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Polonium, 84Po
Polonium
Pronunciation/pəˈloʊniəm/ ​(pə-LOH-nee-əm)
Allotropesα, β
Appearancesilvery
Mass number[209]
Polonium 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
Te
↑
Po
↓
Lv
bismuth ← polonium → astatine
Atomic number (Z)84
Groupgroup 16 (chalcogens)
Periodperiod 6
Block  p-block
Electron configuration[Xe] 4f14 5d10 6s2 6p4
Electrons per shell2, 8, 18, 32, 18, 6
Physical properties
Phase at STPsolid
Melting point527 K ​(254 °C, ​489 °F)
Boiling point1235 K ​(962 °C, ​1764 °F)
Density (near r.t.)α-Po: 9.196 g/cm3
β-Po: 9.398 g/cm3
Heat of fusionca. 13 kJ/mol
Heat of vaporization102.91 kJ/mol
Molar heat capacity26.4 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) (846) 1003 1236
Atomic properties
Oxidation statescommon: −2, +2, +4
+5[1] +6,[2]
ElectronegativityPauling scale: 2.0
Ionization energies
  • 1st: 812.1 kJ/mol
Atomic radiusempirical: 168 pm
Covalent radius140±4 pm
Van der Waals radius197 pm
Color lines in a spectral range
Spectral lines of polonium
Other properties
Natural occurrencefrom decay
Crystal structure ​cubic
Cubic crystal structure for polonium

α-Po
Crystal structure ​rhombohedral
Rhombohedral crystal structure for polonium

β-Po
Thermal expansion23.5 µm/(m⋅K) (at 25 °C)
Thermal conductivity20 W/(m⋅K) (?)
Electrical resistivityα-Po: 0.40 µΩ⋅m (at 0 °C)
Magnetic orderingnonmagnetic
CAS Number7440-08-6
History
Namingafter Polonia, Latin for Poland, homeland of Marie Curie
DiscoveryPierre and Marie Curie (1898)
First isolationWilly Marckwald (1902)
Isotopes of polonium
Main isotopes[3] Decay
abun­dance half-life (t1/2) mode pro­duct
208Po synth 2.898 y α 204Pb
β+ 208Bi
209Po synth 124 y α 205Pb
β+ 209Bi
210Po trace 138.376 d α 206Pb
 Category: Polonium
| references

Polonium (Template:PronEng) is a chemical element that has the symbol Po and atomic number 84. A rare and highly radioactive metalloid,[4] polonium is chemically similar to tellurium and bismuth, and it occurs in uranium ores. Polonium has been studied for possible use in heating spacecraft. It is unstable; all isotopes of polonium are radioactive.

Notable characteristics

Polonium is a radioactive element that exists in two metallic allotropes.[5]

Isotopes

Main article: Isotopes of polonium

Polonium has 25 known isotopes, all of which are radioactive. They have atomic masses that range from 194u to 218u. 210Po (half-life 138.376 days) is the most widely available. 209Po (half-life 103 years) and 208Po (half-life 2.9 years) can be made through the alpha, proton, or deuteron bombardment of lead or bismuth in a cyclotron.

210Po

210Po is an alpha emitter that has a half-life of 138.376 days; it decays directly to its daughter isotope 206Pb. A milligram of 210Po emits about as many alpha particles per second as 4.5 grams of 226Ra. A few curies (1 curie equals 37 gigabecquerels) of 210Po emit a blue glow which is caused by excitation of surrounding air. A single gram of 210Po generates 140 watts of power.[6] Because it emits many alpha particles, which are stopped within a very short distance in dense media and release their energy, 210Po has been used as a lightweight heat source to power thermoelectric cells in artificial satellites; for instance, 210Po heat source was also used in each of the Lunokhod rovers deployed on the surface of the Moon, to keep their internal components warm during the lunar nights.[7] Some anti-static brushes contain up to 500 microcuries of 210Po as a source of charged particles for neutralizing static electricity in materials like photographic film. 210Po was also used as a murder weapon in the Alexander Litvinenko poisoning[8]

The majority of the time 210Po decays by emission of an alpha particle only, not by emission of an alpha particle and a gamma ray. About one in 100,000 alpha emissions causes an excitation in the nucleus which then results in the emission of a gamma ray.[9] This low gamma ray production rate (and the short range of alpha particles) makes it difficult to find and identify this isotope. Rather than gamma ray spectroscopy, alpha spectroscopy is the best method of measuring this isotope.

