in the crystalline residue, particularly if it contains HREE-compatible minerals like garnet . The result is that all magma formed from partial melting will always have greater concentrations of LREE than HREE, and individual minerals may be dominated by either HREE or LREE, depending on which range of ionic radii best fits the crystal lattice. Among
3540-507: A mine in the village of Ytterby in Sweden ; four of the rare-earth elements bear names derived from this single location. A table listing the 17 rare-earth elements, their atomic number and symbol, the etymology of their names, and their main uses (see also Applications of lanthanides ) is provided here. Some of the rare-earth elements are named after the scientists who discovered them, or elucidated their elemental properties, and some after
3717-475: A mixture of O 2 /Ar. Iron(IV) is a common intermediate in many biochemical oxidation reactions. Numerous organoiron compounds contain formal oxidation states of +1, 0, −1, or even −2. The oxidation states and other bonding properties are often assessed using the technique of Mössbauer spectroscopy . Many mixed valence compounds contain both iron(II) and iron(III) centers, such as magnetite and Prussian blue ( Fe 4 (Fe[CN] 6 ) 3 ). The latter
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#17328019642033894-471: A mixture of three to all 15 of the lanthanides (along with yttrium as a 16th) occur in minerals, such as monazite and samarskite (for which samarium is named). These minerals can also contain group 3 elements, and actinides such as uranium and thorium. A majority of the rare earths were discovered at the same mine in Ytterby , Sweden and four of them are named (yttrium, ytterbium, erbium, terbium) after
4071-477: A purified metal. The diverse applications of refined metals and their compounds can be attributed to the subtle and pronounced variations in their electronic, electrical, optical, and magnetic properties. By way of example of the term meaning "hidden" rather than "scarce", cerium is almost as abundant as copper; on the other hand promethium , with no stable or long-lived isotopes, is truly rare. * Between initial Xe and final 6s electronic shells ** Sm has
4248-411: A quarry in the village of Ytterby , Sweden and termed "rare" because it had never yet been seen. Arrhenius's "ytterbite" reached Johan Gadolin , a Royal Academy of Turku professor, and his analysis yielded an unknown oxide ("earth" in the geological parlance of the day), which he called yttria . Anders Gustav Ekeberg isolated beryllium from the gadolinite but failed to recognize other elements in
4425-456: 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 have very similar chemical and physical properties. During the 1940s, Frank Spedding and others in
4602-518: A relatively stable +2 oxidation state for Eu and Yb is usually explained by the stability (exchange energy) of half filled (f ) and fully filled f . GdI 2 possesses the layered MoS 2 structure, is ferromagnetic and exhibits colossal magnetoresistance . The sesquihalides Ln 2 X 3 and the Ln 7 I 12 compounds listed in the table contain metal clusters , discrete Ln 6 I 12 clusters in Ln 7 I 12 and condensed clusters forming chains in
4779-471: A result, mercury is traded in standardized 76 pound flasks (34 kg) made of iron. Iron is by far the most reactive element in its group; it is pyrophoric when finely divided and dissolves easily in dilute acids, giving Fe . However, it does not react with concentrated nitric acid and other oxidizing acids due to the formation of an impervious oxide layer, which can nevertheless react with hydrochloric acid . High-purity iron, called electrolytic iron ,
4956-400: A rock salt structure. EuO is ferromagnetic at low temperatures, and is a semiconductor with possible applications in spintronics . A mixed Eu /Eu oxide Eu 3 O 4 can be produced by reducing Eu 2 O 3 in a stream of hydrogen. Neodymium and samarium also form monoxides, but these are shiny conducting solids, although the existence of samarium monoxide is considered dubious. All of
5133-403: A separate group of rare-earth elements (the terbium group), or europium was included in the cerium group, and gadolinium and terbium were included in the yttrium group. In the latter case, the f-block elements are split into half: the first half (La–Eu) form the cerium group, and the second half (Gd–Yb) together with group 3 (Sc, Y, Lu) form the yttrium group. The reason for this division arose from
5310-419: A similar effect. In sedimentary rocks, rare-earth elements in clastic sediments are a representation of provenance. The rare-earth element concentrations are not typically affected by sea and river waters, as rare-earth elements are insoluble and thus have very low concentrations in these fluids. As a result, when sediment is transported, rare-earth element concentrations are unaffected by the fluid and instead
5487-591: A stoichiometric dioxide, CeO 2 , where cerium has an oxidation state of +4. CeO 2 is basic and dissolves with difficulty in acid to form Ce solutions, from which Ce salts can be isolated, for example the hydrated nitrate Ce(NO 3 ) 4 .5H 2 O. CeO 2 is used as an oxidation catalyst in catalytic converters. Praseodymium and terbium form non-stoichiometric oxides containing Ln , although more extreme reaction conditions can produce stoichiometric (or near stoichiometric) PrO 2 and TbO 2 . Europium and ytterbium form salt-like monoxides, EuO and YbO, which have
Rare-earth element - Misplaced Pages Continue
5664-421: A temperature of 400 °C (752 °F). These elements and their compounds have no biological function other than in several specialized enzymes, such as in lanthanide-dependent methanol dehydrogenases in bacteria. The water-soluble compounds are mildly to moderately toxic, but the insoluble ones are not. All isotopes of promethium are radioactive, and it does not occur naturally in the earth's crust, except for
5841-515: A trace amount generated by spontaneous fission of uranium-238 . They are often found in minerals with thorium , and less commonly uranium . Though rare-earth elements are technically relatively plentiful in the entire Earth's crust ( cerium being the 25th-most-abundant element at 68 parts per million, more abundant than copper ), in practice this is spread thin across trace impurities, so to obtain rare earths at usable purity requires processing enormous amounts of raw ore at great expense, thus
6018-455: A type of rock consisting of repeated thin layers of iron oxides alternating with bands of iron-poor shale and chert . The banded iron formations were laid down in the time between 3,700 million years ago and 1,800 million years ago . Materials containing finely ground iron(III) oxides or oxide-hydroxides, such as ochre , have been used as yellow, red, and brown pigments since pre-historical times. They contribute as well to
6195-462: A valence of 3 and form sesquioxides (cerium forms CeO 2 ). Five different crystal structures are known, depending on the element and the temperature. The X-phase and the H-phase are only stable above 2000 K. At lower temperatures, there are the hexagonal A-phase, the monoclinic B-phase, and the cubic C-phase, which is the stable form at room temperature for most of the elements. The C-phase
6372-435: A very large coordination and organometallic chemistry : indeed, it was the discovery of an iron compound, ferrocene , that revolutionalized the latter field in the 1950s. Iron is sometimes considered as a prototype for the entire block of transition metals, due to its abundance and the immense role it has played in the technological progress of humanity. Its 26 electrons are arranged in the configuration [Ar]3d 4s , of which
6549-490: A well-known IV state, as removing the 4th electron in this case produces a half-full 4f configuration. The additional stable valences for Ce and Eu mean that their abundances in rocks sometimes varies significantly relative to the other rare earth elements: see cerium anomaly and europium anomaly . The similarity in ionic radius between adjacent lanthanide elements makes it difficult to separate them from each other in naturally occurring ores and other mixtures. Historically,
6726-823: Is a chemical element ; it has the symbol Fe (from Latin ferrum 'iron') and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table . It is, by mass, the most common element on Earth , forming much of Earth's outer and inner core . It is the fourth most abundant element in the Earth's crust , being mainly deposited by meteorites in its metallic state. Extracting usable metal from iron ores requires kilns or furnaces capable of reaching 1,500 °C (2,730 °F), about 500 °C (932 °F) higher than that required to smelt copper . Humans started to master that process in Eurasia during
