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holmium
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Properties
Holmium is the eleventh member of the lanthanide series. In the periodic table, it appears in period 6, between the lanthanides dysprosium to its left and erbium to its right, and above the actinide einsteinium.Physical properties
With a boiling point of {{convert|3000|K|C}}, holmium is the sixth most volatile lanthanide after ytterbium, europium, samarium, thulium and dysprosium. At standard temperature and pressure, holmium, like many of the second half of the lanthanides, normally assumes a hexagonally close-packed (hcp) structure.JOURNAL, Strandburg, D. L., Legvold, S., Spedding, F. H., 1962-09-15, Electrical and Magnetic Properties of Holmium Single Crystals,weblink Physical Review, 127, 6, 2046â2051, 10.1103/PhysRev.127.2046, 1962PhRv..127.2046S, subscription, Its 67 electrons are arranged in the configuration [Xe] 4f11 6s2, so that it has thirteen valence electrons filling the 4f and 6s subshells.{{citation required|date=August 2023}}Holmium, like all of the lanthanides, at paramagnetic in standard temperature and pressure.BOOK, Cullity, B. D., Graham, C. D., 2005, 172, Introduction to Magnetic Materials, However, holmium is ferromagnetic at temperatures below {{convert|19|K|C F}}.BOOK, Introduction to magnetism and magnetic materials, Jiles, David, 228, 1998, It has the highest magnetic moment ({{val|10.6|u=μB}}) of any naturally occurring element and possesses other unusual magnetic properties. When combined with yttrium, it forms highly magnetic compounds.Chemical properties
Holmium metal tarnishes slowly in air, forming a yellowish oxide layer that has an appearance similar to that of iron rust. It burns readily to form holmium(III) oxide:JOURNAL, Wahyudi, Tatang, 2015, Reviewing the properties of rare earth element-bearing minerals, rare-earth elements and cerium oxide compound,weblink Indonesian Mining Journal, en, 18, 2, 92â108, 10.30556/imj.Vol18.No2.2015.293, 31 January 2024, 2527-8797,
4 Ho + 3 O2 â 2 Ho2O3
It is a relatively soft and malleable element that is fairly corrosion-resistant and chemically stable in dry air at standard temperature and pressure. In moist air and at higher temperatures, however, it quickly oxidizes, forming a yellowish oxide.JOURNAL, Phillips, W. L., 1964-08-01, Oxidation of several lanthanide elements,weblink Journal of the Less Common Metals, en, 7, 2, 139â143, 10.1016/0022-5088(64)90056-6, 0022-5088, subscription, In pure form, holmium possesses a metallic, bright silvery luster.Holmium is quite electropositive: on the Pauling electronegativity scale, it has an electronegativity of 1.23.WEB, Winter, Mark J., Holmium - 67Ho: electronegativity,weblink WebElements, University of Sheffield, 4 August 2023, It is generally trivalent. It reacts slowly with cold water and quickly with hot water to form holmium(III) hydroxide:JOURNAL, An, Tao, Dou, Chunyue, Ju, Jinning, Wei, Wenlong, Ji, Quanzeng, 2019-06-01, Microstructure, morphology, wettability and mechanical properties of Ho2O3 films prepared by glancing angle deposition,weblink Vacuum, en, 164, 405â410, 10.1016/j.vacuum.2019.03.057, 2019Vacuu.164..405A, 133466738, 0042-207X, subscription,
2 Ho (s) + 6 H2O (l) â 2 Ho(OH)3 (aq) + 3 H2 (g)
Holmium metal reacts with all the stable halogens:
2 Ho (s) + 3 F2 (g) â 2 HoF3 (s) [pink]
2 Ho (s) + 3 Cl2 (g) â 2 HoCl3 (s) [yellow]
2 Ho (s) + 3 Br2 (g) â 2 HoBr3 (s) [yellow]
2 Ho (s) + 3 I2 (g) â 2 HoI3 (s) [yellow]
Holmium dissolves readily in dilute sulfuric acid to form solutions containing the yellow Ho(III) ions, which exist as a [Ho(OH2)9]3+ complexes:WEB,weblink Chemical reactions of Holmium, Webelements, 2009-06-06,
2 Ho (s) + 3 H2SO4 (aq) â 2 Ho3+ (aq) + 3 {{chem|SO|4|2-}} (aq) + 3 H2 (g)
Oxidation states
As with many lanthanides, holmium is usually found in the +3 oxidation state, forming compounds such as holmium(III) fluoride (HoF3) and holmium(III) chloride (HoCl3). Holmium in solution is in the form of Ho3+ surrounded by nine molecules of water. Holmium dissolves in acids.BOOK, Emsley, John, Nature's Building Blocks, 226, 2011, However, holmium is also found to exist in the +2, +1 and 0 oxidation states.{{citation required|date=August 2023}}Isotopes
{{further|Isotopes of holmium}}The isotopes of holmium range from 140Ho to 175Ho. The primary decay mode before the most abundant stable isotope, 165Ho, is positron emission, and the primary mode after is beta minus decay. The primary decay products before 165Ho are terbium and dysprosium isotopes, and the primary products after are erbium isotopes.Natural holmium consists of one primordial isotope, holmium-165; it is the only isotope of holmium that is thought to be stable, although it is predicted to undergo alpha decay to terbium-161 with a very long half-life.JOURNAL, Belli, P., Bernabei, R., Danevich, F. A., Incicchitti, A., Tretyak, V. I., 3, Experimental searches for rare alpha and beta decays, European Physical Journal A, 2019, 55, 8, 140â1â140â7, 10.1140/epja/i2019-12823-2, 1434-601X, 1908.11458, 2019EPJA...55..140B, 201664098, Of the 35 synthetic radioactive isotopes that are known, the most stable one is holmium-163 (163Ho), with a half-life of 4570 years.JOURNAL, Naumann, R. A., Michel, M. C., Power, J. L., Preparation of long-lived holmium-163, September 1960, 4120223, Journal of Inorganic and Nuclear Chemistry, en, 15, 1â2, 195â196, 10.1016/0022-1902(60)80035-8, All other radioisotopes have ground-state half-lives not greater than 1.117 days, with the longest, holmium-166 (166Ho) having a half-life of 26.83 hours,JOURNAL, Suzuki, Yuka S, 1998, Biodistribution and kinetics of holmium-166-chitosan complex (DW-166HC) in rats and mice.,weblink Journal of Nuclar Medicine, 39, 12, 2161â2166, 9867162, and most have half-lives under 3 hours.166m1Ho has a half-life of around 1200 years.JOURNAL, Klaassen, Nienke J. M., Arntz, Mark J., Gil Arranja, Alexandra, Roosen, Joey, Nijsen, J. Frank W., 2019-08-05, The various therapeutic applications of the medical isotope holmium-166: a narrative review, EJNMMI Radiopharmacy and Chemistry, 4, 1, 19, 10.1186/s41181-019-0066-3, 2365-421X, 31659560, 6682843, free, The high excitation energy, resulting in a particularly rich spectrum of decay gamma rays produced when the metastable state de-excites, makes this isotope useful as a means for calibrating gamma ray spectrometers.WEB, Oliveira, Bernardes, Estela Maria de, 2001-01-01, Holmium-166m: multi-gamma standard to determine the activity of radionuclides in semiconductor detectors,weblink Portuguese,Compounds
Oxides and chalcogenides
missing image!