Solid state form

The alpha form of solid polonium has a simple cubic crystal structure with an edge length of 3.352 Å.

The beta form of polonium is rhombohedral; it has been reported in the chemical literature, along with the alpha form, several times. A picture of it is present on the web.[10]

Two papers report X-ray diffraction experiments on polonium metal.[11][12] The first report of the crystal structure of polonium was done using electron diffraction.[13]

Chemistry

The chemistry of polonium is similar to that of tellurium and bismuth. Polonium dissolves readily in dilute acids, but is only slightly soluble in alkalis. The hydrogen compound PoH2 is liquid at room temperature (M.P. -36.1°C to B.P. 35.3°C). Halides of the structure PoX2, PoX4 and PoX6 are known. The two oxides PoO2 and PoO3 are the products of oxidation of polonium.[14]

210Po (in common with 238Pu) has the ability to become airborne with ease: if a sample is heated in air to 328 K (55°C, 131°F), 50% of it is vaporized in 45 hours, even though the melting point of polonium is 527 K (254°C, 489°F) and its boiling point is 1235 K (962°C, 1763°F).[15] More than one hypothesis exists for how polonium does this; one suggestion is that small clusters of polonium atoms are spalled off by the alpha decay.

It has been reported that some microbes can methylate polonium by the action of methylcobalamin.[16][17]This is similar to the way in which mercury, selenium and tellurium are methylated in living things to create organometallic compounds. As a result when considering the biochemistry of polonium one should consider the possibility that the polonium will follow the same biochemical pathways as selenium and tellurium.

The alpha form of solid polonium.

Compounds

History

Also tentatively called "Radium F", polonium was discovered by Marie Skłodowska-Curie and her husband Pierre Curie in 1898[18] and was later named after Marie Curie's native land of Poland (Latin: Polonia).[19][20] Poland at the time was under Russian, Prussian, and Austrian partition, and did not exist as an independent country. It was Curie's hope that naming the element after her native land would publicize its lack of independence. Polonium may be the first element named to highlight a political controversy.[21]

This element was the first one discovered by the Curies while they were investigating the cause of pitchblende radioactivity. The pitchblende, after removal of the radioactive elements uranium and thorium, was more radioactive than both the uranium and thorium put together. This spurred the Curies on to find additional radioactive elements. The Curies first separated out polonium from the pitchblende, and then within a few years, also isolated radium.



Detection

Intensity against photon energy for three isotopes.

Gamma counting

By means of radiometric methods such as gamma spectroscopy (or a method using a chemical separation followed by an activity measurement with a non-energy-dispersive counter), it is possible to measure the concentrations of radioisotopes and to distinguish one from another. In practice, background noise would be present and depending on the detector, the line width would be larger which would make it harder to identify and measure the isotope. In biological/medical work it is common to use the natural 40K present in all tissues/body fluids as a check of the equipment and as an internal standard.

Intensity against alpha energy for four isotopes, note that the line width is narrow and the fine details can be seen.
Intensity against alpha energy for four isotopes, note that the line width is wide and some of the fine details can not be seen. This is for liquid scintillation counting where random effects cause a variation in the number of visible photons generated per alpha decay.

Alpha counting

The best way to test for (and measure) many alpha emitters is to use alpha-particle spectroscopy as it is common to place a drop of the test solution on a metal disk which is then dried out to give a uniform coating on the disk. This is then used as the test sample. If the thickness of the layer formed on the disk is too thick then the lines of the spectrum are broadened, this is because some of the energy of the alpha particles is lost during their movement through the layer of active material. An alternative method is to use internal liquid scintillation where the sample is mixed with a scintillation cocktail. When the light emitted is then counted, some machines will record the amount of light energy per radioactive decay event. Due to the imperfections of the liquid scintillation method (such as a failure for all the photons to be detected, cloudy or coloured samples can be difficult to count) and the fact that random quenching can reduce the number of photons generated per radioactive decay it is possible to get a broadening of the alpha spectra obtained through liquid scintillation. It is likely that these liquid scintillation spectra will be subject to a Gaussian broadening rather than the distortion exhibited when the layer of active material on a disk is too thick.