6903-555: Is a low-lying excited state for La, Ce, and Gd; for Lu, the 4f shell is already full, and the fifteenth electron has no choice but to enter 5d). With the exception of lutetium, the 4f orbitals are chemically active in all lanthanides and produce profound differences between lanthanide chemistry and transition metal chemistry. The 4f orbitals penetrate the [Xe] core and are isolated, and thus they do not participate much in bonding. This explains why crystal field effects are small and why they do not form π bonds. As there are seven 4f orbitals,
7080-542: Is a useful oxidizing agent. The Ce(IV) is the exception owing to the tendency to form an unfilled f shell. Otherwise tetravalent lanthanides are rare. However, recently Tb(IV) and Pr(IV) complexes have been shown to exist. Lanthanide metals react exothermically with hydrogen to form LnH 2 , dihydrides. With the exception of Eu and Yb, which resemble the Ba and Ca hydrides (non-conducting, transparent salt-like compounds), they form black, pyrophoric , conducting compounds where
7257-420: Is added to molten steel to remove oxygen and sulfur, stable oxysulfides are produced that form an immiscible solid. All of the lanthanides form a mononitride, LnN, with the rock salt structure. The mononitrides have attracted interest because of their unusual physical properties. SmN and EuN are reported as being " half metals ". NdN, GdN, TbN and DyN are ferromagnetic, SmN is antiferromagnetic. Applications in
Rare-earth element - Misplaced Pages Continue
7434-646: Is also rarely found in basalts that have formed from magmas that have come into contact with carbon-rich sedimentary rocks, which have reduced the oxygen fugacity sufficiently for iron to crystallize. This is known as telluric iron and is described from a few localities, such as Disko Island in West Greenland, Yakutia in Russia and Bühl in Germany. Ferropericlase (Mg,Fe)O , a solid solution of periclase (MgO) and wüstite (FeO), makes up about 20% of
7611-536: Is also sometimes considered a lanthanide, despite being a d-block element and a transition metal. The informal chemical symbol Ln is used in general discussions of lanthanide chemistry to refer to any lanthanide. All but one of the lanthanides are f-block elements, corresponding to the filling of the 4f electron shell . Lutetium is a d-block element (thus also a transition metal ), and on this basis its inclusion has been questioned; however, like its congeners scandium and yttrium in group 3, it behaves similarly to
7788-468: Is also true of transition metals . However, transition metals are able to use vibronic coupling to break this rule. The valence orbitals in lanthanides are almost entirely non-bonding and as such little effective vibronic coupling takes, hence the spectra from f → f transitions are much weaker and narrower than those from d → d transitions. In general this makes the colors of lanthanide complexes far fainter than those of transition metal complexes. Viewing
7965-413: Is called the bixbyite structure, as it occurs in a mineral of that name ( (Mn,Fe) 2 O 3 ). As seen in the chart, rare-earth elements are found on Earth at similar concentrations to many common transition metals. The most abundant rare-earth element is cerium , which is actually the 25th most abundant element in Earth's crust , having 68 parts per million (about as common as copper). The exception
8142-407: Is considered to be resistant to rust, due to its oxide layer. Iron forms various oxide and hydroxide compounds ; the most common are iron(II,III) oxide (Fe 3 O 4 ), and iron(III) oxide (Fe 2 O 3 ). Iron(II) oxide also exists, though it is unstable at room temperature. Despite their names, they are actually all non-stoichiometric compounds whose compositions may vary. These oxides are
8319-499: Is due to its abundant production during the runaway fusion and explosion of type Ia supernovae , which scatters the iron into space. Metallic or native iron is rarely found on the surface of the Earth because it tends to oxidize. However, both the Earth's inner and outer core , which together account for 35% of the mass of the whole Earth, are believed to consist largely of an iron alloy, possibly with nickel . Electric currents in
8496-474: Is experimentally well defined for pressures less than 50 GPa. For greater pressures, published data (as of 2007) still varies by tens of gigapascals and over a thousand kelvin. Below its Curie point of 770 °C (1,420 °F; 1,040 K), α-iron changes from paramagnetic to ferromagnetic : the spins of the two unpaired electrons in each atom generally align with the spins of its neighbors, creating an overall magnetic field . This happens because
8673-527: Is extracted into kerosene containing tri- n -butylphosphate . The strength of the complexes formed increases as the ionic radius decreases, so solubility in the organic phase increases. Complete separation can be achieved continuously by use of countercurrent exchange methods. The elements can also be separated by ion-exchange chromatography , making use of the fact that the stability constant for formation of EDTA complexes increases for log K ≈ 15.5 for [La(EDTA)] to log K ≈ 19.8 for [Lu(EDTA)] . When in
8850-611: Is high, weathering forms a thick argillized regolith, this process is called supergene enrichment and produces laterite deposits; heavy rare-earth elements are incorporated into the residual clay by absorption. This kind of deposit is only mined for REE in Southern China, where the majority of global heavy rare-earth element production occurs. REE-laterites do form elsewhere, including over the carbonatite at Mount Weld in Australia. REE may also be extracted from placer deposits if
9027-443: Is in Earth's crust only amounts to about 5% of the overall mass of the crust and is thus only the fourth most abundant element in that layer (after oxygen , silicon , and aluminium ). Most of the iron in the crust is combined with various other elements to form many iron minerals . An important class is the iron oxide minerals such as hematite (Fe 2 O 3 ), magnetite (Fe 3 O 4 ), and siderite (FeCO 3 ), which are
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#17328019642039204-492: Is known as the alkaline earth elements for much the same reason. The "rare" in the name "rare earths" has more to do with the difficulty of separating of the individual elements than the scarcity of any of them. By way of the Greek dysprositos for "hard to get at", element 66, dysprosium was similarly named. The elements 57 (La) to 71 (Lu) are very similar chemically to one another and frequently occur together in nature. Often
9381-401: Is not like that of Mn with its weak, spin-forbidden d–d bands, because Fe has higher positive charge and is more polarizing, lowering the energy of its ligand-to-metal charge transfer absorptions. Thus, all the above complexes are rather strongly colored, with the single exception of the hexaquo ion – and even that has a spectrum dominated by charge transfer in the near ultraviolet region. On
9558-414: Is often explained by the poor shielding of the 5s and 5p electrons by the 4f electrons. The chemistry of the lanthanides is dominated by the +3 oxidation state, and in Ln compounds the 6s electrons and (usually) one 4f electron are lost and the ions have the configuration [Xe]4f . All the lanthanide elements exhibit the oxidation state +3. In addition, Ce can lose its single f electron to form Ce with
9735-444: Is possible to observe the serial trend of the REE by reporting their normalized concentrations against the atomic number. The trends that are observed in "spider" diagrams are typically referred to as "patterns", which may be diagnostic of petrological processes that have affected the material of interest. According to the general shape of the patterns or thanks to the presence (or absence) of so-called "anomalies", information regarding
9912-407: Is possible, but nonetheless the sequence does effectively end at Ni because conditions in stellar interiors cause the competition between photodisintegration and the alpha process to favor photodisintegration around Ni. This Ni, which has a half-life of about 6 days, is created in quantity in these stars, but soon decays by two successive positron emissions within supernova decay products in
10089-548: Is somewhat different). Pieces of magnetite with natural permanent magnetization ( lodestones ) provided the earliest compasses for navigation. Particles of magnetite were extensively used in magnetic recording media such as core memories , magnetic tapes , floppies , and disks , until they were replaced by cobalt -based materials. Iron has four stable isotopes : Fe (5.845% of natural iron), Fe (91.754%), Fe (2.119%) and Fe (0.282%). Twenty-four artificial isotopes have also been created. Of these stable isotopes, only Fe has
10266-442: Is such a strong oxidizing agent that it oxidizes ammonia to nitrogen (N 2 ) and water to oxygen: The pale-violet hex aquo complex [Fe(H 2 O) 6 ] is an acid such that above pH 0 it is fully hydrolyzed: As pH rises above 0 the above yellow hydrolyzed species form and as it rises above 2–3, reddish-brown hydrous iron(III) oxide precipitates out of solution. Although Fe has a d configuration, its absorption spectrum
