Thulium: Difference between revisions

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{{Short description | Chemical element with symbol Tm, atomic number 69}}
{{Distinguish|Thallium}}
{{Distinguish|Thallium}}
{{Good article}}
{{Good article}}
{{Infobox thulium}}
{{Infobox thulium}}
'''Thulium''' is a [[chemical element]]; it has [[Symbol (chemistry)|symbol]] '''Tm''' and [[atomic number]] 69. It is the thirteenth element in the [[lanthanide]] series of [[metal]]s. It is the second-least abundant lanthanide in the Earth's crust, after radioactively unstable [[promethium]]. It is an easily workable metal with a bright silvery-gray luster. It is fairly soft and slowly [[tarnish]]es in air. Despite its high price and rarity, thulium is used as a [[dopant]] in [[solid-state laser]]s, and as the radiation source in some portable [[X-ray]] devices. It has no significant biological role and is not particularly toxic.
'''Thulium''' is a [[chemical element]]; it has [[Symbol (chemistry)|symbol]] '''Tm''' and [[atomic number]] 69. It is the thirteenth element in the [[lanthanide]] series of [[metal]]s. It is the second-least abundant lanthanide in the Earth's crust, after radioactively unstable [[promethium]]. It is an easily workable metal with a bright silvery-gray luster. It is fairly soft and slowly [[tarnish]]es in air. Despite its high price and rarity, thulium is used as a [[dopant]] in [[solid-state laser]]s. It has no significant biological role and is not particularly toxic. Artificial radioactive [[isotopes of thulium]] are used as [[#X-ray source|radiation sources]] in some portable [[X-ray]] devices.


In 1879, the Swedish chemist [[Per Teodor Cleve]] separated two previously unknown components, which he called [[holmium(III) oxide|holmia]] and [[thulium(III) oxide|thulia]], from the [[rare-earth]] mineral [[erbium(III) oxide|erbia]]; these were the oxides of [[holmium]] and thulium, respectively. His example of thulium oxide contained impurities of ytterbium oxide. A relatively pure sample of thulium oxide was first obtained in 1911. The metal itself was first obtained in 1936 by [[Wilhelm Klemm]] and Heinrich Bommer.<ref>{{cite journal|author1=W. Klemm|author2=H. Bommer|title=Zur Kenntnis der Metalle der seltenen Erden.|lang=de|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=231|year=1937|issue=1–2 |pages=138–171|doi=10.1002/zaac.19372310115}}.</ref>
In 1879, the Swedish chemist [[Per Teodor Cleve]] separated two previously unknown components, which he called [[holmium(III) oxide|holmia]] and [[thulium(III) oxide|thulia]], from the [[rare-earth]] mineral [[erbium(III) oxide|erbia]]; these were the oxides of [[holmium]] and thulium, respectively. His example of thulium oxide contained impurities of ytterbium oxide. A relatively pure sample of thulium oxide was first obtained in 1911. The metal itself was first obtained in 1936 by [[Wilhelm Klemm]] and Heinrich Bommer.<ref>{{cite journal|author1=W. Klemm|author2=H. Bommer|title=Zur Kenntnis der Metalle der seltenen Erden.|lang=de|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=231|year=1937|issue=1–2 |pages=138–171|doi=10.1002/zaac.19372310115 |bibcode=1937ZAACh.231..138K |url=https://pbc.gda.pl/dlibra/publication/edition/36/content }}.</ref>


Like the other lanthanides, its most common [[oxidation state]] is +3, seen in its oxide, halides and other compounds. In [[aqueous solution]], like compounds of other late lanthanides, soluble thulium compounds form [[coordination complex]]es with nine water molecules.
Like the other lanthanides, its most common [[oxidation state]] is +3, seen in its oxide, halides and other compounds. In [[aqueous solution]], like compounds of other late lanthanides, soluble thulium compounds form [[coordination complex]]es with nine water molecules.
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: {{chem2|4Tm + 3O2 → 2Tm2O3}}
: {{chem2|4Tm + 3O2 → 2Tm2O3}}
Thulium [[dust]] can cause [[explosion]]s and [[fires]].<ref>{{cite web |author1=Thermo Fisher Scientific Chemicals, Inc. |title=SAFETY DATA SHEET |url=https://www.fishersci.com/store/msds?partNumber=AA4416803&productDescription=THULIUM+PWR+-40+MESH+99.9%25+1G&vendorId=VN00024248&countryCode=US&language=en |website=fisher scientific |access-date=1 June 2024 |location=Section: 5. Fire-fighting measures |date=28 March 2024}}</ref>


Thulium is quite [[electropositive]] and reacts slowly with cold water and quite quickly with hot water to form thulium hydroxide:
Thulium is quite [[electropositive]] and reacts slowly with cold water and quite quickly with hot water to form thulium hydroxide:
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: {{chem2|2Tm_{(s)} + 3H2SO4_{(aq)} → 2Tm(3+)_{(aq)} + 3SO4(2-)_{(aq)} + 3H2_{(aq)}|}}
: {{chem2|2Tm_{(s)} + 3H2SO4_{(aq)} → 2Tm(3+)_{(aq)} + 3SO4(2-)_{(aq)} + 3H2_{(aq)}|}}