A third energy dispersive method for counting alpha particles is to use a semiconductor detector.

From left to right the peaks are due to 209Po, 210Po, 239Pu and 241Am. The fact that isotopes such as 239Pu and 241Am have more than one alpha line indicates that the nucleus has the ability to be in different discrete energy levels (like a molecule can).

Occurrence and production

Polonium is a very rare element in nature because of the short half-life of all its isotopes. It is found in uranium ores at about 100 micrograms per metric ton (1 part in 1010), which is approximately 0.2% of the abundance of radium. The amounts in the Earth's crust are not harmful. Polonium has been found in tobacco smoke from tobacco leaves grown with phosphate fertilizers, though similar amounts occur in everything from cherries to human tissue.[22][23]

Neutron capture

Synthesis by (n,) reaction

In 1934 an experiment showed that when natural 209Bi is bombarded with neutrons, 210Bi is created, which then decays to 210Po via β decay. Polonium may now be made in milligram amounts in this procedure which uses high neutron fluxes found in nuclear reactors. Only about 100 grams are produced each year, practically all of it in Russia, making polonium exceedingly rare.[24] [25]

Proton capture

Synthesis by (p, n) and (p,2n) reactions

It has been found that the longer-lived isotopes of polonium can be formed by proton bombardment of bismuth using a cyclotron. Other more neutron rich isotopes can be formed by the irradiation of platinum with carbon nuclei.[26]

Applications

When it is mixed or alloyed with beryllium, polonium can be a neutron source: beryllium releases a neutron upon absorption of an alpha particle that is supplied by 210Po. It has been used in this capacity as a neutron trigger or initiator for nuclear weapons. Other uses include

  • Devices that eliminate static charges in textile mills and other places.[27] However, beta particle sources are more commonly used and are less dangerous. A non-radioactive alternative is to use a high-voltage DC power supply to ionise air positively or negatively as required.[28]
  • 210Po can be used as an atomic heat source to power radioisotope thermoelectric generators via thermoelectric materials.
  • Because of its very high toxicity, polonium can be used as a poison (see, for example, Alexander Litvinenko poisoning).
  • Polonium is also used to get rid of dust on film

Toxicity

Overview

By mass, polonium-210 is around 250,000 times more toxic than hydrogen cyanide (the actual LD50 for 210Po is about 1 microgram for an 80 kg person (see below) compared to about 250 milligram for hydrogen cyanide[29]). The main hazard is its intense radioactivity (as an alpha emitter), which makes it very difficult to handle safely: one gram of Po will self-heat to a temperature of around 500 °C. Even in microgram amounts, handling 210Po is extremely dangerous, requiring specialized equipment and strict handling procedures. Alpha particles emitted by polonium will damage organic tissue easily if polonium is ingested, inhaled, or absorbed (though they do not penetrate the epidermis and hence are not hazardous if the polonium is outside the body).

Acute effects

The median lethal dose (LD50) for acute radiation exposure is generally about 4.5 Sv.[30] The committed effective dose equivalent 210Po is 0.51 µSv/Bq if ingested, and 2.5 µSv/Bq if inhaled.[31] Since 210Po has an activity of 166 TBq (4486.5 Ci) per gram[31] (1 gram produces 166×1012 decays per second), a fatal 4.5 Sv (J/kg) dose can be caused by ingesting 8.8 MBq/kg (238 microcuries, or about 24 mCi for 80 kg person), about 50 nanograms per kilogram (ng/kg), or inhaling 1.8 MBq/kg (48 microcuries, or about 4 mCi for 80 kg person), about 10 ng/kg. One gram of 210Po could thus in theory poison 2 million (50 kg each) people of whom 1 million would die. The actual toxicity of 210Po is lower than these estimates, because radiation exposure that is spread out over several weeks (the biological half-life of polonium in humans is 30 to 50 days[32]) is somewhat less damaging than an instantaneous dose. It has been estimated that a minimal lethal dose of 210Po for an 80 kg person is 0.15 GBq (4 millicuries), or 0.89 micrograms, still an extremely small amount. [33][34]