10443-729: Is suggested. The resistivities of the lanthanide metals are relatively high, ranging from 29 to 134 μΩ·cm. These values can be compared to a good conductor such as aluminium, which has a resistivity of 2.655 μΩ·cm. With the exceptions of La, Yb, and Lu (which have no unpaired f electrons), the lanthanides are strongly paramagnetic, and this is reflected in their magnetic susceptibilities. Gadolinium becomes ferromagnetic at below 16 °C ( Curie point ). The other heavier lanthanides – terbium, dysprosium, holmium, erbium, thulium, and ytterbium – become ferromagnetic at much lower temperatures. 4f * Not including initial [Xe] core f → f transitions are symmetry forbidden (or Laporte-forbidden), which
10620-502: Is supposed to have an orthorhombic or a double hcp structure. (Confusingly, the term "β-iron" is sometimes also used to refer to α-iron above its Curie point, when it changes from being ferromagnetic to paramagnetic, even though its crystal structure has not changed. ) The inner core of the Earth is generally presumed to consist of an iron- nickel alloy with ε (or β) structure. The melting and boiling points of iron, along with its enthalpy of atomization , are lower than those of
10797-443: Is synthetically produced in nuclear reactors. Due to their chemical similarity, the concentrations of rare earths in rocks are only slowly changed by geochemical processes, making their proportions useful for geochronology and dating fossils. Rare-earth elements occur in nature in combination with phosphate ( monazite ), carbonate - fluoride ( bastnäsite ), and oxygen anions. In their oxides, most rare-earth elements only have
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#173280196420310974-465: Is the highest of the lanthanides. The sum of the first two ionization energies for ytterbium are the second lowest in the series and its third ionization energy is the second highest. The high third ionization energy for Eu and Yb correlate with the half filling 4f and complete filling 4f of the 4f subshell, and the stability afforded by such configurations due to exchange energy. Europium and ytterbium form salt like compounds with Eu and Yb , for example
11151-516: Is the highly unstable and radioactive promethium "rare earth" is quite scarce. The longest-lived isotope of promethium has a half-life of 17.7 years, so the element exists in nature in only negligible amounts (approximately 572 g in the entire Earth's crust). Promethium is one of the two elements that do not have stable (non-radioactive) isotopes and are followed by (i.e. with higher atomic number) stable elements (the other being technetium ). The rare-earth elements are often found together. During
11328-418: Is thus very important economically, and iron is the cheapest metal, with a price of a few dollars per kilogram or pound. Pristine and smooth pure iron surfaces are a mirror-like silvery-gray. Iron reacts readily with oxygen and water to produce brown-to-black hydrated iron oxides , commonly known as rust . Unlike the oxides of some other metals that form passivating layers, rust occupies more volume than
11505-451: Is used as the traditional "blue" in blueprints . Iron is the first of the transition metals that cannot reach its group oxidation state of +8, although its heavier congeners ruthenium and osmium can, with ruthenium having more difficulty than osmium. Ruthenium exhibits an aqueous cationic chemistry in its low oxidation states similar to that of iron, but osmium does not, favoring high oxidation states in which it forms anionic complexes. In
11682-437: Is used in chemical actinometry and along with its sodium salt undergoes photoreduction applied in old-style photographic processes. The dihydrate of iron(II) oxalate has a polymeric structure with co-planar oxalate ions bridging between iron centres with the water of crystallisation located forming the caps of each octahedron, as illustrated below. Iron(III) complexes are quite similar to those of chromium (III) with
11859-568: The 2nd millennium BC and the use of iron tools and weapons began to displace copper alloys – in some regions, only around 1200 BC. That event is considered the transition from the Bronze Age to the Iron Age . In the modern world , iron alloys, such as steel , stainless steel , cast iron and special steels , are by far the most common industrial metals, due to their mechanical properties and low cost. The iron and steel industry
12036-562: The Oddo–Harkins rule : even-numbered REE at abundances of about 5% each, and odd-numbered REE at abundances of about 1% each. Similar compositions are found in xenotime or gadolinite. Well-known minerals containing yttrium, and other HREE, include gadolinite, xenotime, samarskite , euxenite , fergusonite , yttrotantalite, yttrotungstite, yttrofluorite (a variety of fluorite ), thalenite, and yttrialite . Small amounts occur in zircon , which derives its typical yellow fluorescence from some of
12213-432: The supernova remnant gas cloud, first to radioactive Co, and then to stable Fe. As such, iron is the most abundant element in the core of red giants , and is the most abundant metal in iron meteorites and in the dense metal cores of planets such as Earth . It is also very common in the universe, relative to other stable metals of approximately the same atomic weight . Iron is the sixth most abundant element in
12390-491: The trans - chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II) complex is used as a starting material for compounds with the Fe( dppe ) 2 moiety . The ferrioxalate ion with three oxalate ligands displays helical chirality with its two non-superposable geometries labelled Λ (lambda) for the left-handed screw axis and Δ (delta) for the right-handed screw axis, in line with IUPAC conventions. Potassium ferrioxalate
12567-466: The universe , and the most common refractory element. Although a further tiny energy gain could be extracted by synthesizing Ni , which has a marginally higher binding energy than Fe, conditions in stars are unsuitable for this process. Element production in supernovas greatly favor iron over nickel, and in any case, Fe still has a lower mass per nucleon than Ni due to its higher fraction of lighter protons. Hence, elements heavier than iron require
12744-483: The upper mantle (200 to 600 km depth). This melt becomes enriched in incompatible elements, like the rare-earth elements, by leaching them out of the crystalline residue. The resultant magma rises as a diapir , or diatreme , along pre-existing fractures, and can be emplaced deep in the crust , or erupted at the surface. Typical REE enriched deposits types forming in rift settings are carbonatites, and A- and M-Type granitoids. Near subduction zones, partial melting of
12921-428: The "heavy" group from 6.965 (ytterbium) to 9.32 (thulium), as well as including yttrium at 4.47. Europium has a density of 5.24. Rare-earth elements, except scandium , are heavier than iron and thus are produced by supernova nucleosynthesis or by the s-process in asymptotic giant branch stars. In nature, spontaneous fission of uranium-238 produces trace amounts of radioactive promethium , but most promethium
13098-570: The 3d and 4s electrons are relatively close in energy, and thus a number of electrons can be ionized. Iron forms compounds mainly in the oxidation states +2 ( iron(II) , "ferrous") and +3 ( iron(III) , "ferric"). Iron also occurs in higher oxidation states , e.g., the purple potassium ferrate (K 2 FeO 4 ), which contains iron in its +6 oxidation state. The anion [FeO 4 ] with iron in its +7 oxidation state, along with an iron(V)-peroxo isomer, has been detected by infrared spectroscopy at 4 K after cocondensation of laser-ablated Fe atoms with
13275-567: The 4 f orbital which acts against the electrons of the 6 s and 5 d orbitals. The lanthanide contraction has a direct effect on the geochemistry of the lanthanides, which show a different behaviour depending on the systems and processes in which they are involved. The effect of the lanthanide contraction can be observed in the REE behaviour both in a CHARAC-type geochemical system (CHArge-and-RAdius-Controlled) where elements with similar charge and radius should show coherent geochemical behaviour, and in non-CHARAC systems, such as aqueous solutions, where
13452-603: The Earth's surface. Items made of cold-worked meteoritic iron have been found in various archaeological sites dating from a time when iron smelting had not yet been developed; and the Inuit in Greenland have been reported to use iron from the Cape York meteorite for tools and hunting weapons. About 1 in 20 meteorites consist of the unique iron-nickel minerals taenite (35–80% iron) and kamacite (90–95% iron). Native iron