- Holmium(III) oxide.jpg -
right|Ho2O3, left: natural light, right: under a cold-cathode fluorescent lamp
Holmium(III) oxide is the only oxide of holmium. It changes its color depending on the lighting conditions. In daylight, it has a yellowish color. Under trichromatic light, it appears orange red, almost indistinguishable from the appearance of erbium oxide under the same lighting conditions.BOOK, Ganjali, Mohammad Reza, Lanthanides Series Determination by Various Analytical Methods, Gupta, Vinod Kumar, Faridbod, Farnoush, Norouzi, Parviz, 2016-02-25, 27, The color change is related to the sharp emission lines of trivalent holmium ions acting as red phosphors.JOURNAL, 10.1246/cl.2008.762, Hydrothermal Synthesis of GdVO4:Ho3+ Nanorods with a Novel White-light Emission, 2008, Su, Yiguo, Chemistry Letters, 37, 762â763, 7, Li, Guangshe, Chen, Xiaobo, Liu, Junjie, Li, Liping, Holmium(III) oxide appears pink under a cold-cathode fluorescent lamp.Other chalcogenides are known for holmium. Holmium(III) sulfide has orange-yellow crystals in the monoclinic crystal system, with the space group P21/m (No. 11).BOOK,weblink Ho2S3: crystal structure, physical properties, 2021-06-22, 2018-09-01,weblink live, 10.1007/10681735_623, Non-Tetrahedrally Bonded Binary Compounds II, Landolt-Börnstein - Group III Condensed Matter, 2000, 41D, 1â3, 3-540-64966-2, Under high pressure, holmium(III) sulfide can form in the cubic and orthorhombic crystal systems.BOOK, E. Yu, Tonkov, Compounds and Alloys Under High Pressure A Handbook, 1998, 272, It can be obtained by the reaction of holmium(III) oxide and hydrogen sulfide at {{convert|1598|K|C F}}.BOOK, G. Meyer, Lester R. Morss, Synthesis of Lanthanide and Actinide Compounds, 1991, 329, Holmium(III) selenide is also known. It is antiferromagnetic below 6 K.JOURNAL, Bespyatov, M. A., Musikhin, A. E., Naumov, V. N., Zelenina, L. N., Chusova, T. P., Nikolaev, R. E., Naumov, N. G., 2018-03-01, Low-temperature thermodynamic properties of holmium selenide (2:3),weblink The Journal of Chemical Thermodynamics, en, 118, 21â25, 10.1016/j.jct.2017.10.013, 0021-9614, subscription, - Holmium(III) oxide.jpg -
right|Ho2O3, left: natural light, right: under a cold-cathode fluorescent lamp
Halides
All four trihalides of holmium are known. Holmium(III) fluoride is a yellowish powder that can be produced by reacting holmium(III) oxide and ammonium fluoride, then crystallising it from the ammonium salt formed in solution.BOOK, Riedel, moderne anorganische Chemie, 2012, De Gruyter, Erwin Riedel, Christoph Janiak, Hans-Jürgen Meyer, Holmium(III) chloride can be prepared in a similar way, with ammonium chloride instead of ammonium fluoride.WEB, Holmium chloride {{!, 10138-62-2 |url=https://www.chemicalbook.com/ChemicalProductProperty_EN_CB0255341.htm |access-date=2023-08-09 |website=ChemicalBook |language=en}} It has the YCl3 layer structure in the solid state.BOOK, Wells, A. F., Structural inorganic chemistry, 421, These compounds, as well as holmium(III) bromide and holmium(III) iodide, can be obtained by the direct reaction of the elements:
2 Ho + 3 X2 â 2 HoX3
In addition, holmium(III) iodide can be obtained by the direct reaction of holmium and mercury(II) iodide, then removing the mercury by distillation.JOURNAL, 10.1021/ic50018a015, Preparation and crystal data for lanthanide and actinide triiodides, 1964, Asprey, L. B., Keenan, T. K., Kruse, F. H., Inorganic Chemistry, 3, 8, 1137â1141,weblink subscription, Organoholmium compounds