Thulium reacts with various metallic and non-metallic elements forming a range of binary compounds, including {{chem2|TmN}}, {{chem2|TmS}}, {{chem2|TmC2}}, {{chem2|Tm2C3}}, {{chem2|TmH2}}, {{chem2|TmH3}}, {{chem2|TmSi2}}, {{chem2|TmGe3}}, {{chem2|TmB4}}, {{chem2|TmB6}} and {{chem2|TmB12}}.{{citation needed|date=March 2014}} Like most lanthanides, the +3 state is most common and is the only state observed in thulium solutions.<ref name="patnaik">{{cite book |last= Patnaik |first= Pradyot |date= 2003 |title= Handbook of Inorganic Chemical Compounds |publisher= McGraw-Hill |page= 934 |isbn= 0-07-049439-8 |url= https://books.google.com/books?id=Xqj-TTzkvTEC&pg=PA934}}</ref> Thulium exists as a {{chem2|Tm(3+)}} ion in solution. In this state, the thulium ion is surrounded by nine molecules of water.<ref name="history" /> {{chem2|Tm(3+)}} ions exhibit a bright blue luminescence.<ref name="history" /> Because it occurs late in the [[lanthanide series|series]], the +2 oxidation state can also exist, stabilized by the nearly full 4f [[electron shell]], but occurs only in solids.{{cn|date=April 2022}}
Thulium reacts with various metallic and non-metallic elements forming a range of binary compounds, including {{chem2|TmN}}, {{chem2|TmS}}, {{chem2|TmC2}}, {{chem2|Tm2C3}}, {{chem2|TmH2}}, {{chem2|TmH3}}, {{chem2|TmSi2}}, {{chem2|TmGe3}}, {{chem2|TmB4}}, {{chem2|TmB6}} and {{chem2|TmB12}}.{{citation needed|date=March 2014}} Like most lanthanides, the +3 state is most common and is the only state observed in thulium solutions.<ref name="patnaik">{{cite book |last= Patnaik |first= Pradyot |date= 2003 |title= Handbook of Inorganic Chemical Compounds |publisher= McGraw-Hill |page= 934 |isbn= 0-07-049439-8 |url= https://books.google.com/books?id=Xqj-TTzkvTEC&pg=PA934}}</ref> Thulium exists as a {{chem2|Tm(3+)}} ion in solution. In this state, the thulium ion is surrounded by nine molecules of water.<ref name="history" /> {{chem2|Tm(3+)}} ions exhibit a bright blue luminescence.<ref name="history" /> Because it occurs late in the [[lanthanide series|series]], the +2 oxidation state can also exist, stabilized by the nearly full 4f [[electron shell]], but occurs only in solids.{{citation needed|date=April 2022}}


Thulium's only known oxide is [[thulium oxide|{{chem2|Tm2O3}}]]. This oxide is sometimes called "thulia".<ref name= "hist and use">{{cite book |url= https://books.google.com/books?id=yb9xTj72vNAC&pg=PA300 |title= The History and Use of Our Earth's Chemical Elements: A Reference Guide |isbn= 978-0-313-33438-2 |author= Krebs, Robert E |date= 2006|publisher= Greenwood Publishing }}</ref> Reddish-purple thulium(II) compounds can be made by the [[chemical reduction|reduction]] of thulium(III) compounds. Examples of thulium(II) compounds include the halides (except the fluoride). Some hydrated thulium compounds, such as {{chem2|TmCl3*7H2O}} and {{chem2|Tm2(C2O4)3*6H2O}} are green or greenish-white.<ref name= "concise encyclopedia">{{cite book |url=https://books.google.com/books?id=Owuv-c9L_IMC&pg=PA1105 |title=Concise Encyclopedia Chemistry |isbn=978-3-11-011451-5 |last1=Eagleson |first1=Mary |date=1994|publisher=Walter de Gruyter|page=1105}}</ref> Thulium dichloride reacts very vigorously with [[water]]. This reaction results in [[hydrogen]] gas and [[thulium(III) hydroxide|{{chem2|Tm(OH)3}}]] exhibiting a fading reddish color.{{citation needed|date=March 2014}} Combination of thulium and [[chalcogens]] results in thulium [[chalcogenide]]s.<ref>{{cite book |url=https://books.google.com/books?id=es-Pu2hI5swC |title=Advances in Inorganic Chemistry and Radiochemistry |isbn=978-0-08-057869-9 |last1=Emeléus |first1=H. J. |last2=Sharpe |first2=A. G. |date=1977|publisher=Academic Press}}</ref>
Thulium's only known oxide is [[thulium oxide|{{chem2|Tm2O3}}]]. This oxide is sometimes called "thulia".<ref name= "hist and use">{{cite book |url= https://books.google.com/books?id=yb9xTj72vNAC&pg=PA300 |title= The History and Use of Our Earth's Chemical Elements: A Reference Guide |isbn= 978-0-313-33438-2 |author= Krebs, Robert E |date= 2006|publisher= Greenwood Publishing }}</ref> Reddish-purple thulium(II) compounds can be made by the [[chemical reduction|reduction]] of thulium(III) compounds. Examples of thulium(II) compounds include the halides (except the fluoride). Some hydrated thulium compounds, such as {{chem2|TmCl3*7H2O}} and {{chem2|Tm2(C2O4)3*6H2O}} are green or greenish-white.<ref name= "concise encyclopedia">{{cite book |url=https://books.google.com/books?id=Owuv-c9L_IMC&pg=PA1105 |title=Concise Encyclopedia Chemistry |isbn=978-3-11-011451-5 |last1=Eagleson |first1=Mary |date=1994|publisher=Walter de Gruyter|page=1105}}</ref> Thulium dichloride reacts very vigorously with [[water]]. This reaction results in [[hydrogen]] gas and [[thulium(III) hydroxide|{{chem2|Tm(OH)3}}]] exhibiting a fading reddish color.{{citation needed|date=March 2014}} Combination of thulium and [[chalcogen]]s results in thulium [[chalcogenide]]s.<ref>{{cite book |url=https://books.google.com/books?id=es-Pu2hI5swC |title=Advances in Inorganic Chemistry and Radiochemistry |isbn=978-0-08-057869-9 |last1=Emeléus |first1=H. J. |last2=Sharpe |first2=A. G. |date=1977|publisher=Academic Press}}</ref>


Thulium reacts with [[hydrogen chloride]] to produce hydrogen gas and thulium chloride. With [[nitric acid]] it yields thulium nitrate, or {{chem2|Tm(NO3)3}}.<ref name="cool">{{Cite web|title=Thulium|url=http://www.chemicool.com/elements/thulium.html|access-date=2023-03-10|website=www.chemicool.com}}</ref>
Thulium reacts with [[hydrogen chloride]] to produce hydrogen gas and thulium chloride. With [[nitric acid]] it yields thulium nitrate, {{chem2|Tm(NO3)3}}.<ref name="cool">{{Cite web|title=Thulium|url=http://www.chemicool.com/elements/thulium.html|access-date=2023-03-10|website=www.chemicool.com}}</ref>


