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Not to be confused with Thallium or Thorium.
Thulium, 69Tm
Thulium
Pronunciation/ˈθjuːliəm/ ​(THEW-lee-əm)
Appearancesilvery gray
Standard atomic weight Ar°(Tm)
Thulium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
–
↑
Tm
↓
Md
erbium ← thulium → ytterbium
Atomic number (Z)69
Groupf-block groups (no number)
Periodperiod 6
Block  f-block
Electron configuration[Xe] 4f13 6s2
Electrons per shell2, 8, 18, 31, 8, 2
Physical properties
Phase at STPsolid
Melting point1818 K ​(1545 °C, ​2813 °F)
Boiling point2223 K ​(1950 °C, ​3542 °F)
Density (at 20° C)9.320 g/cm3 [3]
when liquid (at m.p.)8.56 g/cm3
Heat of fusion16.84 kJ/mol
Heat of vaporization191 kJ/mol
Molar heat capacity27.03 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1117 1235 1381 1570 (1821) (2217)
Atomic properties
Oxidation statescommon: +3
0,[4] +1,[5] +2[6]
ElectronegativityPauling scale: 1.25
Ionization energies
  • 1st: 596.7 kJ/mol
  • 2nd: 1160 kJ/mol
  • 3rd: 2285 kJ/mol
Atomic radiusempirical: 176 pm
Covalent radius190±10 pm
Color lines in a spectral range
Spectral lines of thulium
Other properties
Natural occurrenceprimordial
Crystal structure ​hexagonal close-packed (hcp) (hP2)
Lattice constants
Hexagonal close packed crystal structure for thulium
a = 353.77 pm
c = 555.39 pm (at 20 °C)[3]
Thermal expansionpoly: 13.3 µm/(m⋅K) (at r.t.)
Thermal conductivity16.9 W/(m⋅K)
Electrical resistivitypoly: 676 nΩ⋅m (at r.t.)
Magnetic orderingparamagnetic (at 300 K)
Molar magnetic susceptibility+25500×10−6 cm3/mol (291 K)[7]
Young's modulus74.0 GPa
Shear modulus30.5 GPa
Bulk modulus44.5 GPa
Poisson ratio0.213
Vickers hardness470–650 MPa
Brinell hardness470–900 MPa
CAS Number7440-30-4
History
Namingafter Thule, a mythical region in Scandinavia
Discovery and first isolationPer Teodor Cleve (1879)
Isotopes of thulium
Main isotopes[8] Decay
abun­dance half-life (t1/2) mode pro­duct
167Tm synth 9.25 d ε 167Er
168Tm synth 93.1 d β+ 168Er
169Tm 100% stable
170Tm synth 128.6 d β− 170Yb
171Tm synth 1.92 y β− 171Yb
 Category: Thulium
| references

Thulium (/[invalid input: 'icon']ˈθjuːliəm/ THEW-lee-əm) is a chemical element that has the symbol Tm and atomic number 69. Thulium is the second least abundant of the lanthanides (promethium is only found in trace quantities on Earth). It is an easily workable metal with a bright silvery-gray luster. Despite its high price and rarity, thulium is used as the radiation source in portable X-ray devices and in solid-state lasers.

Properties

Physical properties

Pure thulium metal has a bright, silvery luster. It is reasonably stable in air, but should be protected from moisture. The metal is soft, malleable, and ductile.[9] Thulium is ferromagnetic below 32 K, antiferromagnetic between 32 and 56 K and paramagnetic above 56 K.[10]

Chemical properties

Thulium metal tarnishes slowly in air and burns readily at 150 °C to form thulium(III) oxide:

4 Tm + 3 O2 → 2 Tm2O3

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

2 Tm (s) + 6 H2O (l) → 2 Tm(OH)3 (aq) + 3 H2 (g)

Thulium reacts with all the halogens. Reactions are slow at room temperature, but are vigorous above 200 °C:

2 Tm (s) + 3 F2 (g) → 2 TmF3 (s) [white]
2 Tm (s) + 3 Cl2 (g) → 2 TmCl3 (s) [yellow]
2 Tm (s) + 3 Br2 (g) → 2 TmBr3 (s) [white]
2 Tm (s) + 3 I2 (g) → 2 TmI3 (s) [yellow]

Thulium dissolves readily in dilute sulfuric acid to form solutions containing the pale green Tm(III) ions, which exist as a [Tm(OH2)9]3+ complexes:[11]

2 Tm (s) + 3 H2SO4 (aq) → 2 Tm3+ (aq) + 3 SO2−
4 (aq) + 3 H2 (g)

Thulium reacts with various metallic and non-metallic elements forming a range of binary compounds, including TmN, TmS, TmC2, Tm2C3, TmH2, TmH3, TmSi2, TmGe3, TmB4, TmB6 and TmB12. In those compounds, thulium exhibits valence states +2, +3 and +4, however, the +3 state is most common and only this state has been observed in Tm solutions.[12]

Isotopes

Main article: Isotopes of thulium

Naturally occurring thulium is composed of one stable isotope, Tm-169 (100% natural abundance). Thirty one radioisotopes have been characterized, with the most stable being Tm-171 with a half-life of 1.92 years, Tm-170 with a half-life of 128.6 days, Tm-168 with a half-life of 93.1 days, and Tm-167 with a half-life of 9.25 days. All of the remaining radioactive isotopes have half-lives that are less than 64 hours, and the majority of these have half-lives that are less than 2 minutes. This element also has 14 meta states, with the most stable being Tm-164m (t½ 5.1 minutes), Tm-160m (t½ 74.5 seconds) and Tm-155m (t½ 45 seconds).