{{See also|Organolanthanide chemistry}}Organoholmium compounds are very similar to those of the other lanthanides, as they all share an inability to undergo Ï backbonding. They are thus mostly restricted to the mostly ionic cyclopentadienides (isostructural with those of lanthanum) and the Ï-bonded simple alkyls and aryls, some of which may be polymeric.Greenwood and Earnshaw, pp. 1248{{ndash}}1249History
Holmium (, Latin name for Stockholm) was discovered by the Swiss chemists Jacques-Louis Soret and Marc Delafontaine in 1878 who noticed the aberrant spectrographic emission spectrum of the then-unknown element (they called it "Element X").JOURNAL, Sur les spectres d'absorption ultra-violets des terres de la gadolinite, Jacques-Louis Soret, Comptes rendus de l'Académie des sciences, 87, 1062, 1878,weblink JOURNAL, Sur le spectre des terres faisant partie du groupe de l'yttriajournal = Comptes rendus de l'Académie des sciences | pages = 521 | url =weblink The Swedish chemist Per Teodor Cleve also independently discovered the element while he was working on erbia earth (erbium oxide). He was the first to isolate the new element.WEB, Holmium,weblink Royal Society of Chemistry, 2020, 4 January 2020, JOURNAL, Marshall, James L. Marshall, Marshall, Virginia R. Marshall, Rediscovery of the elements: The Rare EarthsâThe Confusing Years, The Hexagon, 2015, 72â77,weblink 30 December 2019, BOOK, Weeks, Mary Elvira, The discovery of the elements, 1956, Journal of Chemical Education, 710, Using the method developed by the Swedish chemist Carl Gustaf Mosander, Cleve first removed all of the known contaminants from erbia. The result of that effort was two new materials, one brown and one green. He named the brown substance holmia (after the Latin name for Cleve's home town, Stockholm) and the green one thulia. Holmia was later found to be the holmium oxide, and thulia was thulium oxide.In the English physicist Henry Moseley's classic paper on atomic numbers, holmium was assigned the value 66. The holmium preparation he had been given to investigate had been impure, dominated by neighboring (at the time undiscovered) dysprosium. He would have seen x-ray emission lines for both elements, but assumed that the dominant ones belonged to holmium, instead of the dysprosium impurity.JOURNAL, Moseley, H.G.J., The high-frequency spectra of the elements, Philosophical Magazine, 1913, 26, 1024â1034,weblink 6th series, Occurrence and productionFile:Gadolinitas.jpg|thumb|A specimen of gadolinitegadoliniteLike all the other rare-earth elements, holmium is not naturally found as a free element. It occurs combined with other elements in gadolinite, monazite and other rare-earth minerals. No holmium-dominant mineral has yet been found. The main mining areas are China, United States, Brazil, India, Sri Lanka, and Australia with reserves of holmium estimated as 400,000 tonnes. The annual production of holmium metal is of about 10 tonnes per year.WEB, Ho - Holmium,weblink 5 December 2022, MMTA, Holmium makes up 1.3 parts per million of the Earth's crust by mass.ABUNDANCE OF ELEMENTS IN THE EARTHâS CRUST AND IN THE SEA, CRC Handbook of Chemistry and Physics, 97th edition (2016â2017), p. 14-17 Holmium makes up 1 part per million of the soils, 400 parts per quadrillion of seawater, and almost none of Earth's atmosphere, which is very rare for a lanthanide.BOOK, Emsley, John, Nature's Building Blocks, 225, 2011, It makes up 500 parts per trillion of the universe by mass.WEB,weblink WebElements Periodic Table » Periodicity » Abundance in the universe » periodicity, Mark Winter, University of Sheffield and WebElements, Ltd, www.webelements.com, 27 March 2018,weblink 2017-09-29, Holmium is commercially extracted by ion exchange