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[[Image:Thallium rod corroded.jpg|thumb|left|Corroded thallium rod]]
[[Image:Thallium rod corroded.jpg|thumb|left|Corroded thallium rod]]


Although the metal is reasonably abundant in the [[Earth]]'s crust at a concentration estimated to be about 0.7 mg/kg, mostly in association with [[potassium]] minerals in [[clay]]s, [[soil]]s, and [[granite]]s, it is not generally considered to be commercially recoverable from those forms. The major source of commercial thallium is the trace amounts found in [[copper]], [[lead]], [[zinc]], and other [[sulfide]] [[ore]]s.
Although the metal is reasonably abundant in the [[Earth]]'s crust at a concentration estimated to be about 0.7&nbsp;mg/kg, mostly in association with [[potassium]] minerals in [[clay]]s, [[soil]]s, and [[granite]]s, it is not generally considered to be commercially recoverable from those forms. The major source of commercial thallium is the trace amounts found in [[copper]], [[lead]], [[zinc]], and other [[sulfide]] [[ore]]s.<ref>{{cite journal | doi =10.1007/BF01684859 pages =23–30}}</ref><ref name="Vira">{{cite journal | doi = 10.1016/j.envint.2004.09.003 | title = Thallium: a review of public health and environmental concerns | year = 2005 | last1 = Peter | first1 = A | last2 = Viraraghavan | first2 = T | journal = Environment International | volume = 31 | pages = 493 | pmid = 15788190 | issue = 4}}</ref>


Thallium is found in the minerals [[crookesite]] TlCu<sub>7</sub>Se<sub>4</sub>, [[hutchinsonite]] TlPbAs<sub>5</sub>S<sub>9</sub>, and [[lorandite]] TlAsS<sub>2</sub>.<ref>{{cite journal | doi = 10.1016/0016-7037(52)90003-3 | title = The geochemistry of thallium | year = 1952 | last1 = Shaw | first1 = D | journal = Geochimica et Cosmochimica Acta | volume = 2 | pages = 118}}</ref> It also occurs as trace in [[pyrite]] and extracted as a by-product of roasting this ore for sulfuric acid production.<ref name="sl2001">{{cite web|title=Chemical fact sheet&nbsp;— Thallium|publisher=''Spectrum Laboratories''|year=2001|month=April|url=http://www.speclab.com/elements/thallium.htm|accessdate=2008-02-02}}</ref><ref name="Downs">{{cite web|title = Chemistry of Aluminium, Gallium, Indium, and Thallium|first =Anthony John|last = Downs|publisher = Springer|year = 1993|isbn = 9780751401035|pages = 89 and 106|url = http://books.google.com/books?id=v-04Kn758yIC}}</ref> The metal can be obtained from the [[smelting]] of lead and zinc rich ores. [[Manganese nodule]]s found on the [[ocean floor]] also contain thallium, but nodule extraction is prohibitively expensive and potentially environmentally destructive. In addition, several other thallium minerals, containing 16% to 60% thallium, occur in nature as sulfide or selenide complexes with [[antimony]], [[arsenic]], copper, lead, and [[silver]], but are rare, and have no commercial importance as sources of this element.
Thallium is found in the minerals [[crookesite]] TlCu<sub>7</sub>Se<sub>4</sub>, [[hutchinsonite]] TlPbAs<sub>5</sub>S<sub>9</sub>, and [[lorandite]] TlAsS<sub>2</sub>.<ref>{{cite journal | doi = 10.1016/0016-7037(52)90003-3 | title = The geochemistry of thallium | year = 1952 | last1 = Shaw | first1 = D | journal = Geochimica et Cosmochimica Acta | volume = 2 | pages = 118–154 }}</ref> It also occurs as trace in [[pyrite]] and extracted as a by-product of roasting this ore for sulfuric acid production.<ref name="sl2001">{{cite web|title=Chemical fact sheet&nbsp;— Thallium|publisher=''Spectrum Laboratories''|year=2001|month=April|url=http://www.speclab.com/elements/thallium.htm|accessdate=2008-02-02}}</ref><ref name="Downs">{{cite web|title = Chemistry of Aluminium, Gallium, Indium, and Thallium|first =Anthony John|last = Downs|publisher = Springer|year = 1993|isbn = 9780751401035|pages = 89 and 106|url = http://books.google.com/books?id=v-04Kn758yIC}}</ref> The metal can be obtained from the [[smelting]] of lead and zinc rich ores. [[Manganese nodule]]s found on the [[ocean floor]] also contain thallium, but nodule extraction is prohibitively expensive and potentially environmentally destructive.<ref>{{cite journal | doi = 10.1016/j.marchem.2003.09.006 | pages 125–139}}</ref> In addition, several other thallium minerals, containing 16% to 60% thallium, occur in nature as sulfide or selenide complexes with [[antimony]], [[arsenic]], copper, lead, and [[silver]], but are rare, and have no commercial importance as sources of this element.


