Lutetium is a chemical element; it has symbolLu and atomic number 71. It is a silvery white metal, which resists corrosion in dry air, but not in moist air. Lutetium is the last element in the lanthanide series, and it is traditionally counted among the rare earth elements; it can also be classified as the first element of the 6th-period transition metals.[8]
Lutetium was independently discovered in 1907 by French scientist Georges Urbain, Austrian mineralogist BaronCarl Auer von Welsbach, and American chemist Charles James.[9] All of these researchers found lutetium as an impurity in the mineral ytterbia, which was previously thought to consist entirely of ytterbium and oxygen. The dispute on the priority of the discovery occurred shortly after, with Urbain and Welsbach accusing each other of publishing results influenced by the published research of the other; the naming honor went to Urbain, as he had published his results earlier. He chose the name lutecium for the new element, but in 1949 the spelling was changed to lutetium. In 1909, the priority was finally granted to Urbain and his names were adopted as official ones; however, the name cassiopeium (or later cassiopium) for element 71 proposed by Welsbach was used by many German scientists until the 1950s.[10]
Lutetium is not a particularly abundant element, although it is significantly more common than silver in the Earth's crust. It has few specific uses. Lutetium-176 is a relatively abundant (2.5%) radioactive isotope with a half-life of about 38 billion years, used to determine the age of minerals and meteorites. Lutetium usually occurs in association with the element yttrium[11] and is sometimes used in metal alloys and as a catalyst in various chemical reactions. 177Lu-DOTA-TATE is used for radionuclide therapy (see Nuclear medicine) on neuroendocrine tumours. Lutetium has the highest Brinell hardness of any lanthanide, at 890–1300 MPa.[12]
Characteristics
Physical properties
A lutetium atom has 71 electrons, arranged in the configuration [Xe] 4f145d16s2.[13] Lutetium is generally encountered in the 3+ oxidation state, having lost its two outermost 6s and the single 5d-electron. The lutetium atom is the smallest among the lanthanide atoms, due to the lanthanide contraction,[14] and as a result lutetium has the highest density, melting point, and hardness of the lanthanides.[15] As lutetium's 4f orbitals are highly stabilized only the 5d and 6s orbitals are involved in chemical reactions and bonding;[16][17] thus it is characterized as a d-block rather than an f-block element,[18] and on this basis some consider it not to be a lanthanide at all, but a transition metal like its lighter congeners scandium and yttrium.[19][20]
Lutetium's compounds almost always contain the element in the 3+ oxidation state.[21] Aqueous solutions of most lutetium salts are colorless and form white crystalline solids upon drying, with the common exception of the iodide, which is brown. The soluble salts, such as nitrate, sulfate and acetate form hydrates upon crystallization. The oxide, hydroxide, fluoride, carbonate, phosphate and oxalate are insoluble in water.[22]
Lutetium metal is slightly unstable in air at standard conditions, but it burns readily at 150 °C to form lutetium oxide. The resulting compound is known to absorb water and carbon dioxide, and it may be used to remove vapors of these compounds from closed atmospheres.[23] Similar observations are made during reaction between lutetium and water (slow when cold and fast when hot); lutetium hydroxide is formed in the reaction.[24] Lutetium metal is known to react with the four lightest halogens to form trihalides; except the fluoride they are soluble in water. [citation needed]
Lutetium dissolves readily in weak acids[23] and dilute sulfuric acid to form solutions containing the colorless lutetium ions, which are coordinated by between seven and nine water molecules, the average being [Lu(H2O)8.2]3+.[25]
2 Lu + 3 H2SO4 → 2 Lu3+ + 3 SO2−4 + 3 H2↑
Oxidation states
Lutetium is usually found in the +3 oxidation state, like most other lanthanides. However, it can also be in the 0, +1 and +2 states as well.