=== Isotopes ===
=== Isotopes ===
{{Main|Isotopes of thulium}}
{{Main|Isotopes of thulium}}


The isotopes of thulium range from {{chem2|^{144}Tm}} to {{chem2|^{183}Tm}}.{{NUBASE2020|ref}}<ref name=PRL132.7>{{cite journal |first1=O. B. |last1=Tarasov |first2=A. |last2=Gade |first3=K. |last3=Fukushima |display-authors=et al. |title=Observation of New Isotopes in the Fragmentation of <sup>198</sup>Pt at FRIB |journal=Physical Review Letters |volume=132 |number=72501 |date=2024 |page=072501 |doi=10.1103/PhysRevLett.132.072501|pmid=38427880 |bibcode=2024PhRvL.132g2501T }}</ref> The primary [[decay mode]] before the most abundant stable isotope, {{chem2|^{169}Tm}}, is [[electron capture]], and the primary mode after is [[beta emission]]. The primary [[decay product]]s before {{chem2|^{169}Tm}} are element 68 ([[erbium]]) isotopes, and the primary products after are element 70 ([[ytterbium]]) isotopes.<ref name="hand">{{cite book |last= Lide |first= David R. |date= 1998|title= Handbook of Chemistry and Physics|edition= 87th |location= Boca Raton, FL |publisher= CRC Press |isbn= 0-8493-0594-2 |chapter= Section 11, Table of the Isotopes}}</ref>
Natural thulium consists of the single stable isotope thulium-169 (it is predicted to undergo [[alpha decay]] to [[holmium]]-165 with a very long half-life.<ref name="history" /><ref name="bellidecay">{{cite journal |last1=Belli |first1=P. |last2=Bernabei |first2=R. |last3=Danevich |first3=F. A. |last4=Incicchitti |first4=A. |last5=Tretyak |first5=V. I. |display-authors=3 |title=Experimental searches for rare alpha and beta decays |journal=European Physical Journal A |date=2019 |volume=55 |issue=8 |pages=140–1–140–7 |doi=10.1140/epja/i2019-12823-2 |issn=1434-601X |arxiv=1908.11458|bibcode=2019EPJA...55..140B |s2cid=201664098 }}</ref>). Known isotopes of thulium range from {{chem2|^{144}Tm}} to {{chem2|^{183}Tm}}.{{NUBASE2020|ref}}<ref name=PRL132.7>{{cite journal |first1=O. B. |last1=Tarasov |first2=A. |last2=Gade |first3=K. |last3=Fukushima |display-authors=et al. |title=Observation of New Isotopes in the Fragmentation of <sup>198</sup>Pt at FRIB |journal=Physical Review Letters |volume=132 |number=72501 |date=2024 |article-number=072501 |doi=10.1103/PhysRevLett.132.072501|pmid=38427880 |bibcode=2024PhRvL.132g2501T |osti=2309727 }}</ref>
 
Thulium-169 is thulium's only [[primordial isotope]] and is the only isotope of thulium that is thought to be stable; it is predicted to undergo [[alpha decay]] to [[holmium]]-165 with a very long half-life.<ref name="history" /><ref name="bellidecay">{{cite journal |last1=Belli |first1=P. |last2=Bernabei |first2=R. |last3=Danevich |first3=F. A. |last4=Incicchitti |first4=A. |last5=Tretyak |first5=V. I. |display-authors=3 |title=Experimental searches for rare alpha and beta decays |journal=European Physical Journal A |date=2019 |volume=55 |issue=8 |pages=140–1–140–7 |doi=10.1140/epja/i2019-12823-2 |issn=1434-601X |arxiv=1908.11458|bibcode=2019EPJA...55..140B |s2cid=201664098 }}</ref> The longest-lived radioisotopes are thulium-171, which has a [[half-life]] of 1.92 years, and [[thulium-170]], which has a half-life of 128.6 days. Most other isotopes have half-lives of a few minutes or less.<ref name="Nudat">
{{cite web
|first=Alejandro
|last=Sonzogni
|url=https://www.nndc.bnl.gov/nudat2/reCenter.jsp?z=69&n=97
|title=Untitled
|publisher=[[National Nuclear Data Center]]
|access-date=2013-02-20
|archive-date=2020-11-21
|archive-url=https://web.archive.org/web/20201121010223/https://www.nndc.bnl.gov/nudat2/reCenter.jsp?z=69&n=97
|url-status=dead
}}</ref>  


In total, 40 isotopes and 26 [[nuclear isomer]]s of thulium have been detected.<ref name="history" /> Most isotopes of thulium lighter than {{val|169|ul=Da}} decay via [[electron capture]] or [[Positron emission|beta-plus decay]], although some exhibit significant [[alpha decay]] or [[proton emission]]. Heavier isotopes undergo [[beta-minus decay]].<ref name="Nudat" />
The primary [[decay mode]] before the stable isotope, {{chem2|^{169}Tm}}, is [[electron capture]] to [[Isotopes of erbium|erbium]] isotopes, and the primary mode after is [[beta emission]] to [[Isotopes of ytterbium|ytterbium]] isotopes. The longest-lived radioisotopes are thulium-171, which has a [[half-life]] of 1.92 years, and [[thulium-170]], which has a half-life of 128.6 days. Most other isotopes have half-lives under 10 minutes.{{NUBASE2020|ref}}