13629-411: The Greek λανθανειν ( lanthanein ), "to lie hidden". Rather than referring to their natural abundance, the word reflects their property of "hiding" behind each other in minerals. The term derives from lanthanum , first discovered in 1838, at that time a so-called new rare-earth element "lying hidden" or "escaping notice" in a cerium mineral, and it is an irony that lanthanum was later identified as
13806-506: The LREE. This has economic consequences: large ore bodies of LREE are known around the world and are being exploited. Ore bodies for HREE are more rare, smaller, and less concentrated. Most of the current supply of HREE originates in the "ion-absorption clay" ores of Southern China. Some versions provide concentrates containing about 65% yttrium oxide, with the HREE being present in ratios reflecting
13983-530: The United States (during the Manhattan Project ) developed chemical ion-exchange procedures for separating and purifying rare-earth elements. This method was first applied to the actinides for separating plutonium-239 and neptunium from uranium , thorium , actinium , and the other actinides in the materials produced in nuclear reactors . Plutonium-239 was very desirable because it is
14160-449: The accompanying HREE. The zirconium mineral eudialyte , such as is found in southern Greenland , contains small but potentially useful amounts of yttrium. Of the above yttrium minerals, most played a part in providing research quantities of lanthanides during the discovery days. Xenotime is occasionally recovered as a byproduct of heavy-sand processing, but is not as abundant as the similarly recovered monazite (which typically contains
14337-448: The anhydrous rare-earth phosphates, it is the tetragonal mineral xenotime that incorporates yttrium and the HREE, whereas the monoclinic monazite phase incorporates cerium and the LREE preferentially. The smaller size of the HREE allows greater solid solubility in the rock-forming minerals that make up Earth's mantle, and thus yttrium and the HREE show less enrichment in Earth's crust relative to chondritic abundance than does cerium and
14514-450: The brown deposits present in a sizeable number of streams. Due to its electronic structure, iron has a very large coordination and organometallic chemistry. Many coordination compounds of iron are known. A typical six-coordinate anion is hexachloroferrate(III), [FeCl 6 ] , found in the mixed salt tetrakis(methylammonium) hexachloroferrate(III) chloride . Complexes with multiple bidentate ligands have geometric isomers . For example,
14691-709: The color of various rocks and clays , including entire geological formations like the Painted Hills in Oregon and the Buntsandstein ("colored sandstone", British Bunter ). Through Eisensandstein (a jurassic 'iron sandstone', e.g. from Donzdorf in Germany) and Bath stone in the UK, iron compounds are responsible for the yellowish color of many historical buildings and sculptures. The proverbial red color of
14868-866: The core of igneous complexes; they consist of fine-grained calcite and hematite, sometimes with significant concentrations of ankerite and minor concentrations of siderite. Large carbonatite deposits enriched in rare-earth elements include Mount Weld in Australia, Thor Lake in Canada, Zandkopsdrift in South Africa, and Mountain Pass in the USA. Peralkaline granites (A-Type granitoids) have very high concentrations of alkaline elements and very low concentrations of phosphorus; they are deposited at moderate depths in extensional zones, often as igneous ring complexes, or as pipes, massive bodies, and lenses. These fluids have very low viscosities and high element mobility, which allows for
15045-464: The cores of the Earth and other planets. Above approximately 10 GPa and temperatures of a few hundred kelvin or less, α-iron changes into another hexagonal close-packed (hcp) structure, which is also known as ε-iron . The higher-temperature γ-phase also changes into ε-iron, but does so at higher pressure. Some controversial experimental evidence exists for a stable β phase at pressures above 50 GPa and temperatures of at least 1500 K. It
15222-408: The crude yttria 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. Due to the difficulty in separating
15399-736: The crystallization of large grains, despite a relatively short crystallization time upon emplacement; their large grain size is why these deposits are commonly referred to as pegmatites. Economically viable pegmatites are divided into Lithium-Cesium-Tantalum (LCT) and Niobium-Yttrium-Fluorine (NYF) types; NYF types are enriched in rare-earth minerals. Examples of rare-earth pegmatite deposits include Strange Lake in Canada and Khaladean-Buregtey in Mongolia. Nepheline syenite (M-Type granitoids) deposits are 90% feldspar and feldspathoid minerals. They are deposited in small, circular massifs and contain high concentrations of rare-earth-bearing accessory minerals . For
15576-412: The difference in solubility of rare-earth double sulfates with sodium and potassium. The sodium double sulfates of the cerium group are poorly soluble, those of the terbium group slightly, and those of the yttrium group are very soluble. Sometimes, the yttrium group was further split into the erbium group (dysprosium, holmium, erbium, and thulium) and the ytterbium group (ytterbium and lutetium), but today
15753-445: The diiodides have relatively short metal-metal separations. The CuTi 2 structure of the lanthanum, cerium and praseodymium diiodides along with HP-NdI 2 contain 4 nets of metal and iodine atoms with short metal-metal bonds (393-386 La-Pr). these compounds should be considered to be two-dimensional metals (two-dimensional in the same way that graphite is). The salt-like dihalides include those of Eu, Dy, Tm, and Yb. The formation of
15930-401: The domains in the new positions, so that the effect persists even after the external field is removed – thus turning the iron object into a (permanent) magnet . Similar behavior is exhibited by some iron compounds, such as the ferrites including the mineral magnetite , a crystalline form of the mixed iron(II,III) oxide Fe 3 O 4 (although the atomic-scale mechanism, ferrimagnetism ,
16107-479: The earlier 3d elements from scandium to chromium , showing the lessened contribution of the 3d electrons to metallic bonding as they are attracted more and more into the inert core by the nucleus; however, they are higher than the values for the previous element manganese because that element has a half-filled 3d sub-shell and consequently its d-electrons are not easily delocalized. This same trend appears for ruthenium but not osmium . The melting point of iron
16284-407: The electron structure is also an important parameter to consider as the lanthanide contraction affects the ionic potential . A direct consequence is that, during the formation of coordination bonds, the REE behaviour gradually changes along the series. Furthermore, the lanthanide contraction causes the ionic radius of Ho (0.901 Å) to be almost identical to that of Y (0.9 Å), justifying the inclusion of
16461-478: The electrophilicity of compounds, with a classic example being the Luche reduction . The large size of the ions coupled with their labile ionic bonding allows even bulky coordinating species to bind and dissociate rapidly, resulting in very high turnover rates; thus excellent yields can often be achieved with loadings of only a few mol%. The lack of orbital interactions combined with the lanthanide contraction means that
16638-651: The element showing the anomaly and the predictable one based on the average of the normalized concentrations of the two elements in the previous and next position in the series, according to the equation: where [ REE i ] n {\displaystyle [{\text{REE}}_{i}]_{n}} is the normalized concentration of the element whose anomaly has to be calculated, [ REE i − 1 ] n {\displaystyle [{\text{REE}}_{i-1}]_{n}} and [ REE i + 1 ] n {\displaystyle [{\text{REE}}_{i+1}]_{n}}
16815-485: The elements or (with the exception of Eu 2 S 3 ) sulfidizing the oxide (Ln 2 O 3 ) with H 2 S. The sesquisulfides, Ln 2 S 3 generally lose sulfur when heated and can form a range of compositions between Ln 2 S 3 and Ln 3 S 4 . The sesquisulfides are insulators but some of the Ln 3 S 4 are metallic conductors (e.g. Ce 3 S 4 ) formulated (Ln ) 3 (S ) 4 (e ), while others (e.g. Eu 3 S 4 and Sm 3 S 4 ) are semiconductors. Structurally
16992-406: The exception of iron(III)'s preference for O -donor instead of N -donor ligands. The latter tend to be rather more unstable than iron(II) complexes and often dissociate in water. Many Fe–O complexes show intense colors and are used as tests for phenols or enols . For example, in the ferric chloride test , used to determine the presence of phenols, iron(III) chloride reacts with a phenol to form