Lutetium occurs on the Earth in form of two isotopes: lutetium-175 and lutetium-176. Out of these two, only the former is stable, making the element monoisotopic. The latter one, lutetium-176, decays via beta decay with a half-life of 3.78×1010 years; it makes up about 2.5% of natural lutetium.[7]
To date, 40 synthetic radioisotopes of the element have been characterized, ranging in mass number from 149 to 190;[7][26] the most stable such isotopes are lutetium-174 with a half-life of 3.31 years, and lutetium-173 with a half-life of 1.37 years.[7] All of the remaining radioactive isotopes have half-lives that are less than 9 days, and the majority of these have half-lives that are less than half an hour.[7] Isotopes lighter than the stable lutetium-175 decay via electron capture (to produce isotopes of ytterbium), with some alpha and positron emission; the heavier isotopes decay primarily via beta decay, producing hafnium isotopes.[7]
The element also has 43 known nuclear isomers, with masses of 150, 151, 153–162, and 166–180 (not every mass number corresponds to only one isomer). The most stable of them are lutetium-177m, with a half-life of 160.4 days, and lutetium-174m, with a half-life of 142 days; these are longer than the half-lives of the ground states of all radioactive lutetium isotopes except lutetium-173, 174, and 176.[7]
History
Lutetium, derived from the Latin Lutetia (Paris), was independently discovered in 1907 by French scientist Georges Urbain, Austrian mineralogist Baron Carl Auer von Welsbach, and American chemist Charles James.[27][28] They found it as an impurity in ytterbia, which was thought by Swiss chemist Jean Charles Galissard de Marignac to consist entirely of ytterbium.[29] The scientists proposed different names for the elements: Urbain chose neoytterbium and lutecium,[30] whereas Welsbach chose aldebaranium and cassiopeium (after Aldebaran and Cassiopeia).[31] Both of these articles accused the other man of publishing results based on those of the author.[32][33][34][35][36]
The International Commission on Atomic Weights, which was then responsible for the attribution of new element names, settled the dispute in 1909 by granting priority to Urbain and adopting his names as official ones, based on the fact that the separation of lutetium from Marignac's ytterbium was first described by Urbain;[29] after Urbain's names were recognized, neoytterbium was reverted to ytterbium. An obvious issue with this decision is that Urbain was on the International Commission of Atomic Weights.[37] Until the 1950s, some German-speaking chemists called lutetium by Welsbach's name, cassiopeium; in 1949, the spelling of element 71 was changed to lutetium. The reason for this was that Welsbach's 1907 samples of lutetium had been pure, while Urbain's 1907 samples only contained traces of lutetium.[38] This later misled Urbain into thinking that he had discovered element 72, which he named celtium, which was actually very pure lutetium. The later discrediting of Urbain's work on element 72 led to a reappraisal of Welsbach's work on element 71, so that the element was renamed to cassiopeium in German-speaking countries for some time.[38] Charles James, who stayed out of the priority argument, worked on a much larger scale and possessed the largest supply of lutetium at the time.[39] Pure lutetium metal was first produced in 1953.[39]
Occurrence and production
Monazite
Found with almost all other rare-earth metals but never by itself, lutetium is very difficult to separate from other elements. Its principal commercial source is as a by-product from the processing of the rare earth phosphate mineral monazite (Ce,La,...)PO 4, which has concentrations of only 0.0001% of the element,[23] not much higher than the abundance of lutetium in the Earth crust of about 0.5 mg/kg. No lutetium-dominant minerals are currently known. [40] The main mining areas are China, United States, Brazil, India, Sri Lanka and Australia. The world production of lutetium (in the form of oxide) is about 10 tonnes per year.[39] Pure lutetium metal is very difficult to prepare. It is one of the rarest and most expensive of the rare earth metals with the price about US$10,000 per kilogram, or about one-fourth that of gold.[41][42]
Crushed minerals are treated with hot concentrated sulfuric acid to produce water-soluble sulfates of rare earths. Thorium precipitates out of solution as hydroxide and is removed. After that the solution is treated with ammonium oxalate to convert rare earths into their insoluble oxalates. The oxalates are converted to oxides by annealing. The oxides are dissolved in nitric acid that excludes one of the main components, cerium, whose oxide is insoluble in HNO3. Several rare earth metals, including lutetium, are separated as a double salt with ammonium nitrate by crystallization. Lutetium is separated by ion exchange. In this process, rare-earth ions are adsorbed onto suitable ion-exchange resin by exchange with hydrogen, ammonium or cupric ions present in the resin. Lutetium salts are then selectively washed out by suitable complexing agent. Lutetium metal is then obtained by reduction of anhydrous LuCl3 or LuF3 by either an alkali metal or alkaline earth metal.[22]
2 LuCl3 + 3 Ca → 2 Lu + 3 CaCl2
177Lu is produced by neutron activation of 176Lu or by indirectly by neutron activation of 176Yb followed by beta decay. The 6.693 day half life allows transport from the production reactor to the point of use without significant loss in activity.[43]
Applications
Small quantities of lutetium have many speciality uses.