== History ==
== History ==
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== Occurrence ==
== Occurrence ==
[[File:Monazit - Madagaskar.jpg|thumb|Thulium is found in the mineral monazite]]
[[File:Monazit - Madagaskar.jpg|thumb|Thulium is found in the mineral monazite]]
The element is never found in nature in pure form, but it is found in small quantities in [[mineral]]s with other rare earths. Thulium is often found with minerals containing [[yttrium]] and [[gadolinium]]. In particular, thulium occurs in the mineral [[gadolinite]].<ref name= "handbook of metals">{{cite book|author=Walker, Perrin|author2=Tarn, William H.|name-list-style=amp |title=CRC Handbook of Metal Etchants|url=https://books.google.com/books?id=-2ObmTZTq2QC&pg=PA1241|date=2010|publisher=CRC Press|isbn=978-1-4398-2253-1|pages=1241–}}</ref> Like many other [[lanthanides]], thulium also occurs in the minerals [[monazite]], [[xenotime]], and [[euxenite]]. Thulium has not been found in prevalence over the other rare earths in any mineral yet.<ref>{{cite web |url=https://www.mindat.org/ |title=Mindat.org |author=Hudson Institute of Mineralogy |date=1993–2018 |website=www.mindat.org |access-date=14 January 2018}}</ref> Its [[Abundance of elements in Earth's crust |abundance in the Earth's crust]] is 0.5&nbsp;mg/kg by weight.<ref name=CRCAbundanceTable>ABUNDANCE OF ELEMENTS IN THE EARTH’S CRUST AND IN THE SEA, ''CRC Handbook of Chemistry and Physics'', 97th edition (2016–2017), p. 14–17</ref>  
The element is never found in nature in pure form, but it is found in small quantities in [[mineral]]s with other rare earths. Thulium is often found with minerals containing [[yttrium]] and [[gadolinium]]. In particular, thulium occurs in the mineral [[gadolinite]].<ref name= "handbook of metals">{{cite book|author=Walker, Perrin|author2=Tarn, William H.|name-list-style=amp |title=CRC Handbook of Metal Etchants|url=https://books.google.com/books?id=-2ObmTZTq2QC&pg=PA1241|date=2010|publisher=CRC Press|isbn=978-1-4398-2253-1|pages=1241–}}</ref> Like many other [[lanthanides]], thulium also occurs in the minerals [[monazite]], [[xenotime]], and [[euxenite]]. Thulium has not been found in prevalence over the other rare earths in any mineral yet.<ref>{{cite web |url=https://www.mindat.org/ |title=Mindat.org |author=Hudson Institute of Mineralogy |date=1993–2018 |website=www.mindat.org |access-date=14 January 2018}}</ref> Its [[Abundance of elements in Earth's crust |abundance in the Earth's crust]] is 0.5&nbsp;mg/kg by weight.<ref name=CRCAbundanceTable>ABUNDANCE OF ELEMENTS IN THE EARTH'S CRUST AND IN THE SEA, ''CRC Handbook of Chemistry and Physics'', 97th edition (2016–2017), p. 14–17</ref>


Thulium makes up approximately 0.5 parts per million of [[soil]], although this value can range from 0.4 to 0.8 parts per million. Thulium makes up 250 parts per quadrillion of [[seawater]].<ref name="history">{{cite book |pages=442–443 |url= https://books.google.com/books?id=Yhi5X7OwuGkC&pg=PA442 |title= Nature's building blocks: an A-Z guide to the elements |author= Emsley, John |publisher=Oxford University Press |location= US |date= 2001 |isbn= 0-19-850341-5}}</ref> In the [[Solar System]], thulium exists in concentrations of 200 parts per trillion by weight and 1&nbsp;part per trillion by moles.<ref name="cool" /> Thulium ore occurs most commonly in [[China]]. [[Australia]], [[Brazil]], [[Greenland]], [[India]], [[Tanzania]], and the [[United States]] also have large reserves of thulium. In 2001, the total world reserves of thulium were approximately 100,000 [[tonne]]s. Thulium is the least abundant [[lanthanide]] on Earth except for the radioactive [[promethium]].<ref name="history" />
Thulium makes up approximately 0.5 parts per million of [[soil]], although this value can range from 0.4 to 0.8 parts per million. Thulium makes up 250 parts per quadrillion of [[seawater]].<ref name="history">{{cite book |pages=442–443 |url= https://books.google.com/books?id=Yhi5X7OwuGkC&pg=PA442 |title= Nature's building blocks: an A-Z guide to the elements |author= Emsley, John |publisher=Oxford University Press |location= US |date= 2001 |isbn= 0-19-850341-5}}</ref> In the [[Solar System]], thulium exists in concentrations of 200 parts per trillion by weight and 1&nbsp;part per trillion by moles.<ref name="cool" /> Thulium ore occurs most commonly in [[China]]. [[Australia]], [[Brazil]], [[Greenland]], [[India]], [[Tanzania]], and the [[United States]] also have large reserves of thulium. In 2001, the total world reserves of thulium were approximately 100,000 [[tonne]]s. Thulium is the least abundant [[lanthanide]] on Earth except for the radioactive [[promethium]].<ref name="history" />
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=== Others ===
=== Others ===
Thulium has been used in [[high-temperature superconductor]]s similarly to [[yttrium]]. Thulium potentially has use in [[ferrite (magnet)|ferrite]]s, ceramic magnetic materials that are used in [[microwave]] equipment.<ref name="appl" /> Thulium is also similar to [[scandium]] in that it is used in arc lighting for its unusual spectrum, in this case, its green emission lines, which are not covered by other elements.<ref>{{cite book |page= [https://archive.org/details/elementsvisualex0000gray/page/159 159] |url= https://archive.org/details/elementsvisualex0000gray/page/159 |title= The Elements: A Visual Exploration of Every Known Atom In The Universe |author= Gray, Theodore W. |author2= Mann, Nick |name-list-style= amp |publisher= Black Dog & Leventhal Publishers |date= 2009 |isbn= 978-1-57912-814-2 }}</ref> Because thulium [[fluoresce]]s with a blue color when exposed to [[ultraviolet|ultraviolet light]], thulium is put into [[euro]] [[banknotes]] as a measure against [[counterfeit]]ing.<ref name="Photochemistry">{{cite book |url= https://books.google.com/books?id=XAjIWgENf5UC&pg=PA75 |page= 75 |title= Principles and Applications of Photochemistry |isbn= 978-0-470-71013-5 |last1= Wardle |first1= Brian |date= 2009-11-06|publisher= John Wiley & Sons }}</ref>  
Thulium has been used in [[high-temperature superconductor]]s similarly to [[yttrium]]. Thulium potentially has use in [[ferrite (magnet)|ferrite]]s, ceramic magnetic materials that are used in [[microwave]] equipment.<ref name="appl" /> Thulium is also similar to [[scandium]] in that it is used in arc lighting for its unusual spectrum, in this case, its green emission lines, which are not covered by other elements.<ref>{{cite book |page=[https://archive.org/details/elementsvisualex0000gray/page/159 159] |url=https://archive.org/details/elementsvisualex0000gray/page/159 |title=The Elements: A Visual Exploration of Every Known Atom In The Universe |author=Gray, Theodore W. |author2=Mann, Nick |name-list-style=amp |publisher=Black Dog & Leventhal Publishers |date=2009 |isbn=978-1-57912-814-2 }}</ref> Because thulium [[fluoresce]]s with a blue color when exposed to [[ultraviolet|ultraviolet light]], thulium is put into [[euro]] [[banknotes]] as a measure against [[counterfeit]]ing.<ref name="Photochemistry">{{cite book |url=https://books.google.com/books?id=XAjIWgENf5UC&pg=PA75 |page=75 |title=Principles and Applications of Photochemistry |isbn=978-0-470-71013-5 |last1=Wardle |first1=Brian |date=2009-11-06|publisher=John Wiley & Sons}}</ref>