17169-417: 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 called uranotantalum (now called " samarskite ") an oxide of a mixture of elements such as yttrium, ytterbium, iron, uranium, thorium, calcium, niobium, and tantalum. This mineral from Miass in
17346-405: The field of spintronics are being investigated. CeN is unusual as it is a metallic conductor, contrasting with the other nitrides also with the other cerium pnictides. A simple description is Ce N (e–) but the interatomic distances are a better match for the trivalent state rather than for the tetravalent state. A number of different explanations have been offered. The nitrides can be prepared by
17523-649: The first in an entire series of chemically similar elements and gave its name to the whole series. Together with the stable elements of group 3, scandium , yttrium , and lutetium , the trivial name " rare earths " is sometimes used to describe the set of lanthanides. The "earth" in the name "rare earths" arises from the minerals from which they were isolated, which were uncommon oxide-type minerals. However, these elements are neither rare in abundance nor "earths" (an obsolete term for water-insoluble strongly basic oxides of electropositive metals incapable of being smelted into metal using late 18th century technology). Group 2
17700-511: The following observations apply: anomalies in europium are dominated by the crystallization of feldspars . Hornblende , controls the enrichment of MREE compared to LREE and HREE. Depletion of LREE relative to HREE may be due to the crystallization of olivine , orthopyroxene , and clinopyroxene . On the other hand, the depletion of HREE relative to LREE may be due to the presence of garnet , as garnet preferentially incorporates HREE into its crystal structure. The presence of zircon may also cause
17877-470: The form of coordination complexes , lanthanides exist overwhelmingly in their +3 oxidation state , although particularly stable 4f configurations can also give +4 (Ce, Pr, Tb) or +2 (Sm, Eu, Yb) ions. All of these forms are strongly electropositive and thus lanthanide ions are hard Lewis acids . The oxidation states are also very stable; with the exceptions of SmI 2 and cerium(IV) salts , lanthanides are not used for redox chemistry. 4f electrons have
18054-431: The form of Ce and Eu depending on the redox conditions of the system. Consequentially, REE are characterized by a substantial identity in their chemical reactivity, which results in a serial behaviour during geochemical processes rather than being characteristic of a single element of the series. Sc, Y, and Lu can be electronically distinguished from the other rare earths because they do not have f valence electrons, whereas
18231-565: The fractionation of trace elements (including rare-earth elements) into the liquid phase (the melt/magma) into the solid phase (the mineral). If an element preferentially remains in the solid phase it is termed 'compatible', and if it preferentially partitions into the melt phase it is described as 'incompatible'. Each element has a different partition coefficient, and therefore fractionates into solid and liquid phases distinctly. These concepts are also applicable to metamorphic and sedimentary petrology. In igneous rocks, particularly in felsic melts,
18408-442: The gas phase the trihalides are planar or approximately planar, the lighter lanthanides have a lower % of dimers, the heavier lanthanides a higher proportion. The dimers have a similar structure to Al 2 Cl 6 . Some of the dihalides are conducting while the rest are insulators. The conducting forms can be considered as Ln electride compounds where the electron is delocalised into a conduction band, Ln (X ) 2 (e ). All of
18585-404: The geographical locations where discovered. A mnemonic for the names of the sixth-row elements in order is "Lately college parties never produce sexy European girls that drink heavily even though you look". Rare earths were mainly discovered as components of minerals. Ytterbium was found in the "ytterbite" (renamed to gadolinite in 1800) discovered by Lieutenant Carl Axel Arrhenius in 1787 at
18762-462: The global stock of iron in use in society is 2,200 kg per capita. More-developed countries differ in this respect from less-developed countries (7,000–14,000 vs 2,000 kg per capita). Ocean science demonstrated the role of the iron in the ancient seas in both marine biota and climate. Iron shows the characteristic chemical properties of the transition metals , namely the ability to form variable oxidation states differing by steps of one and
18939-446: The heavy rare-earth elements (HREE), and those that fall in between are typically referred to as the middle rare-earth elements (MREE). Commonly, rare-earth elements with atomic numbers 57 to 61 (lanthanum to promethium) are classified as light and those with atomic numbers 62 and greater are classified as heavy rare-earth elements. Increasing atomic numbers between light and heavy rare-earth elements and decreasing atomic radii throughout
19116-419: The iodides form soluble complexes with ethers, e.g. TmI 2 (dimethoxyethane) 3 . Samarium(II) iodide is a useful reducing agent. Ln(II) complexes can be synthesized by transmetalation reactions. The normal range of oxidation states can be expanded via the use of sterically bulky cyclopentadienyl ligands , in this way many lanthanides can be isolated as Ln(II) compounds. Ce(IV) in ceric ammonium nitrate
19293-574: The laboratory and there are currently few examples them being used on an industrial scale. Lanthanides exist in many forms other than coordination complexes and many of these are industrially useful. In particular lanthanide metal oxides are used as heterogeneous catalysts in various industrial processes. The trivalent lanthanides mostly form ionic salts. The trivalent ions are hard acceptors and form more stable complexes with oxygen-donor ligands than with nitrogen-donor ligands. The larger ions are 9-coordinate in aqueous solution, [Ln(H 2 O) 9 ] but
19470-419: The lanthanides can be compared with aluminium. In aluminium the sum of the first three ionization energies is 5139 kJ·mol , whereas the lanthanides fall in the range 3455 – 4186 kJ·mol . This correlates with the highly reactive nature of the lanthanides. The sum of the first two ionization energies for europium, 1632 kJ·mol can be compared with that of barium 1468.1 kJ·mol and europium's third ionization energy
19647-409: The lanthanides change in size across the series but that their chemistry remains much the same. This allows for easy tuning of the steric environments and examples exist where this has been used to improve the catalytic activity of the complex and change the nuclearity of metal clusters. Despite this, the use of lanthanide coordination complexes as homogeneous catalysts is largely restricted to
19824-416: The lanthanides form hydroxides, Ln(OH) 3 . With the exception of lutetium hydroxide, which has a cubic structure, they have the hexagonal UCl 3 structure. The hydroxides can be precipitated from solutions of Ln . They can also be formed by the reaction of the sesquioxide, Ln 2 O 3 , with water, but although this reaction is thermodynamically favorable it is kinetically slow for the heavier members of
20001-510: The lanthanides form monochalcogenides, LnQ, (Q= S, Se, Te). The majority of the monochalcogenides are conducting, indicating a formulation Ln Q (e-) where the electron is in conduction bands. The exceptions are SmQ, EuQ and YbQ which are semiconductors or insulators but exhibit a pressure induced transition to a conducting state. Compounds LnQ 2 are known but these do not contain Ln but are Ln compounds containing polychalcogenide anions. Oxysulfides Ln 2 O 2 S are well known, they all have
20178-401: The lanthanides from left to right in the periodic table, the seven 4f atomic orbitals become progressively more filled (see above and Periodic table § Electron configuration table ). The electronic configuration of most neutral gas-phase lanthanide atoms is [Xe]6s 4f , where n is 56 less than the atomic number Z . Exceptions are La, Ce, Gd, and Lu, which have 4f 5d (though even then 4f
20355-470: The latter among the REE. The application of rare-earth elements to geology is important to understanding the petrological processes of igneous , sedimentary and metamorphic rock formation. In geochemistry , rare-earth elements can be used to infer the petrological mechanisms that have affected a rock due to the subtle atomic size differences between the elements, which causes preferential fractionation of some rare earths relative to others depending on
20532-453: The liquid outer core are believed to be the origin of the Earth's magnetic field . The other terrestrial planets ( Mercury , Venus , and Mars ) as well as the Moon are believed to have a metallic core consisting mostly of iron. The M-type asteroids are also believed to be partly or mostly made of metallic iron alloy. The rare iron meteorites are the main form of natural metallic iron on