Long term (chronic) effects

In addition to the acute effects, radiation exposure (both internal and external) carries a long-term risk of death from cancer of 5–10% per Sv.[30] The general population is exposed to small amounts of polonium as a radon daughter in indoor air; the isotopes 214Po and 218Po are thought to cause the majority[35] of the estimated 15,000-22,000 lung cancer deaths in the US every year that have been attributed to indoor radon.[36] Tobacco smoking causes additional exposure to Po.[37]

Regulatory exposure limits

The maximum allowable body burden for ingested 210Po is only 1,100 Bq (0.03 microcurie), which is equivalent to a particle weighing only 6.8 picograms. The maximum permissible workplace concentration of airborne 210Po is about 10 Bq/m³ (3 × 10-10 µCi/cm³).[38] The target organs for polonium in humans are the spleen and liver.[39] As the spleen (150 g) and the liver (1.3 to 3 kg) are much smaller than the rest of the body, if the polonium is concentrated in these vital organs, it is a greater threat to life than the dose which would be suffered (on average) by the whole body if it were spread evenly throughout the body, in the same way as caesium or tritium (as T2O).

210Po is widely used in industry, and readily available with little regulation or restriction. In the US, a tracking system run by the Nuclear Regulatory Commission will be implemented in 2007 to register purchases of more than 16 curies of polonium 210 (enough to make up 5,000 lethal doses). The IAEA "is said to be considering tighter regulations... There is talk that it might tighten the polonium reporting requirement by a factor of 10, to 1.6 curies."[40]

Famous poisoning cases

Notably, the murder of Alexander Litvinenko, a Russian dissident, in 2006 was announced as due to 210Po poisoning [41][42] (see Alexander Litvinenko poisoning). According to Nick Priest, a radiation expert speaking on Sky News on December 2, Litvinenko was probably the first person ever to die of the acute α-radiation effects of 210Po.[43]

It has also been suggested that Irène Joliot-Curie was the first person ever to die from the radiation effects of polonium (due to a single intake) in 1956.[44] She was accidentally exposed to polonium in 1946 when a sealed capsule of the element exploded on her laboratory bench. A decade later, on 17 March 1956, she died in Paris from leukemia which may or may not have been caused by that exposure.

According to the book The Bomb in the Basement, several death cases in Israel during 1957-1969 were caused by 210Po.[45] A leak was discovered at a Weizmann Institute laboratory in 1957. Traces of 210Po were found on the hands of Prof. Dror Sadeh, a physicist who researched radioactive materials. Medical tests indicated no harm, but the tests did not include bone marrow. Sadeh died from cancer. One of his students died of leukemia, and two colleagues died after a few years, both from cancer. The issue was investigated secretly, and there was never any formal admission that a connection between the leak and the deaths had existed.[citation needed]

Treatment

It has been suggested that chelation agents such as British Anti-Lewisite (dimercaprol) can be used to decontaminate humans.[46][47] In one experiment, rats were given a fatal dose of 1.45 MBq/kg (8.7 ng/kg) of 210Po; all untreated rats were dead after 44 days, but 90% of the rats treated with the chelation agent HOEtTTC remained alive after 5 months.[48]