==Isotopes==
==Isotopes==

Revision as of 20:11, 10 May 2010

Thallium, 81Tl
Thallium
Pronunciation/ˈθæliəm/ (THAL-ee-əm)
Appearancesilvery white
Standard atomic weight Ar°(Tl)
Thallium 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
In

Tl

Nh
mercurythalliumlead
Atomic number (Z)81
Groupgroup 13 (boron group)
Periodperiod 6
Block  p-block
Electron configuration[Xe] 4f14 5d10 6s2 6p1
Electrons per shell2, 8, 18, 32, 18, 3
Physical properties
Phase at STPsolid
Melting point577 K ​(304 °C, ​579 °F)
Boiling point1746 K ​(1473 °C, ​2683 °F)
Density (at 20° C)11.873 g/cm3[3]
when liquid (at m.p.)11.22 g/cm3
Heat of fusion4.14 kJ/mol
Heat of vaporization165 kJ/mol
Molar heat capacity26.32 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 882 977 1097 1252 1461 1758
Atomic properties
Oxidation states−5,[4] −2, −1, +1, +2, +3 (a mildly basic oxide)
ElectronegativityPauling scale: 1.62
Ionization energies
  • 1st: 589.4 kJ/mol
  • 2nd: 1971 kJ/mol
  • 3rd: 2878 kJ/mol
Atomic radiusempirical: 170 pm
Covalent radius145±7 pm
Van der Waals radius196 pm
Color lines in a spectral range
Spectral lines of thallium
Other properties
Natural occurrenceprimordial
Crystal structurehexagonal close-packed (hcp) (hP2)
Lattice constants
Hexagonal close packed crystal structure for thallium
a = 345.66 pm
c = 552.52 pm (at 20 °C)[3]
Thermal expansion29.9 µm/(m⋅K) (at 25 °C)
Thermal conductivity46.1 W/(m⋅K)
Electrical resistivity0.18 µΩ⋅m (at 20 °C)
Magnetic orderingdiamagnetic[5]
Molar magnetic susceptibility−50.9×10−6 cm3/mol (298 K)[6]
Young's modulus8 GPa
Shear modulus2.8 GPa
Bulk modulus43 GPa
Speed of sound thin rod818 m/s (at 20 °C)
Poisson ratio0.45
Mohs hardness1.2
Brinell hardness26.5–44.7 MPa
CAS Number7440-28-0
History
Namingafter Greek thallos, green shoot or twig
DiscoveryWilliam Crookes (1861)
First isolationClaude-Auguste Lamy (1862)
Isotopes of thallium
Main isotopes[7] Decay
abun­dance half-life (t1/2) mode pro­duct
201Tl synth 3.0421 d ε 201Hg
203Tl 29.5% stable
204Tl synth 3.78 y β 204Pb
ε + β+ 204Hg
205Tl 70.5% stable
 Category: Thallium
| references

Thallium is a chemical element with the symbol Tl and atomic number 81. This soft gray malleable poor metal resembles tin but discolors when exposed to air. Approximately 60-70% of thallium production is used in the electronics industry, and the rest is used in the pharmaceutical industry and in glass manufacturing.[8] It is also used in infrared detectors. Thallium is highly toxic and is used in rat poisons and insecticides, but its use has been cut back or eliminated in many countries. Because of its use for murder, thallium has gained the nicknames "The Poisoner's Poison" and "Inheritance Powder" (alongside arsenic).

Characteristics

Thallium is very soft and malleable and can be cut with a knife at room temperature. It has a metallic luster, but when exposed to air, it quickly tarnishes with a bluish-grey tinge that resembles lead. (It is preserved by keeping it under oil). A heavy layer of oxide builds up on thallium if left in air. In the presence of water, thallium hydroxide is formed.