20709-446: The literature, this mineral phase of the lower mantle is also often called magnesiowüstite. Silicate perovskite may form up to 93% of the lower mantle, and the magnesium iron form, (Mg,Fe)SiO 3 , is considered to be the most abundant mineral in the Earth, making up 38% of its volume. While iron is the most abundant element on Earth, most of this iron is concentrated in the inner and outer cores. The fraction of iron that
20886-418: The logarithm to the base 10 of the value. Commonly, the rare-earth elements are normalized to chondritic meteorites , as these are believed to be the closest representation of unfractionated Solar System material. However, other normalizing standards can be applied depending on the purpose of the study. Normalization to a standard reference value, especially of a material believed to be unfractionated, allows
21063-470: The main grouping is between the cerium and the yttrium groups. Today, the rare-earth elements are classified as light or heavy rare-earth elements, rather than in cerium and yttrium groups. The classification of rare-earth elements is inconsistent between authors. The most common distinction between rare-earth elements is made by atomic numbers ; those with low atomic numbers are referred to as light rare-earth elements (LREE), those with high atomic numbers are
21240-407: The major ores of iron . Many igneous rocks also contain the sulfide minerals pyrrhotite and pentlandite . During weathering , iron tends to leach from sulfide deposits as the sulfate and from silicate deposits as the bicarbonate. Both of these are oxidized in aqueous solution and precipitate in even mildly elevated pH as iron(III) oxide . Large deposits of iron are banded iron formations ,
21417-775: The metal and thus flakes off, exposing more fresh surfaces for corrosion. Chemically, the most common oxidation states of iron are iron(II) and iron(III) . Iron shares many properties of other transition metals, including the other group 8 elements , ruthenium and osmium . Iron forms compounds in a wide range of oxidation states , −4 to +7. Iron also forms many coordination compounds ; some of them, such as ferrocene , ferrioxalate , and Prussian blue have substantial industrial, medical, or research applications. The body of an adult human contains about 4 grams (0.005% body weight) of iron, mostly in hemoglobin and myoglobin . These two proteins play essential roles in oxygen transport by blood and oxygen storage in muscles . To maintain
21594-438: The metal sub-lattice is face centred cubic and the H atoms occupy tetrahedral sites. Further hydrogenation produces a trihydride which is non-stoichiometric , non-conducting, more salt like. The formation of trihydride is associated with and increase in 8–10% volume and this is linked to greater localization of charge on the hydrogen atoms which become more anionic (H hydride anion) in character. The only tetrahalides known are
21771-431: The metal typically has little effect on the complex (other than size), especially when compared to transition metals . Complexes are held together by weaker electrostatic forces which are omni-directional and thus the ligands alone dictate the symmetry and coordination of complexes. Steric factors therefore dominate, with coordinative saturation of the metal being balanced against inter-ligand repulsion. This results in
21948-519: The metals (and determining the separation is complete), the total number of false discoveries was dozens, with some putting the total number of discoveries at over a hundred. 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 found several new spectral lines in didymia. Also in 1879, Paul Émile Lecoq de Boisbaudran isolated
22125-612: The meteorites Semarkona and Chervony Kut, a correlation between the concentration of Ni, the granddaughter of Fe, and the abundance of the stable iron isotopes provided evidence for the existence of Fe at the time of formation of the Solar System . Possibly the energy released by the decay of Fe, along with that released by Al , contributed to the remelting and differentiation of asteroids after their formation 4.6 billion years ago. The abundance of Ni present in extraterrestrial material may bring further insight into
22302-643: The most part, these deposits are small but important examples include Illimaussaq-Kvanefeld in Greenland, and Lovozera in Russia. Rare-earth elements can also be enriched in deposits by secondary alteration either by interactions with hydrothermal fluids or meteoric water or by erosion and transport of resistate REE-bearing minerals. Argillization of primary minerals enriches insoluble elements by leaching out silica and other soluble elements, recrystallizing feldspar into clay minerals such kaolinite, halloysite, and montmorillonite. In tropical regions where precipitation
22479-414: The name "rare" earths. Because of their geochemical properties, rare-earth elements are typically dispersed and not often found concentrated in rare-earth minerals . Consequently, economically exploitable ore deposits are sparse. The first rare-earth mineral discovered (1787) was gadolinite , a black mineral composed of cerium, yttrium, iron, silicon, and other elements. This mineral was extracted from
22656-559: The necessary levels, human iron metabolism requires a minimum of iron in the diet. Iron is also the metal at the active site of many important redox enzymes dealing with cellular respiration and oxidation and reduction in plants and animals. At least four allotropes of iron (differing atom arrangements in the solid) are known, conventionally denoted α , γ , δ , and ε . The first three forms are observed at ordinary pressures. As molten iron cools past its freezing point of 1538 °C, it crystallizes into its δ allotrope, which has
22833-560: The new element samarium 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, yttria, and samarskite by William Crookes , Lecoq de Boisbaudran and Eugène-Anatole Demarçay yielded several new spectral lines that indicated
23010-423: The normalized concentration, [ REE i ] sam {\displaystyle {[{\text{REE}}_{i}]_{\text{sam}}}} the analytical concentration of the element measured in the sample, and [ REE i ] ref {\displaystyle {[{\text{REE}}_{i}]_{\text{ref}}}} the concentration of the same element in the reference material. It
23187-426: The normalized concentrations of the respectively previous and next elements along the series. The rare-earth elements patterns observed in igneous rocks are primarily a function of the chemistry of the source where the rock came from, as well as the fractionation history the rock has undergone. Fractionation is in turn a function of the partition coefficients of each element. Partition coefficients are responsible for
23364-419: The number of unpaired electrons can be as high as 7, which gives rise to the large magnetic moments observed for lanthanide compounds. Measuring the magnetic moment can be used to investigate the 4f electron configuration, and this is a useful tool in providing an insight into the chemical bonding. The lanthanide contraction , i.e. the reduction in size of the Ln ion from La (103 pm) to Lu (86.1 pm),
23541-432: The observed abundances to be compared to the initial abundances of the element. Normalization also removes the pronounced 'zig-zag' pattern caused by the differences in abundance between even and odd atomic numbers . Normalization is carried out by dividing the analytical concentrations of each element of the series by the concentration of the same element in a given standard, according to the equation: where n indicates
23718-436: The orbitals of those two electrons (d z and d x − y ) do not point toward neighboring atoms in the lattice, and therefore are not involved in metallic bonding. In the absence of an external source of magnetic field, the atoms get spontaneously partitioned into magnetic domains , about 10 micrometers across, such that the atoms in each domain have parallel spins, but some domains have other orientations. Thus
23895-524: The ore. After this discovery in 1794, a mineral from Bastnäs near Riddarhyttan , Sweden, which was believed to be an iron – tungsten mineral, was re-examined by Jöns 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 . It took another 30 years for researchers to determine that other elements were contained in
24072-539: The origin and early history of the Solar System . The most abundant iron isotope Fe is of particular interest to nuclear scientists because it represents the most common endpoint of nucleosynthesis . Since Ni (14 alpha particles ) is easily produced from lighter nuclei in the alpha process in nuclear reactions in supernovae (see silicon burning process ), it is the endpoint of fusion chains inside extremely massive stars . Although adding more alpha particles