The blue fluorescence of Tm-doped calcium sulfate has been used in personal dosimeters for visual monitoring of radiation.<ref name="history" /> Tm-doped halides in which Tm is in its 2+ oxidation state are luminescent materials that are proposed for electric power generating windows based on the principle of a [[luminescent solar concentrator]].<ref name="Richards 2023">{{cite journal | last1=Richards | first1=Bryce S. | last2=Howard | first2=Ian A. | title=Luminescent solar concentrators for building integrated photovoltaics: opportunities and challenges | journal=Energy & Environmental Science | volume=16 | issue=8 | date=2023 | issn=1754-5692 | doi=10.1039/D3EE00331K | pages=3214–3239| doi-access=free | bibcode=2023EnEnS..16.3214R }}</ref>
The blue fluorescence of Tm-doped calcium sulfate has been used in personal dosimeters for visual monitoring of radiation.<ref name="history" /> Tm-doped halides in which Tm is in its 2+ oxidation state are luminescent materials that are proposed for electric power generating windows based on the principle of a [[luminescent solar concentrator]].<ref name="Richards 2023">{{cite journal | last1=Richards | first1=Bryce S. | last2=Howard | first2=Ian A. | title=Luminescent solar concentrators for building integrated photovoltaics: opportunities and challenges | journal=Energy & Environmental Science | volume=16 | issue=8 | date=2023 | issn=1754-5692 | doi=10.1039/D3EE00331K | pages=3214–3239| doi-access=free | bibcode=2023EnEnS..16.3214R }}</ref>


== Biological role and precautions ==
== Biological role ==
Soluble thulium salts are mildly [[toxicity|toxic]], but insoluble thulium salts are completely [[nontoxic]].<ref name="history" /> When injected, thulium can cause degeneration of the [[liver]] and [[spleen]] and can also cause [[hemoglobin]] concentration to fluctuate. Liver damage from thulium is more prevalent in male [[Mouse|mice]] than female mice. Despite this, thulium has a low level of toxicity.<ref>{{Cite book |last=Ayres |first=D. C. |url=https://www.worldcat.org/oclc/1301431003 |title=Dictionary of environmentally important chemicals |publisher=CRC Press |others=Desmond Hellier |date=15 February 2022 |isbn=978-1-315-14115-2 |edition=1st |location=United States |pages=299 |language=English |oclc=1301431003}}</ref><ref>{{Cite book |last=Jha |first=A. R. |url=https://www.worldcat.org/oclc/880825396 |title=Rare Earth Materials : Properties and Applications. |date=2014 |publisher=CRC Press |isbn=978-1-4665-6403-9 |location=Boca Raton |pages=63 |oclc=880825396}}</ref><!--The following refs don't exactly support the statement here, which needs to be rewritten slightly: <ref>{{cite journal |pmid=1141999 |year=1975 |last1=Hutcheson |first1=D. P. |last2=Gray |first2=D. H. |last3=Venugopal |first3=B. |last4=Luckey |first4=T. D. |title=Studies of nutritional safety of some heavy metals in mice |volume=105 |issue=6 |pages=670–5 |journal=The Journal of Nutrition|doi=10.1093/jn/105.6.670 }}</ref><ref>{{cite journal |doi=10.1016/0041-008X(63)90014-0 |title=Pharmacology and toxicology of terbium, thulium, and ytterbium chlorides |year=1963 |last1=Haley |first1=Thomas J. |last2=Komesu |first2=N. |last3=Flesher |first3=A. M. |last4=Mavis |first4=L. |last5=Cawthorne |first5=J. |last6=Upham |first6=H. C. |journal=Toxicology and Applied Pharmacology |volume=5 |issue=4 |pages=427–436}}</ref><ref>{{cite journal |doi=10.1002/jps.2600540502 |title=Pharmacology and toxicology of the rare earth elements |year=1965 |last1=Haley |first1=Thomas J. |journal=Journal of Pharmaceutical Sciences |volume=54 |issue=5 |pages=663–70 |pmid=5321124}}</ref><ref>{{cite journal |doi=10.1016/0041-008X(63)90067-X |title=The acute mammalian toxicity of rare earth nitrates and oxides |year=1963 |last1=Bruce |first1=David W. |last2=Hietbrink |first2=Bernard E. |last3=Dubois |first3=Kenneth P. |journal=Toxicology and Applied Pharmacology |volume=5 |issue=6 |pages=750–759 |pmid=14082480 |bibcode=1963ToxAP...5..750B}}</ref>-->
Soluble thulium salts are mildly [[toxicity|toxic]], but insoluble thulium salts are completely [[nontoxic]].<ref name="history" /> When injected, thulium can cause degeneration of the [[liver]] and [[spleen]] and can also cause [[hemoglobin]] concentration to fluctuate. Liver damage from thulium is more prevalent in male [[Mouse|mice]] than female mice. Despite this, thulium has a low level of toxicity.<ref>{{Cite book |last=Ayres |first=D. C. |title=Dictionary of environmentally important chemicals |publisher=CRC Press |others=Desmond Hellier |date=15 February 2022 |isbn=978-1-315-14115-2 |edition=1st |location=United States |page=299 |language=English |oclc=1301431003}}</ref><ref>{{Cite book |last=Jha |first=A. R. |title=Rare Earth Materials: Properties and Applications. |date=2014 |publisher=CRC Press |isbn=978-1-4665-6403-9 |location=Boca Raton |page=63 |oclc=880825396}}</ref><!--The following refs don't exactly support the statement here, which needs to be rewritten slightly: <ref>{{cite journal |pmid=1141999 |year=1975 |last1=Hutcheson |first1=D. P. |last2=Gray |first2=D. H. |last3=Venugopal |first3=B. |last4=Luckey |first4=T. D. |title=Studies of nutritional safety of some heavy metals in mice |volume=105 |issue=6 |pages=670–5 |journal=The Journal of Nutrition|doi=10.1093/jn/105.6.670}}</ref><ref>{{cite journal |doi=10.1016/0041-008X(63)90014-0 |title=Pharmacology and toxicology of terbium, thulium, and ytterbium chlorides |year=1963 |last1=Haley |first1=Thomas J. |last2=Komesu |first2=N. |last3=Flesher |first3=A. M. |last4=Mavis |first4=L. |last5=Cawthorne |first5=J. |last6=Upham |first6=H. C. |journal=Toxicology and Applied Pharmacology |volume=5 |issue=4 |pages=427–436}}</ref><ref>{{cite journal |doi=10.1002/jps.2600540502 |title=Pharmacology and toxicology of the rare earth elements |year=1965 |last1=Haley |first1=Thomas J. |journal=Journal of Pharmaceutical Sciences |volume=54 |issue=5 |pages=663–70 |pmid=5321124}}</ref><ref>{{cite journal |doi=10.1016/0041-008X(63)90067-X |title=The acute mammalian toxicity of rare earth nitrates and oxides |year=1963 |last1=Bruce |first1=David W. |last2=Hietbrink |first2=Bernard E. |last3=Dubois |first3=Kenneth P. |journal=Toxicology and Applied Pharmacology |volume=5 |issue=6 |pages=750–759 |pmid=14082480 |bibcode=1963ToxAP...5..750B}}</ref>-->
 