Lutetium tantalate (LuTaO4) is the densest known stable white material (density 9.81 g/cm3)[51] and therefore is an ideal host for X-ray phosphors.[52][53] The only denser white material is thorium dioxide, with density of 10 g/cm3, but the thorium it contains is radioactive.
The isotope 177Lu emits low-energy beta particles and gamma rays and has a half-life around 7 days, positive characteristics for commercial applications, especially in therapeutic nuclear medicine.[43]
The synthetic isotope lutetium-177 bound to octreotate (a somatostatin analogue), is used experimentally in targeted radionuclide therapy for neuroendocrine tumors.[56] Lutetium-177 is used as a radionuclide in neuroendocrine tumor therapy and bone pain palliation.[57][58]
Like other rare-earth metals, lutetium is regarded as having a low degree of toxicity, but its compounds should be handled with care nonetheless: for example, lutetium fluoride inhalation is dangerous and the compound irritates skin.[23] Lutetium nitrate may be dangerous as it may explode and burn once heated. Lutetium oxide powder is toxic as well if inhaled or ingested.[23]
Similarly to the other rare-earth metals, lutetium has no known biological role, but it is found even in humans, concentrating in bones, and to a lesser extent in the liver and kidneys.[39] Lutetium salts are known to occur together with other lanthanide salts in nature; the element is the least abundant in the human body of all lanthanides.[39] Human diets have not been monitored for lutetium content, so it is not known how much the average human takes in, but estimations show the amount is only about several micrograms per year, all coming from tiny amounts absorbed by plants. Soluble lutetium salts are mildly toxic, but insoluble ones are not.[39]
^ abArblaster, John W. (2018). Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International. ISBN978-1-62708-155-9.
^Yttrium and all lanthanides except Ce and Pm have been observed in the oxidation state 0 in bis(1,3,5-tri-t-butylbenzene) complexes, see Cloke, F. Geoffrey N. (1993). "Zero Oxidation State Compounds of Scandium, Yttrium, and the Lanthanides". Chem. Soc. Rev. 22: 17–24. doi:10.1039/CS9932200017. and Arnold, Polly L.; Petrukhina, Marina A.; Bochenkov, Vladimir E.; Shabatina, Tatyana I.; Zagorskii, Vyacheslav V.; Cloke (2003-12-15). "Arene complexation of Sm, Eu, Tm and Yb atoms: a variable temperature spectroscopic investigation". Journal of Organometallic Chemistry. 688 (1–2): 49–55. doi:10.1016/j.jorganchem.2003.08.028.
^All the lanthanides, except Pm, in the +2 oxidation state have been observed in organometallic molecular complexes, see Lanthanides Topple Assumptions and Meyer, G. (2014). "All the Lanthanides Do It and Even Uranium Does Oxidation State +2". Angewandte Chemie International Edition. 53 (14): 3550–51. doi:10.1002/anie.201311325. PMID24616202.. Additionally, all the lanthanides (La–Lu) form dihydrides (LnH2), dicarbides (LnC2), monosulfides (LnS), monoselenides (LnSe), and monotellurides (LnTe), but for most elements these compounds have Ln3+ ions with electrons delocalized into conduction bands, e. g. Ln3+(H−)2(e−).
^Krinsky, Jamin L.; Minasian, Stefan G.; Arnold, John (2010-12-08). "Covalent Lanthanide Chemistry Near the Limit of Weak Bonding: Observation of (CpSiMe3)3Ce−ECp* and a Comprehensive Density Functional Theory Analysis of Cp3Ln−ECp (E = Al, Ga)". Inorganic Chemistry. 50 (1). American Chemical Society (ACS): 345–357. doi:10.1021/ic102028d. ISSN0020-1669. PMID21141834.