24249-406: The other 14. The term rare-earth element or rare-earth metal is often used to include the stable group 3 elements Sc, Y, and Lu in addition to the 4f elements. All lanthanide elements form trivalent cations, Ln , whose chemistry is largely determined by the ionic radius , which decreases steadily from lanthanum (La) to lutetium (Lu). These elements are called lanthanides because the elements in
24426-444: The other hand, the pale green iron(II) hexaquo ion [Fe(H 2 O) 6 ] does not undergo appreciable hydrolysis. Carbon dioxide is not evolved when carbonate anions are added, which instead results in white iron(II) carbonate being precipitated out. In excess carbon dioxide this forms the slightly soluble bicarbonate, which occurs commonly in groundwater, but it oxidises quickly in air to form iron(III) oxide that accounts for
24603-414: The others do, but the chemical behaviour is almost the same. A distinguishing factor in the geochemical behaviour of the REE is linked to the so-called " lanthanide contraction " which represents a higher-than-expected decrease in the atomic/ionic radius of the elements along the series. This is determined by the variation of the shielding effect towards the nuclear charge due to the progressive filling of
24780-581: The oxidizing power of Fe and the high reducing power of I : Ferric iodide, a black solid, is not stable in ordinary conditions, but can be prepared through the reaction of iron pentacarbonyl with iodine and carbon monoxide in the presence of hexane and light at the temperature of −20 °C, with oxygen and water excluded. Complexes of ferric iodide with some soft bases are known to be stable compounds. The standard reduction potentials in acidic aqueous solution for some common iron ions are given below: The red-purple tetrahedral ferrate (VI) anion
24957-497: The past work on isotopic composition of iron has focused on the nucleosynthesis of Fe through studies of meteorites and ore formation. In the last decade, advances in mass spectrometry have allowed the detection and quantification of minute, naturally occurring variations in the ratios of the stable isotopes of iron. Much of this work is driven by the Earth and planetary science communities, although applications to biological and industrial systems are emerging. In phases of
25134-487: The polymorphic form. The colors of the γ-sesquisulfides are La 2 S 3 , white/yellow; Ce 2 S 3 , dark red; Pr 2 S 3 , green; Nd 2 S 3 , light green; Gd 2 S 3 , sand; Tb 2 S 3 , light yellow and Dy 2 S 3 , orange. The shade of γ-Ce 2 S 3 can be varied by doping with Na or Ca with hues ranging from dark red to yellow, and Ce 2 S 3 based pigments are used commercially and are seen as low toxicity substitutes for cadmium based pigments. All of
25311-414: The principal ores for the production of iron (see bloomery and blast furnace). They are also used in the production of ferrites , useful magnetic storage media in computers, and pigments. The best known sulfide is iron pyrite (FeS 2 ), also known as fool's gold owing to its golden luster. It is not an iron(IV) compound, but is actually an iron(II) polysulfide containing Fe and S 2 ions in
25488-444: The principal ores of cerium and the light lanthanides. Enriched deposits of rare-earth elements at the surface of the Earth, carbonatites and pegmatites , are related to alkaline plutonism , an uncommon kind of magmatism that occurs in tectonic settings where there is rifting or that are near subduction zones. In a rift setting, the alkaline magma is produced by very small degrees of partial melting (<1%) of garnet peridotite in
25665-440: The processes at work. The geochemical study of the REE is not carried out on absolute concentrations – as it is usually done with other chemical elements – but on normalized concentrations in order to observe their serial behaviour. In geochemistry, rare-earth elements are typically presented in normalized "spider" diagrams, in which concentration of rare-earth elements are normalized to a reference standard and are then expressed as
25842-419: 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. Some ilmenite concentrates contain small amounts of scandium and other rare-earth elements, which could be analysed by X-ray fluorescence (XRF). Before
26019-499: The reaction of lanthanum metals with nitrogen. Some nitride is produced along with the oxide, when lanthanum metals are ignited in air. Alternative methods of synthesis are a high temperature reaction of lanthanide metals with ammonia or the decomposition of lanthanide amides, Ln(NH 2 ) 3 . Achieving pure stoichiometric compounds, and crystals with low defect density has proved difficult. The lanthanide nitrides are sensitive to air and hydrolyse producing ammonia. Iron Iron
26196-434: The rock retains the rare-earth element concentration from its source. Lanthanide The lanthanide ( / ˈ l æ n θ ə n aɪ d / ) or lanthanoid ( / ˈ l æ n θ ə n ɔɪ d / ) series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium . In the periodic table, they fill the 4f orbitals. Lutetium (element 71)
26373-459: The salt like dihydrides. Both europium and ytterbium dissolve in liquid ammonia forming solutions of Ln (NH 3 ) x again demonstrating their similarities to the alkaline earth metals. The relative ease with which the 4th electron can be removed in cerium and (to a lesser extent praseodymium) indicates why Ce(IV) and Pr(IV) compounds can be formed, for example CeO 2 is formed rather than Ce 2 O 3 when cerium reacts with oxygen. Also Tb has
26550-481: The same ore deposits as the lanthanides and exhibit similar chemical properties, but have different electrical and magnetic properties . The term 'rare-earth' is a misnomer because they are not actually scarce, although historically it took a long time to isolate these elements. These metals tarnish slowly in air at room temperature and react slowly with cold water to form hydroxides, liberating hydrogen. They react with steam to form oxides and ignite spontaneously at
26727-406: The same structure with 7-coordinate Ln atoms, and 3 sulfur and 4 oxygen atoms as near neighbours. Doping these with other lanthanide elements produces phosphors. As an example, gadolinium oxysulfide , Gd 2 O 2 S doped with Tb produces visible photons when irradiated with high energy X-rays and is used as a scintillator in flat panel detectors. When mischmetal , an alloy of lanthanide metals,
26904-636: The seafloor, bit by bit, over tens of millions of years. One square patch of metal-rich mud 2.3 kilometers wide might contain enough rare earths to meet most of the global demand for a year, Japanese geologists report in Nature Geoscience ." "I believe that rare[-]earth resources undersea are much more promising than on-land resources," said Kato. "[C]oncentrations of rare earths were comparable to those found in clays mined in China. Some deposits contained twice as much heavy rare earths such as dysprosium,
27081-437: The second half of the 3d transition series, vertical similarities down the groups compete with the horizontal similarities of iron with its neighbors cobalt and nickel in the periodic table, which are also ferromagnetic at room temperature and share similar chemistry. As such, iron, cobalt, and nickel are sometimes grouped together as the iron triad . Unlike many other metals, iron does not form amalgams with mercury . As
27258-492: The sedimentary parent lithology contains REE-bearing, heavy resistate minerals. In 2011, Yasuhiro Kato, a geologist at the University of Tokyo who led a study of Pacific Ocean seabed mud, published results indicating the mud could hold rich concentrations of rare-earth minerals. The deposits, studied at 78 sites, came from "[h]ot plumes from hydrothermal vents pull[ing] these materials out of seawater and deposit[ing] them on
27435-417: The sequential accretion of the Earth, the dense rare-earth elements were incorporated into the deeper portions of the planet. Early differentiation of molten material largely incorporated the rare earths into mantle rocks. The high field strength and large ionic radii of rare earths make them incompatible with the crystal lattices of most rock-forming minerals, so REE will undergo strong partitioning into
27612-485: The series are chemically similar to lanthanum . Because "lanthanide" means "like lanthanum", it has been argued that lanthanum cannot logically be a lanthanide, but the International Union of Pure and Applied Chemistry (IUPAC) acknowledges its inclusion based on common usage. In presentations of the periodic table , the f-block elements are customarily shown as two additional rows below the main body of
27789-491: The series causes chemical variations. Europium is exempt of this classification as it has two valence states: Eu and Eu. Yttrium is grouped as heavy rare-earth element due to chemical similarities. The break between the two groups is sometimes put elsewhere, such as between elements 63 (europium) and 64 (gadolinium). The actual metallic densities of these two groups overlap, with the "light" group having densities from 6.145 (lanthanum) to 7.26 (promethium) or 7.52 (samarium) g/cc, and