In humans, thulium occurs in the highest amounts in the [[liver]], [[kidney]]s, and [[bone]]s. Humans typically consume several micrograms of thulium per year. The roots of [[plant]]s do not take up thulium, and the [[dry matter]] of vegetables usually contains one [[parts per billion|part per billion]] of thulium.<ref name="history" /> Thulium metal has low to moderate toxicity.<ref>{{cite web |author1=<!--not stated--> |title=Thulium |url=https://periodic.lanl.gov/69.shtml |website=Los Alamos National Laboratory |publisher=Triad National Security, LLC |access-date=1 June 2024}}</ref> Thulium [[dust]] can cause [[explosion]]s and [[fires]].<ref>{{cite web |author1=Thermo Fisher Scientific Chemicals, Inc. |title=SAFETY DATA SHEET |url=https://www.fishersci.com/store/msds?partNumber=AA4416803&productDescription=THULIUM+PWR+-40+MESH+99.9%25+1G&vendorId=VN00024248&countryCode=US&language=en |website=fisher scientific |access-date=1 June 2024 |location=Section: 5. Fire-fighting measures |date=28 March 2024}}</ref>


In humans, thulium occurs in the highest amounts in the [[liver]], [[kidney]]s, and [[bone]]s. Humans typically consume several micrograms of thulium per year. The roots of [[plant]]s do not take up thulium, and the [[dry matter]] of vegetables usually contains one [[parts per billion|part per billion]] of thulium.<ref name="history" /> Thulium metal has low to moderate toxicity.<ref>{{cite web |author1=<!--not stated--> |title=Thulium |url=https://periodic.lanl.gov/69.shtml |website=Los Alamos National Laboratory |publisher=Triad National Security, LLC |access-date=1 June 2024}}</ref>
== See also ==
== See also ==
* {{Category link|Thulium compounds}}
* {{Category link|Thulium compounds}}
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{{Authority control}}
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[[Category:Thulium| ]]
[[Category:Thulium| ]]
[[Category:Chemical elements]]
[[Category:Chemical elements]]

Latest revision as of 06:30, 9 November 2025

Script error: No such module "Distinguish". Template:Good article Template:Short descriptionScript error: No such module "Infobox".Template:Template otherScript error: No such module "Check for unknown parameters". Thulium is a chemical element; it has symbol Tm and atomic number 69. It is the thirteenth element in the lanthanide series of metals. It is the second-least abundant lanthanide in the Earth's crust, after radioactively unstable promethium. It is an easily workable metal with a bright silvery-gray luster. It is fairly soft and slowly tarnishes in air. Despite its high price and rarity, thulium is used as a dopant in solid-state lasers. It has no significant biological role and is not particularly toxic. Artificial radioactive isotopes of thulium are used as radiation sources in some portable X-ray devices.

In 1879, the Swedish chemist Per Teodor Cleve separated two previously unknown components, which he called holmia and thulia, from the rare-earth mineral erbia; these were the oxides of holmium and thulium, respectively. His example of thulium oxide contained impurities of ytterbium oxide. A relatively pure sample of thulium oxide was first obtained in 1911. The metal itself was first obtained in 1936 by Wilhelm Klemm and Heinrich Bommer.[1]

Like the other lanthanides, its most common oxidation state is +3, seen in its oxide, halides and other compounds. In aqueous solution, like compounds of other late lanthanides, soluble thulium compounds form coordination complexes with nine water molecules.