History

Thallium (Greek θαλλός, thallos, meaning "a green shoot or twig")[9] was discovered by flame spectroscopy in 1862. The name comes from thallium's bright green spectral emission lines.[10]

After the publication of the improved method of flame spectroscopy by Robert Bunsen and Gustav Kirchhoff[11] and the discovery of caesium and rubidium in the years 1859 to 1860 flame spectroscopy became an approved method to determine the composition of minerals and chemical products. William Crookes and Claude-Auguste Lamy both started to use the new method. William Crookes used it to make spectroscopic determinations for tellurium on selenium compounds deposited in the lead chamber of a sulfuric acid production plant near Tilkerode in the Harz mountains. He had obtained the samples for his research on selenium cyanide from August Hofmann years earlier.[12][13] By 1862 Crookes was able to isolate small quantities of the element and determine the properties of a few compounds.[14] Claude-Auguste Lamy used a similar spectrometer to Crookes' to determine the composition of a selenium-containing substance which was deposited during the production of sulfuric acid from pyrite. He also noticed the new green line in the spectra and concluded that a new element was present. Lamy had received this material from the sulfuric acid plant of his friend Fréd Kuhlmann and this by-product was available in large quantities. Lamy started to isolate the new element from that source.[15] The fact that Lamy was able to work ample quantities of thallium enabled him to determine the properties of several compounds and in addition he prepared a small ingot of metallic thallium which he prepared by remelting thallium he had obtained by electrolysis of thallium salts.

As both scientists discovered thallium independently and a large part of the work, especially the isolation of the metallic thallium was done by Lamy, Crookes tried to secure his priority on the work. Lamy was awarded a medal at the International Exhibition in London 1862: For the discovery of a new and abundant source of thallium and after heavy protest Crookes also received a medal: thallium, for the discovery of the new element. The controversy between both scientists continued through 1862 and 1863. Most of the discussion ended after Crookes was elected Fellow of the Royal Society in June 1863.[16][17]

Occurrence and production

Corroded thallium rod

Although the metal is reasonably abundant in the Earth's crust at a concentration estimated to be about 0.7 mg/kg, mostly in association with potassium minerals in clays, soils, and granites, it is not generally considered to be commercially recoverable from those forms. The major source of commercial thallium is the trace amounts found in copper, lead, zinc, and other sulfide ores.[18][19]

Thallium is found in the minerals crookesite TlCu7Se4, hutchinsonite TlPbAs5S9, and lorandite TlAsS2.[20] It also occurs as trace in pyrite and extracted as a by-product of roasting this ore for sulfuric acid production.[8][21] The metal can be obtained from the smelting of lead and zinc rich ores. Manganese nodules found on the ocean floor also contain thallium, but nodule extraction is prohibitively expensive and potentially environmentally destructive.[22] In addition, several other thallium minerals, containing 16% to 60% thallium, occur in nature as sulfide or selenide complexes with antimony, arsenic, copper, lead, and silver, but are rare, and have no commercial importance as sources of this element.

Isotopes

Thallium has 25 isotopes which have atomic masses that range from 184 to 210. 203Tl and 205Tl are the only stable isotopes, and 204Tl is the most stable radioisotope, with a half-life of 3.78 years.[23]

202Tl (half life 12.23 days) can be made in a cyclotron,[24] while 204Tl (half life 3.78 years) is made by the neutron activation of stable thallium in a nuclear reactor.[25][23]

201Tl (half-life 73 hrs), decays by electron capture, emitting Hg x-rays (~ 70-80 keV), and photons of 135 and 167 keV in 10% total abundance;[23] therefore it has good imaging characteristics without excessive patient radiation dose. It is the most popular isotope used for thallium nuclear cardiac stress tests.[26]

Compounds

Fluorides: Thallium(I) fluoride (TlF), Thallium(III) fluoride (TlF3)
Chlorides: Thallium(I) chloride (TlCl), Thallium(II) chloride (TlCl2), Thallium(III) chloride (TlCl3)
Bromides: Thallium(I) bromide (TlBr), Thallium(II) bromide (Tl2Br4)
Iodides: Thallium iodide (TlI), Thallium triiodide (TlI3)
Hydrides: none listed
Oxides: Thallium(I) oxide (Tl2O), Thallium(III) oxide (Tl2O3)
Sulfates: Thallium(I) sulfate Tl2SO4
Sulfides: Thallium(I) sulfide Tl2S
Selenides: Thallium(I) selenide Tl2Se
Tellurides: none listed
Nitrides: none listed

Applications

The odorless and tasteless thallium sulfate was once widely used as rat poison and ant killer. Since 1975, this use in the United States and many other countries is prohibited due to safety concerns.[8] Other uses:

The saturated solution of equal parts of thallium(I) formate (Tl(CHO2)) and thallium(I) malonate (Tl(C3H3O4)) in water is known as Clerici solution. It is a mobile odorless liquid whose color changes from yellowish to clear upon reducing the concentration of the thallium salts. With the density of 4.25 g/cm3 at 20 °C, Clerici solution is one of the heaviest aqueous solutions known. It was used in the 20th century for measuring density of minerals by the flotation method, but the use is discontinued due to the high toxicity and corrosiveness of the solution.[33][34]

Research activity with thallium is ongoing to develop high-temperature superconducting materials for such applications as magnetic resonance imaging, storage of magnetic energy, magnetic propulsion, and electric power generation and transmission. After the discovery of the first thallium barium calcium copper oxide superconductor in 1988 the research in applications started.[35]

Toxicity

Thallium and its compounds are extremely toxic, and should be handled with great care. Contact with skin is dangerous, and adequate ventilation should be provided when melting this metal. Thallium(I) compounds have a high aqueous solubility and are readily absorbed through the skin. Exposure to them should not exceed 0.1 mg per m² of skin in an 8-hour time-weighted average (40-hour work week). Thallium is a suspected human carcinogen.[36] For a long time thallium compounds where easyly available as rat poison This fact and that is water soluable and nearly tastless led to frequent intoxications by accident or by criminal intent.[17]

Treatment and internal decontamination

One of the main methods of removing thallium (both radioactive and normal) from humans is to use Prussian blue, which is a solid ion exchange material which absorbs thallium and releases potassium. Up to 20 g per day of Prussian blue is fed by mouth to the person, and it passes through their digestive system and comes out in the stool. Hemodialysis and hemoperfusion are also used to remove thallium from the blood serum. At later stage of the treatment additional potassium is used to mobilize thallium from the tissue.[37][38]

Thallium pollution

According to the United States Environmental Protection Agency (EPA), man-made sources of thallium pollution include gaseous emission of cement factories, coal burning power plants, and metal sewers. The main source of elevated thallium concentrations in water is the leaching of thallium from ore processing operations.[39][19]