27966-418: The series. Fajans' rules indicate that the smaller Ln ions will be more polarizing and their salts correspondingly less ionic. The hydroxides of the heavier lanthanides become less basic, for example Yb(OH) 3 and Lu(OH) 3 are still basic hydroxides but will dissolve in hot concentrated NaOH . All of the lanthanides form Ln 2 Q 3 (Q= S, Se, Te). The sesquisulfides can be produced by reaction of
28143-408: The series. Europium stands out, as it has the lowest density in the series at 5.24 g/cm and the largest metallic radius in the series at 208.4 pm. It can be compared to barium, which has a metallic radius of 222 pm. It is believed that the metal contains the larger Eu ion and that there are only two electrons in the conduction band. Ytterbium also has a large metallic radius, and a similar explanation
28320-438: The sesquihalides. Scandium forms a similar cluster compound with chlorine, Sc 7 Cl 12 Unlike many transition metal clusters these lanthanide clusters do not have strong metal-metal interactions and this is due to the low number of valence electrons involved, but instead are stabilised by the surrounding halogen atoms. LaI and TmI are the only known monohalides. LaI, prepared from the reaction of LaI 3 and La metal, it has
28497-415: The sesquisulfides adopt structures that vary according to the size of the Ln metal. The lighter and larger lanthanides favoring 7-coordinate metal atoms, the heaviest and smallest lanthanides (Yb and Lu) favoring 6 coordination and the rest structures with a mixture of 6 and 7 coordination. Polymorphism is common amongst the sesquisulfides. The colors of the sesquisulfides vary metal to metal and depend on
28674-407: The smaller ions are 8-coordinate, [Ln(H 2 O) 8 ] . There is some evidence that the later lanthanides have more water molecules in the second coordination sphere. Complexation with monodentate ligands is generally weak because it is difficult to displace water molecules from the first coordination sphere. Stronger complexes are formed with chelating ligands because of the chelate effect , such as
28851-401: The southern Ural Mountains was documented by Gustav 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
29028-575: The stable electronic configuration of xenon. Also, Eu can gain an electron to form Eu with the f configuration that has the extra stability of a half-filled shell. Other than Ce(IV) and Eu(II), none of the lanthanides are stable in oxidation states other than +3 in aqueous solution. In terms of reduction potentials, the Ln couples are nearly the same for all lanthanides, ranging from −1.99 (for Eu) to −2.35 V (for Pr). Thus these metals are highly reducing, with reducing power similar to alkaline earth metals such as Mg (−2.36 V). The ionization energies for
29205-763: The subducting plate within the asthenosphere (80 to 200 km depth) produces a volatile-rich magma (high concentrations of CO 2 and water), with high concentrations of alkaline elements, and high element mobility that the rare earths are strongly partitioned into. This melt may also rise along pre-existing fractures, and be emplaced in the crust above the subducting slab or erupted at the surface. REE-enriched deposits forming from these melts are typically S-Type granitoids. Alkaline magmas enriched with rare-earth elements include carbonatites, peralkaline granites (pegmatites), and nepheline syenite . Carbonatites crystallize from CO 2 -rich fluids, which can be produced by partial melting of hydrous-carbonated lherzolite to produce
29382-564: The surface of Mars is derived from an iron oxide-rich regolith . Significant amounts of iron occur in the iron sulfide mineral pyrite (FeS 2 ), but it is difficult to extract iron from it and it is therefore not exploited. In fact, iron is so common that production generally focuses only on ores with very high quantities of it. According to the International Resource Panel 's Metal Stocks in Society report ,
29559-399: The system under examination and the occurring geochemical processes can be obtained. The anomalies represent enrichment (positive anomalies) or depletion (negative anomalies) of specific elements along the series and are graphically recognizable as positive or negative "peaks" along the REE patterns. The anomalies can be numerically quantified as the ratio between the normalized concentration of
29736-400: The table. This convention is entirely a matter of aesthetics and formatting practicality; a rarely used wide-formatted periodic table inserts the 4f and 5f series in their proper places, as parts of the table's sixth and seventh rows (periods), respectively. The 1985 IUPAC "Red Book" (p. 45) recommends using lanthanoid instead of lanthanide , as the ending -ide normally indicates
29913-517: The tetra-anion derived from 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid ( DOTA ). The most common divalent derivatives of the lanthanides are for Eu(II), which achieves a favorable f configuration. Divalent halide derivatives are known for all of the lanthanides. They are either conventional salts or are Ln(III) " electride "-like salts. The simple salts include YbI 2 , EuI 2 , and SmI 2 . The electride-like salts, described as Ln , 2I , e , include LaI 2 , CeI 2 and GdI 2 . Many of
30090-590: The tetrafluorides of cerium , praseodymium , terbium , neodymium and dysprosium, the last two known only under matrix isolation conditions. All of the lanthanides form trihalides with fluorine, chlorine, bromine and iodine. They are all high melting and predominantly ionic in nature. The fluorides are only slightly soluble in water and are not sensitive to air, and this contrasts with the other halides which are air sensitive, readily soluble in water and react at high temperature to form oxohalides. The trihalides were important as pure metal can be prepared from them. In
30267-479: The time that ion exchange methods and elution were available, the separation of the rare earths was primarily achieved by repeated precipitation or crystallization . In those days, the first separation was into two main groups, the cerium earths (lanthanum, cerium, praseodymium, neodymium, and samarium) and the yttrium earths (scandium, yttrium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). Europium, gadolinium, and terbium were either considered as
30444-484: The two ores ceria and yttria (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,
30621-492: The very laborious processes of cascading and fractional crystallization were used. Because the lanthanide ions have slightly different radii, the lattice energy of their salts and hydration energies of the ions will be slightly different, leading to a small difference in solubility . Salts of the formula Ln(NO 3 ) 3 ·2NH 4 NO 3 ·4H 2 O can be used. Industrially, the elements are separated from each other by solvent extraction . Typically an aqueous solution of nitrates
30798-487: The village and a fifth (holmium) after Stockholm; scandium is named after Scandinavia , thulium after the old name Thule , and the immediately-following group 4 element (number 72) hafnium is named for the Latin name of the city of Copenhagen . The properties of the lanthanides arise from the order in which the electron shells of these elements are filled—the outermost (6s) has the same configuration for all of them, and
30975-455: The volume of the lower mantle of the Earth, which makes it the second most abundant mineral phase in that region after silicate perovskite (Mg,Fe)SiO 3 ; it also is the major host for iron in the lower mantle. At the bottom of the transition zone of the mantle, the reaction γ- (Mg,Fe) 2 [SiO 4 ] ↔ (Mg,Fe)[SiO 3 ] + (Mg,Fe)O transforms γ-olivine into a mixture of silicate perovskite and ferropericlase and vice versa. In
31152-492: Was in fact still a mixture of oxides. In 1842 Mosander also separated the yttria into three oxides: pure yttria, terbia, and erbia (all the names are derived from the town name "Ytterby"). The earth giving pink salts he called terbium ; the one that yielded yellow peroxide he called erbium . In 1842 the number of known rare-earth elements had reached six: yttrium, cerium, lanthanum, didymium, erbium, and terbium. Nils Johan Berlin and Marc Delafontaine tried also to separate
31329-493: Was once thought to be in space group I 2 1 3 (no. 199), but is now known to be in space group Ia 3 (no. 206). The structure is similar to that of fluorite or cerium dioxide (in which the cations form a face-centred cubic lattice and the anions sit inside the tetrahedra of cations), except that one-quarter of the anions (oxygen) are missing. The unit cell of these sesquioxides corresponds to eight unit cells of fluorite or cerium dioxide, with 32 cations instead of 4. This
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