from monazite sand (0.05% holmium), but is still difficult to separate from other rare earths. The element has been isolated through the reduction of its anhydrous chloride or fluoride with metallic calcium. Its estimated abundance in the Earth's crust is 1.3 mg/kg. Holmium obeys the OddoâHarkins rule: as an odd-numbered element, it is less abundant than both dysprosium and erbium. However, it is the most abundant of the odd-numbered heavy lanthanides. Of the lanthanides, only promethium, thulium, lutetium and terbium are less abundant on Earth. The principal current source are some of the ion-adsorption clays of southern China. Some of these have a rare-earth composition similar to that found in xenotime or gadolinite. Yttrium makes up about two-thirds of the total by mass; holmium is around 1.5%.BOOK, Patnaik, Pradyot, 2003, Handbook of Inorganic Chemical Compounds, McGraw-Hill, 338â339, 0-07-049439-8,weblink 2009-06-06,weblink 2023-06-14, Holmium is relatively inexpensive for a rare-earth metal with the price about 1000 USD/kg.NEWS, USGS, Rare-Earth Metals, James B. Hedrick, 2009-06-06,weblinkApplicationsFile:HoOxideSolution.jpg|thumb|A solution of 4% holmium oxide in 10% perchloric acid, permanently fused into a quartz cuvettecuvetteGlass containing holmium oxide and holmium oxide solutions (usually in perchloric acid) have sharp optical absorption peaks in the spectral range 200 to 900 nm. They are therefore used as a calibration standard for optical spectrophotometers.JOURNAL, Allen, David W., Holmium oxide glass wavelength standards, Journal of Research of the National Institute of Standards and Technology, 112, 6, 2007, 303â306, 1044-677X, 10.6028/jres.112.024, 27110474, 4655923, JOURNAL, Travis, John C., Zwinkels, Joanne C., Mercader, Flora, etal, An International Evaluation of Holmium Oxide Solution Reference Materials for Wavelength Calibration in Molecular Absorption Spectrophotometry, Analytical Chemistry, 74, 14, 2002-06-05, 0003-2700, 10.1021/ac0255680, 3408â3415, 12139047, JOURNAL,weblink Clinical Chemistry, 10, 1964, Uses for a Holmium Oxide Filter in Spectrophotometry, R. P. MacDonald, 14240747, 12, 1117â20, 10.1093/clinchem/10.12.1117, subscription, The radioactive but long-lived 166m1Ho is used in calibration of gamma-ray spectrometers.JOURNAL, The absolute counting of 166mHo, 58Co and 88Y, Ming-Chen Yuan, Jeng-Hung Lee, Wen-Song Hwang, amp, 10.1016/S0969-8043(01)00226-3, 11839051, Applied Radiation and Isotopes | issue = 1â2 | date = 2002, Holmium is used to create the strongest artificially generated magnetic fields, when placed within high-strength magnets as a magnetic pole piece (also called a magnetic flux concentrator).JOURNAL, IEEE Transactions on Magnetics, 21, 1985, 6, R. W. Hoard, Field enhancement of a 12.5-T magnet using holmium poles, S. C. Mance, R. L. Leber, E. N. Dalder, M. R. Chaplin, K. Blair, D. H. Nelson, D. A. Van Dyke, 2, 448â450, 10.1109/tmag.1985.1063692, 1985ITM....21..448H, 121828376,weblink Holmium is also used in the manufacture of some permanent magnets.Holmium-doped yttrium iron garnet (YIG) and yttrium lithium fluoride have applications in solid-state lasers, and Ho-YIG has applications in optical isolators and in microwave equipment (e.g., YIG spheres). Holmium lasers emit at 2.1 micrometres.JOURNAL, The holmium laser in urology, Journal of Clinical Laser Medicine & Surgery, 9728125, 16, 1, Feb 1998, 13â20, Wollin, T. A., Denstedt, J. D., 10.1089/clm.1998.16.13, They are used in medical, dental, and fiber-optical applications.BOOK, 30,weblink Extractive metallurgy of rare earths, C. K. Gupta, Nagaiyar Krishnamurthy, CRC