The isotopes of thulium range in atomic weight from 145.966 u (Tm-146) to 176.949 u (Tm-177). The primary decay mode before the most abundant stable isotope, Tm-169, is electron capture, and the primary mode after is beta emission. The primary decay products before Tm-169 are element 68 (erbium) isotopes, and the primary products after are element 70 (ytterbium) isotopes.[13]

History

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). Cleve started by removing all of the known contaminants of erbia (Er2O3). 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, Scandinavia.

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. In 1911 he reported his results, having used his discovered method of bromate fractional crystallization to do the purification. He famously needed 15,000 "operations" to establish that the material was homogeneous.[14]

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 has oscillated between US$4,600 and $13,300 in the period from 1959 to 1998 for 99.9% purity, and it was second highest for lanthanides behind lutetium.[15][16]

Occurrence and production

The element is never found in nature in pure form, but it is found in small quantities in minerals with other rare earths. Its abundance in the Earth crust is 0.5 mg/kg.[17] Thulium is principally extracted from monazite (~0.007% thulium) ores 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). 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.[9]

Applications

Rare and expensive, thulium has few applications:

Laser

Holmium-chromium-thulium triple-doped YAG (Ho:Cr:Tm:YAG, or Ho,Cr,Tm:YAG) is an active laser medium material with high efficiency. It lases at 2097 nm and is widely used in military, medicine, and meteorology. Single-element thulium-doped YAG (Tm:YAG) lasers operate between 1930 and 2040 nm.[18] 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.[19]

X-ray source

Despite its high cost, portable X-ray devices use thulium that has been bombarded in a nuclear reactor as a radiation source. These sources are available for 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 protection – only a small cup of lead.[20]

Thulium-170 is gaining popularity as an X-ray source for cancer treatment via brachytherapy.[21] This isotope has a half-life of 128.6 days and five major emission lines of comparable intensity (7.4, 51.354, 52.389, 59.4 and 84.253 keV).[22]

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.[20] 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.[23]

Biological role and precautions

Thulium has no known biological role, although it has been noted that it stimulates metabolism. Soluble thulium salts are regarded as slightly toxic if taken in large amounts, but the insoluble salts are non-toxic. Thulium is not taken up by plant roots to any extent and thus does not get into the human food chain. Vegetables typically contain only one milligram of thulium per tonne (dry weight).[17]

See also

References

  1. ^ "Standard Atomic Weights: Thulium". CIAAW. 2021.
  2. ^ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (2022-05-04). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
  3. ^ a b Arblaster, John W. (2018). Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International. ISBN 978-1-62708-155-9.
  4. ^ 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.
  5. ^ La(I), Pr(I), Tb(I), Tm(I), and Yb(I) have been observed in MB8− clusters; see Li, Wan-Lu; Chen, Teng-Teng; Chen, Wei-Jia; Li, Jun; Wang, Lai-Sheng (2021). "Monovalent lanthanide(I) in borozene complexes". Nature Communications. 12 (1): 6467. doi:10.1038/s41467-021-26785-9. PMC 8578558. PMID 34753931.
  6. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 28. ISBN 978-0-08-037941-8.
  7. ^ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
  8. ^ Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S.; Audi, G. (2021). "The NUBASE2020 evaluation of nuclear properties" (PDF). Chinese Physics C. 45 (3): 030001. doi:10.1088/1674-1137/abddae.
  9. ^ a b C. R. Hammond (2000). The Elements, in Handbook of Chemistry and Physics 81st edition. CRC press. ISBN 0849304814.
  10. ^ M. Jackson (2000). "Magnetism of Rare Earth" (PDF). The IRM quarterly. 10 (3): 1.
  11. ^ "Chemical reactions of Thulium". Webelements. Retrieved 2009-06-06.
  12. ^ Patnaik, Pradyot (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. p. 934. ISBN 0070494398. Retrieved 2009-06-06.
  13. ^ Lide, David R. (1998). "Section 11, Table of the Isotopes". Handbook of Chemistry and Physics (87 ed.). Boca Raton, FL: CRC Press. ISBN 0849305942.
  14. ^ James, Charles (1911). "Thulium I". J. Am. Chem. Soc. 33 (8): 1332–1344. doi:10.1021/ja02221a007.
  15. ^ James B. Hedrick. "Rare-Earth Metals" (PDF). USGS. Retrieved 2009-06-06.
  16. ^ Stephen B. Castor and James B. Hedrick. "Rare Earth Elements" (PDF). Retrieved 2009-06-06.
  17. ^ a b John Emsley (2001). Nature's building blocks: an A-Z guide to the elements. US: Oxford University Press. pp. 442–443. ISBN 0198503415.
  18. ^ Walter Koechner (2006). Solid-state laser engineering. Springer. p. 49. ISBN 038729094X.
  19. ^ Frank J. Duarte (2008). Tunable laser applications. CRC Press. p. 214. ISBN 1420060090.
  20. ^ a b C. K. Gupta, Nagaiyar Krishnamurthy (2004). Extractive metallurgy of rare earths. CRC Press. p. 32. ISBN 0415333407.
  21. ^ Krishnamurthy, Devan (2011). "Comparison of high–dose rate prostate brachytherapy dose distributions with iridium-192, ytterbium-169, and thulium-170 sources". Brachytherapy. 10 (6): 461–465. doi:10.1016/j.brachy.2011.01.012. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  22. ^ Ayoub, Amal Hwaree et al. Development of New Tm-170 Radioactive Seeds for Brachytherapy, Department of Biomedical Engineering, Ben-Gurion University of the Negev
  23. ^ Theodore W. Gray, Nick Mann (2009). The Elements: A Visual Exploration of Every Known Atom In The Universe. Black Dog & Leventhal Publishers. p. 159. ISBN 139781579128142. {{cite book}}: Check |isbn= value: length (help)
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