Properties

Physical properties

Pure thulium metal has a bright, silvery luster, which tarnishes on exposure to air. The metal can be cut with a knife,[2] as it has a Mohs hardness of 2 to 3; it is malleable and ductile.[3] Thulium is ferromagnetic below 32Script error: No such module "String".K, antiferromagnetic between 32 and 56Script error: No such module "String".K, and paramagnetic above 56Script error: No such module "String".K.[4]

Thulium has two major allotropes: the tetragonal α-Tm and the more stable hexagonal β-Tm.[3]

Chemical properties

Thulium tarnishes slowly in air and burns readily at 150Script error: No such module "String".°C to form thulium(III) oxide:[5]

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Thulium dust can cause explosions and fires.[6]

Thulium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form thulium hydroxide:

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Thulium reacts with all the halogens. Reactions are slow at room temperature, but are vigorous above 200Script error: No such module "String".°C:

Template:Chem2 (white)
Template:Chem2 (yellow)
Template:Chem2 (white)
Template:Chem2 (yellow)

Thulium dissolves readily in dilute sulfuric acid to form solutions containing the pale green Tm(III) ions, which exist as Template:Chem2 complexes:[7]

Template:Chem2

Thulium reacts with various metallic and non-metallic elements forming a range of binary compounds, including Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2 and Template:Chem2.Script error: No such module "Unsubst". Like most lanthanides, the +3 state is most common and is the only state observed in thulium solutions.[8] Thulium exists as a Template:Chem2 ion in solution. In this state, the thulium ion is surrounded by nine molecules of water.[2] Template:Chem2 ions exhibit a bright blue luminescence.[2] Because it occurs late in the series, the +2 oxidation state can also exist, stabilized by the nearly full 4f electron shell, but occurs only in solids.Script error: No such module "Unsubst".

Thulium's only known oxide is [[thulium oxide|Template:Chem2]]. This oxide is sometimes called "thulia".[9] Reddish-purple thulium(II) compounds can be made by the reduction of thulium(III) compounds. Examples of thulium(II) compounds include the halides (except the fluoride). Some hydrated thulium compounds, such as Template:Chem2 and Template:Chem2 are green or greenish-white.[10] Thulium dichloride reacts very vigorously with water. This reaction results in hydrogen gas and [[thulium(III) hydroxide|Template:Chem2]] exhibiting a fading reddish color.Script error: No such module "Unsubst". Combination of thulium and chalcogens results in thulium chalcogenides.[11]

Thulium reacts with hydrogen chloride to produce hydrogen gas and thulium chloride. With nitric acid it yields thulium nitrate, Template:Chem2.[12]

Isotopes

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Natural thulium consists of the single stable isotope thulium-169 (it is predicted to undergo alpha decay to holmium-165 with a very long half-life.[2][13]). Known isotopes of thulium range from Template:Chem2 to Template:Chem2.Template:NUBASE2020[14]

The primary decay mode before the stable isotope, Template:Chem2, is electron capture to erbium isotopes, and the primary mode after is beta emission to ytterbium isotopes. The longest-lived radioisotopes are thulium-171, which has a half-life of 1.92 years, and thulium-170, which has a half-life of 128.6 days. Most other isotopes have half-lives under 10 minutes.Template:NUBASE2020

History

File:Per Teodor Cleve c1885.jpg
Per Teodor Cleve, the scientist who discovered thulium as well as holmium.

Thulium was discovered by Swedish chemist Per Teodor Cleve in 1879 by looking for impurities in the oxides of other rare earth elements. This was the same method Carl Gustaf Mosander earlier used to discover some other rare earth elements.[15] Cleve started by removing all of the known contaminants of erbia (Template:Chem2). Upon additional processing, he obtained two new substances; one brown and one green. The brown substance was the oxide of the element holmium and was named holmia by Cleve, and the green substance was the oxide of an unknown element. Cleve named the oxide thulia and its element thulium after Thule, an Ancient Greek place name associated with Scandinavia or Iceland. Thulium's atomic symbol was initially Tu, but laterScript error: No such module "Unsubst". changed to Tm.Template:Why[2][16][17][18][19][20][21]

Thulium was so rare that none of the early workers had enough of it to purify sufficiently to actually see the green color; they had to be content with spectroscopically observing the strengthening of the two characteristic absorption bands, as erbium was progressively removed. The first researcher to obtain nearly pure thulium was Charles James, a British expatriate working on a large scale at New Hampshire College in Durham, USA. In 1911 he reported his results, having used his discovered method of bromate fractional crystallization to do the purification. He famously needed 15,000 purification operations to establish that the material was homogeneous.[22]

High-purity thulium oxide was first offered commercially in the late 1950s, as a result of the adoption of ion-exchange separation technology. Lindsay Chemical Division of American Potash & Chemical Corporation offered it in grades of 99% and 99.9% purity. The price per kilogram oscillated between US$4,600 and $13,300 in the period from 1959 to 1998 for 99.9% purity, and it was the second highest for the lanthanides behind lutetium.[23][24]

Occurrence

File:Monazit - Madagaskar.jpg
Thulium is found in the mineral monazite

The element is never found in nature in pure form, but it is found in small quantities in minerals with other rare earths. Thulium is often found with minerals containing yttrium and gadolinium. In particular, thulium occurs in the mineral gadolinite.[25] Like many other lanthanides, thulium also occurs in the minerals monazite, xenotime, and euxenite. Thulium has not been found in prevalence over the other rare earths in any mineral yet.[26] Its abundance in the Earth's crust is 0.5 mg/kg by weight.[27]

Thulium makes up approximately 0.5 parts per million of soil, although this value can range from 0.4 to 0.8 parts per million. Thulium makes up 250 parts per quadrillion of seawater.[2] In the Solar System, thulium exists in concentrations of 200 parts per trillion by weight and 1 part per trillion by moles.[12] Thulium ore occurs most commonly in China. Australia, Brazil, Greenland, India, Tanzania, and the United States also have large reserves of thulium. In 2001, the total world reserves of thulium were approximately 100,000 tonnes. Thulium is the least abundant lanthanide on Earth except for the radioactive promethium.[2]

Production

Thulium is principally extracted from monazite ores (~0.007% thulium) found in river sands, through ion exchange. Newer ion-exchange and solvent-extraction techniques have led to easier separation of the rare earths, which has yielded much lower costs for thulium production. The principal sources today are the ion adsorption clays of southern China. In these, where about two-thirds of the total rare-earth content is yttrium, thulium is about 0.5% (or about tied with lutetium for rarity).[2]