Press, 2004, 0-415-33340-7, It is also being considered for usage in the enucleation of the prostate.JOURNAL, Gilling, Peter J., Aho, Tevita F., Frampton, Christopher M., King, Colleen J., Fraundorfer, Mark R., 2008-04-01, Holmium Laser Enucleation of the Prostate: Results at 6 Years,weblink European Urology, en, 53, 4, 744â749, 10.1016/j.eururo.2007.04.052, 17475395, 0302-2838, subscription, Since holmium can absorb nuclear fission-bred neutrons, it is used as a burnable poison to regulate nuclear reactors. It is used as a colorant for cubic zirconia, providing pink coloring,JOURNAL, Nassau, Kurt, Spring 1981, Cubic zirconia: An Update., Gems & Gemology, 1, 9â19, 10.5741/GEMS.17.1.9,weblink and for glass, providing yellow-orange coloring.JOURNAL, El-Batal, Hatem A., Azooz, Moenis A., Ezz-El-Din, Fathy M., El-Alaily, Nagia A., 2004-12-20, Interaction of Gamma Rays with Calcium Aluminoborate Glasses Containing Holmium or Erbium,weblink Journal of the American Ceramic Society, en, 84, 9, 2065â2072, 10.1111/j.1151-2916.2001.tb00959.x, subscription, In March 2017, IBM announced that they had developed a technique to store one bit of data on a single holmium atom set on a bed of magnesium oxide.WEB,weblink 2017-03-10, Storing data in a single atom proved possible by IBM researchers, TechCrunch, Coldeway, Devin, March 9, 2017, With sufficient quantum and classical control techniques, holmium may be a good candidate to make quantum computers.JOURNAL, Forrester, Patrick Robert, Patthey, François, Fernandes, Edgar, Sblendorio, Dante Phillipe, Brune, Harald, Natterer, Fabian Donat, 2019-11-19, Quantum state manipulation of single atom magnets using the hyperfine interaction, Physical Review B, en, 100, 18, 180405, 10.1103/PhysRevB.100.180405, 1903.00242, 2469-9950, 2019PhRvB.100r0405F, free, Biological role and precautionsHolmium plays no biological role in humans, but its salts are able to stimulate metabolism.BOOK, C. R. Hammond, The Elements, in Handbook of Chemistry and Physics, 81st, CRC press, 2000, 0-8493-0481-4, Humans typically consume about a milligram of holmium a year. Plants do not readily take up holmium from the soil. Some vegetables have had their holmium content measured, and it amounted to 100 parts per trillion.BOOK, Emsley, John, Nature's Building Blocks, 224, 2011, Holmium and its soluble salts are slightly toxic if ingested, but insoluble holmium salts are nontoxic. Metallic holmium in dust form presents a fire and explosion hazard.JOURNAL, Haley, T. J., Koste, L., Komesu, N., Efros, M., Upham, H. C., 1966, Pharmacology and toxicology of dysprosium, holmium, and erbium chlorides, Toxicology and Applied Pharmacology, 8, 1, 37â43, 10.1016/0041-008x(66)90098-6, 5921895, JOURNAL, Haley, T. J., 1965, Pharmacology and toxicology of the rare earth elements, Journal of Pharmaceutical Sciences, 54, 5, 663â70, 10.1002/jps.2600540502, 5321124, JOURNAL, Bruce, D. W., Hietbrink, B. E., Dubois, K. P., 1963, The acute mammalian toxicity of rare earth nitrates and oxides, Toxicology and Applied Pharmacology, 5, 6, 750â9, 10.1016/0041-008X(63)90067-X, 14082480, Large amounts of holmium salts can cause severe damage if inhaled, consumed orally, or injected. The biological effects of holmium over a long period of time are not known. Holmium has a low level of acute toxicity.WEB, 2011-04-15, Holmium: Biological Action,weblink 2023-03-05,weblink" title="web.archive.org/web/20110415162101weblink">weblink 2011-04-15,See also
References{{Reflist|30em}}Bibliography
Further reading
External links{{Commons|Holmium}}
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