^James, C. (1907). "A new method for the separation of the yttrium earths". Journal of the American Chemical Society. 29 (4): 495–499. doi:10.1021/ja01958a010. In a footnote on page 498, James mentions that Carl Auer von Welsbach had announced " ... the presence of a new element Er, γ, which is undoubtedly the same as here noted, ... ." The article to which James refers is: C. Auer von Welsbach (1907) "Über die Elemente der Yttergruppe, (I. Teil)" (On the elements of the ytterbium group (1st part)), Monatshefte für Chemie und verwandte Teile anderer Wissenschaften (Monthly Journal for Chemistry and Related Fields of Other Sciences), 27 : 935-946.
^Welsbach, Carl A. von (1908). "Die Zerlegung des Ytterbiums in seine Elemente" [Resolution of ytterbium into its elements]. Monatshefte für Chemie. 29 (2): 181–225, 191. doi:10.1007/BF01558944. S2CID197766399. On page 191, Welsbach suggested names for the two new elements: "Ich beantrage für das an das Thulium, beziehungsweise Erbium sich anschließende, in dem vorstehenden Teile dieser Abhandlung mit Yb II bezeichnete Element die Benennung: Aldebaranium mit dem Zeichen Ad — und für das zweite, in dieser Arbeit mit Yb I bezeichnete Element, das letzte in der Reihe der seltenen Erden, die Benennung: Cassiopeïum mit dem Zeichen Cp." (I request for the element that is attached to thulium or erbium and that was denoted by Yb II in the above part of this paper, the designation "Aldebaranium" with the symbol Ad — and for the element that was denoted in this work by Yb I, the last in the series of the rare earths, the designation "Cassiopeïum" with the symbol Cp.)
^Castor, Stephen B.; Hedrick, James B. (2006). "Rare Earth Elements"(PDF). In Jessica Elzea Kogel, Nikhil C. Trivedi and James M. Barker (ed.). Industrial Minerals and Rocks. Society for Mining, Metallurgy and Exploration. pp. 769–792. Archived from the original on 2009-10-07.{{cite book}}: CS1 maint: bot: original URL status unknown (link)
^ abMR Pillai, Ambikalmajan, and Furn F Russ Knapp. "Evolving important role of lutetium-177 for therapeutic nuclear medicine." Current radiopharmaceuticals 8.2 (2015): 78-85.
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^Wahl, R. L. (2002). "Instrumentation". Principles and Practice of Positron Emission Tomography. Philadelphia: Lippincott: Williams and Wilkins. p. 51.
^Daghighian, F.; Shenderov, P.; Pentlow, K. S.; Graham, M. C.; Eshaghian, B.; Melcher, C. L.; Schweitzer, J. S. (1993). "Evaluation of cerium doped lutetium oxyorthosilicate (LSO) scintillation crystals for PET". IEEE Transactions on Nuclear Science. 40 (4): 1045–1047. Bibcode:1993ITNS...40.1045D. doi:10.1109/23.256710. S2CID28011497.
^Simard-Normandin, Martine (2011). "A19 LED bulbs: What's under the frosting?". EE Times (July 18): 44–45. ISSN0192-1541.
^Blasse, G.; Dirksen, G.; Brixner, L.; Crawford, M. (1994). "Luminescence of materials based on LuTaO4". Journal of Alloys and Compounds. 209 (1–2): 1–2. doi:10.1016/0925-8388(94)91069-3.
^Balter, H.; Trindade, V.; Terán, M.; Gaudiano, J.; Ferrando, R.; Paolino, A.; Rodriguez, G.; Hermida, J.; De Marco, E.; Oliver, P. (2015). "177Lu-Labeled Agents for Neuroendocrine Tumor Therapy and Bone Pain Palliation in Uruguay". Current Radiopharmaceuticals. 9 (1): 85–93. doi:10.2174/1874471008666150313112620. PMID25771367.
^Carollo, A.; Papi, S.; Chinol, M. (2015). "Lutetium-177 Labeled Peptides: The European Institute of Oncology Experience". Current Radiopharmaceuticals. 9 (1): 19–32. doi:10.2174/1874471008666150313111633. PMID25771368.