References

  1. ^ "Standard Atomic Weights: Thallium". CIAAW. 2009.
  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. ^ Dong, Z.-C.; Corbett, J. D. (1996). "Na23K9Tl15.3: An Unusual Zintl Compound Containing Apparent Tl57−, Tl48−, Tl37−, and Tl5− Anions". Inorganic Chemistry. 35 (11): 3107–12. doi:10.1021/ic960014z. PMID 11666505.
  5. ^ Lide, D. R., ed. (2005). "Magnetic susceptibility of the elements and inorganic compounds". CRC Handbook of Chemistry and Physics (PDF) (86th ed.). Boca Raton (FL): CRC Press. ISBN 0-8493-0486-5.
  6. ^ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
  7. ^ 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.
  8. ^ a b c d e "Chemical fact sheet — Thallium". Spectrum Laboratories. 2001. Retrieved 2008-02-02. {{cite web}}: Italic or bold markup not allowed in: |publisher= (help); Unknown parameter |month= ignored (help)
  9. ^ Liddell & Scott, A Greek-English Lexicon, sub θαλλος
  10. ^ Weeks, Mary Elvira (1932). "The discovery of the elements. XIII. Supplementary note on the discovery of thallium". Journal of Chemical Education. 9: 2078. doi:10.1021/ed009p2078.
  11. ^ G. Kirchhoff, R. Bunsen (1861). "Chemische Analyse durch Spectralbeobachtungen". Annalen der Physik und Chemie. 189 (7): 337–381. doi:10.1002/andp.18611890702.
  12. ^ Crookes, William (1862 - 1863). "Preliminary Researches on Thallium". Proceedings of the Royal Society of London,. 12: 150–159. doi:10.1098/rspl.1862.0030. {{cite journal}}: Check date values in: |year= (help)CS1 maint: extra punctuation (link)
  13. ^ Crookes, William (1863). "On Thallium". Philosophical Transactions of the Royal Society of London,. 153: 173–192. doi:10.1098/rstl.1863.0009.{{cite journal}}: CS1 maint: extra punctuation (link)
  14. ^ DeKosky, Robert K. (1973). "Spectroscopy and the Elements in the Late Nineteenth Century: The Work of Sir William Crookes". The British Journal for the History of Science. 6 (4): 400–423. doi:10.1017/S0007087400012553.
  15. ^ Lamy, Claude-Auguste (1862). "De l'existencè d'un nouveau métal, le thallium". Comptes Rendus: 1255–.
  16. ^ James, Frank A. J. L. (1984). "Of 'Medals and Muddles' the Context of the Discovery of Thallium: William Crookes's Early". Notes and Records of the Royal Society of London. 39 (1): 65–90. doi:10.1098/rsnr.1984.0005.
  17. ^ a b Emsley, John (2006). "Thallium". The Elements of Murder: A History of Poison. Oxford University Press. pp. 326–327. ISBN 9780192806000.
  18. ^ . doi:10.1007/BF01684859 pages =23–30. {{cite journal}}: Check |doi= value (help); Cite journal requires |journal= (help); Missing or empty |title= (help); Missing pipe in: |doi= (help)
  19. ^ a b Peter, A; Viraraghavan, T (2005). "Thallium: a review of public health and environmental concerns". Environment International. 31 (4): 493. doi:10.1016/j.envint.2004.09.003. PMID 15788190.
  20. ^ Shaw, D (1952). "The geochemistry of thallium". Geochimica et Cosmochimica Acta. 2: 118–154. doi:10.1016/0016-7037(52)90003-3.
  21. ^ Downs, Anthony John (1993). "Chemistry of Aluminium, Gallium, Indium, and Thallium". Springer. pp. 89 and 106. ISBN 9780751401035.
  22. ^ . doi:10.1016/j.marchem.2003.09.006. {{cite journal}}: Cite journal requires |journal= (help); Missing or empty |title= (help); Text "pages 125–139" ignored (help)
  23. ^ a b c Audi, Georges (2003). "The NUBASE Evaluation of Nuclear and Decay Properties". Nuclear Physics A. 729. Atomic Mass Data Center: 3–128. doi:10.1016/j.nuclphysa.2003.11.001.
  24. ^ Thallium Research from Department of Energy
  25. ^ Manual for reactor produced radioisotopes from the International Atomic Energy Agency
  26. ^ Maddahi, Jamshid; Berman, Daniel (2001). "Detection, Evaluation, and Risk Stratification of Coronary Artery Disease by Thallium-201 Myocardial Perfusion Scintigraphy 155". Cardiac SPECT imaging (2 ed.). Lippincott Williams & Wilkins. pp. 155–178. ISBN 9780781720076.
  27. ^ a b c d e f C. R. Hammond. The Elements, in Handbook of Chemistry and Physics 81st edition. CRC press. ISBN 0849304857.
  28. ^ Nayer, P. S, Hamilton, O. (1977). "Thallium selenide infrared detector". Appl. Opt. 16: 2942. doi:10.1364/AO.16.002942.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  29. ^ Thallium Test from Walter Reed Army Medical Center
  30. ^ Thallium Stress Test from the American Heart Association
  31. ^ M. C., Lagunas-Solar (1982). Abstract "An integrally shielded transportable generator system for thallium-201 production". International Journal of Applied Radiation Isotopes. 33 (12): 1439–1443. doi:10.1016/0020-708X(82)90183-1. {{cite journal}}: Check |url= value (help); Unknown parameter |coauthors= ignored (|author= suggested) (help)
  32. ^ Thallium-201 production from Harvard Medical School's Joint Program in Nuclear Medicine
  33. ^ R. H. Jahns (1939). "Clerici solution for the specific gravity determination of small mineral grains" (PDF). 24: 116. {{cite journal}}: Cite journal requires |journal= (help); Unknown parameter |unused_data= ignored (help)
  34. ^ Peter G. Read (1999). Gemmology. Butterworth-Heinemann. pp. 63–64. ISBN 0750644117.
  35. ^ Sheng, Z. Z. (1988). "Bulk superconductivity at 120 K in the Tl–Ca/Ba–Cu–O system". Nature. 332: 138–139. doi:10.1038/332138a0. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  36. ^ "Biology of Thallium". webelemnts. Retrieved 2008-11-11.
  37. ^ Prussian blue fact sheet from the Centers for Disease Control and Prevention
  38. ^ Malbrain, Manu L. N. G. (1997). "= Treatment of Severe Thallium Intoxication". Clinical Toxicology. 35 (1): 97–100. doi:10.3109/15563659709001173. PMID 9022660. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)CS1 maint: extra punctuation (link)
  39. ^ "Factsheet on: Thallium" (PDF). Retrieved 2009-09-15.

External links