The metal can be isolated through reduction of its oxide with lanthanum metal or by calcium reduction in a closed container. None of thulium's natural compounds are commercially important. In 2001, approximately 50 tonnes per year of thulium oxide were produced.[2] In 1996, thulium oxide cost US$20 per gram, and in 2005, 99%-pure thulium metal powder cost US$70 per gram.[3]

Applications

Lasers

Holmium-chromium-thulium triple-doped yttrium aluminium garnet (Template:Chem2, or Template:Chem2) is an active laser medium material with high efficiency. It lases at 2080 nm in the infrared and is widely used in military applications, medicine, and meteorology. Single-element thulium-doped YAG (Tm:YAG) lasers operate at 2010 nm.[28] The wavelength of thulium-based lasers is very efficient for superficial ablation of tissue, with minimal coagulation depth in air or in water. This makes thulium lasers attractive for laser-based surgery.[29]

X-ray source

Despite its high cost, portable X-ray devices use thulium that has been bombarded with neutrons in a nuclear reactor to produce the isotope thulium-170, having a half-life of 128.6 days and five major emission lines of comparable intensity (at 7.4, 51.354, 52.389, 59.4 and 84.253 keV). These radioactive sources have a useful life of about one year, as tools in medical and dental diagnosis, as well as to detect defects in inaccessible mechanical and electronic components. Such sources do not need extensive radiation protectionTemplate:Sndonly a small cup of lead.[30] They are among the most popular radiation sources for use in industrial radiography.[31] Thulium-170 is gaining popularity as an X-ray source for cancer treatment via brachytherapy (sealed source radiation therapy).[32][33]

Others

Thulium has been used in high-temperature superconductors similarly to yttrium. Thulium potentially has use in ferrites, ceramic magnetic materials that are used in microwave equipment.[30] Thulium is also similar to scandium in that it is used in arc lighting for its unusual spectrum, in this case, its green emission lines, which are not covered by other elements.[34] Because thulium fluoresces with a blue color when exposed to ultraviolet light, thulium is put into euro banknotes as a measure against counterfeiting.[35]

The blue fluorescence of Tm-doped calcium sulfate has been used in personal dosimeters for visual monitoring of radiation.[2] Tm-doped halides in which Tm is in its 2+ oxidation state are luminescent materials that are proposed for electric power generating windows based on the principle of a luminescent solar concentrator.[36]

Biological role

Soluble thulium salts are mildly toxic, but insoluble thulium salts are completely nontoxic.[2] When injected, thulium can cause degeneration of the liver and spleen and can also cause hemoglobin concentration to fluctuate. Liver damage from thulium is more prevalent in male mice than female mice. Despite this, thulium has a low level of toxicity.[37][38]

In humans, thulium occurs in the highest amounts in the liver, kidneys, and bones. Humans typically consume several micrograms of thulium per year. The roots of plants do not take up thulium, and the dry matter of vegetables usually contains one part per billion of thulium.[2] Thulium metal has low to moderate toxicity.[39]

See also

References

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  1. ↑ Script error: No such module "Citation/CS1"..
  2. ↑ a b c d e f g h i j k l Script error: No such module "citation/CS1".
  3. ↑ a b c Script error: No such module "citation/CS1".
  4. ↑ Script error: No such module "Citation/CS1".
  5. ↑ Script error: No such module "citation/CS1".
  6. ↑ Script error: No such module "citation/CS1".
  7. ↑ Script error: No such module "citation/CS1".
  8. ↑ Script error: No such module "citation/CS1".
  9. ↑ Script error: No such module "citation/CS1".
  10. ↑ Script error: No such module "citation/CS1".
  11. ↑ Script error: No such module "citation/CS1".
  12. ↑ a b Script error: No such module "citation/CS1".
  13. ↑ Script error: No such module "Citation/CS1".
  14. ↑ Script error: No such module "Citation/CS1".
  15. ↑ See:
    • Script error: No such module "Citation/CS1". Cleve named thulium on p. 480: "Pour le radical de l'oxyde placé entre l'ytterbine et l'erbine, qui est caractérisé par la bande x dans la partie rouge du spectre, je propose la nom de thulium, dérivé de Thulé, le plus ancien nom de la Scandinavie." (For the radical of the oxide located between the oxides of ytterbium and erbium, which is characterized by the x band in the red part of the spectrum, I propose the name of "thulium", [which is] derived from Thule, the oldest name of Scandinavia.)
    • Script error: No such module "Citation/CS1".
    • Script error: No such module "Citation/CS1".
  16. ↑ Script error: No such module "citation/CS1".
  17. ↑ Script error: No such module "citation/CS1".
  18. ↑ Script error: No such module "Citation/CS1".
  19. ↑ Script error: No such module "Citation/CS1".
  20. ↑ Script error: No such module "Citation/CS1".
  21. ↑ Script error: No such module "citation/CS1".
  22. ↑ Script error: No such module "Citation/CS1".
  23. ↑ Script error: No such module "citation/CS1".
  24. ↑ Script error: No such module "citation/CS1".
  25. ↑ Script error: No such module "citation/CS1".
  26. ↑ Script error: No such module "citation/CS1".
  27. ↑ ABUNDANCE OF ELEMENTS IN THE EARTH'S CRUST AND IN THE SEA, CRC Handbook of Chemistry and Physics, 97th edition (2016–2017), p. 14–17
  28. ↑ Script error: No such module "citation/CS1".
  29. ↑ Script error: No such module "citation/CS1".
  30. ↑ a b Script error: No such module "citation/CS1".
  31. ↑ Script error: No such module "citation/CS1".
  32. ↑ Script error: No such module "Citation/CS1".
  33. ↑ Script error: No such module "citation/CS1".
  34. ↑ Script error: No such module "citation/CS1".
  35. ↑ Script error: No such module "citation/CS1".
  36. ↑ Script error: No such module "Citation/CS1".
  37. ↑ Script error: No such module "citation/CS1".
  38. ↑ Script error: No such module "citation/CS1".
  39. ↑ Script error: No such module "citation/CS1".

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External links

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