See also

References

  1. ^ Thayer, John S. (2010). "Relativistic Effects and the Chemistry of the Heavier Main Group Elements". Relativistic Methods for Chemists. Challenges and Advances in Computational Chemistry and Physics. 10: 78. doi:10.1007/978-1-4020-9975-5_2. ISBN 978-1-4020-9974-8.
  2. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 28. ISBN 978-0-08-037941-8.
  3. ^ 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.
  4. ^ Chemical Elements.com - Metalloids
  5. ^ Gary L. Miessler; Donald A. Tarr. Inorganic Chemistry (3 ed.). p. 285. ISBN 0-13-120198-0.{{cite book}}: CS1 maint: multiple names: authors list (link)
  6. ^ Polonium, Argonne National Laboratory
  7. ^ Andrew Wilson, Solar System Log, (London: Jane's Publishing Company Ltd, 1987), p. 64.
  8. ^ Staticmaster
  9. ^ 210PO A DECAY
  10. ^ The beta Po (A_i) Structure
  11. ^ R.J. Desando and R.C Lange, Journal of Inorganic and Nuclear Chemistry, 1966, 28, 1837-1846.
  12. ^ W.H Beamer and C.R. Maxwell, Journal of Chemical Physics, 1946, 14, 569-569.
  13. ^ M.A. Rollier, S.B. Hendricks and L.R. Maxwell, Journal of Chemical Physics, 1936, 4, 648-652.
  14. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  15. ^ Bogdan Wąs, Ryszard Misiak, Mirosław Bartyzel, Barbara Petelenz (2006). "Thermochromatographic Separation of 206,208Po from a Bismuth Target Bombardet with Protons" (PDF). Nukleonica. 51 (Suppl. 2): s3–s5.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  16. ^ Momoshima N., Song L.X., Osaki S.,Maeda Y., (2001). "Formation and emission of volatile polonium compound by microbial activity and polonium methylation with methylcobalamin". Environ Sci Technol. 35 (15): 2956–2960. doi:10.1021/es001730+ S0013-936X(00)01730-2. {{cite journal}}: Check |doi= value (help); Cite has empty unknown parameter: |1= (help)CS1 maint: extra punctuation (link) CS1 maint: multiple names: authors list (link)
  17. ^ Momoshima N., Song L.X., Osaki S.,Maeda Y., (2002). "Biologically induced Po emission from fresh water". J Environ Radioact. 63 (2): 187–197. doi:10.1016/S0265-931X(02)00028-0.{{cite journal}}: CS1 maint: extra punctuation (link) CS1 maint: multiple names: authors list (link)
  18. ^ Curie P., Curie M. (1898). Comptes Rendus. 126: 1101.
  19. ^ Pfützner M. (1999). "Borders of the Nuclear World --- 100 Years After Discovery of Polonium". Acta Physica Polonica B. 30: 1197. {{cite journal}}: Text "issue 5" ignored (help)
  20. ^ Adloff J. P. (681–688). "The centennial of the 1903 Nobel Prize for physics". Radichimica Acta. 91: 2003. doi:10.1524/ract.91.12.681.23428. {{cite journal}}: Text "issue 12" ignored (help)CS1 maint: date format (link)
  21. ^ Kabzinska K. (1998). "Chemical and Polish aspects of polonium and radium discovery". Przemysl Chemiczny. 77: 104–107. {{cite journal}}: Text "issue 3" ignored (help)
  22. ^ Kilthau, Gustave F. "Cancer risk in relation to radioactivity in tobacco". Radiologic Technology. 67: 217–222. {{cite journal}}: Unknown parameter |pim= ignored (help)
  23. ^ Alpha Radioactivity (210 Polonium) and Tobacco Smoke
  24. ^ http://www.rsc.org/chemistryworld/News/2006/November/27110601.asp RSC Chemistry World Q&A
  25. ^ The St. Petersburg Times - News - Most Polonium Made Near the Volga River
  26. ^ Atterling, H., Forsling, W. (1959). "Light Polonium Isotopes from Carbon Ion Bombardments of Platinum". Arkiv for Fysik. 15 (1): 81–88.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  27. ^ BBC News | ENGLAND | College breaches radioactive regulations
  28. ^ http://www.thermo.com/eThermo/CMA/PDFs/Articles/articlesFile_16929.pdf
  29. ^ Hydrogen cyanide msds
  30. ^ a b http://www.pnl.gov/main/publications/external/technical_reports/PNNL-14424.pdf
  31. ^ a b Nuclide Safety Data Sheet: Polonium–210
  32. ^ Effective half-life of polonium in the human
  33. ^ Polonium Poisoning
  34. ^ See also "Polonium-210 as a poison". "The conclusion is reached that 0.1–0.3 GBq or more absorbed to blood of an adult male is likely to be fatal within 1 month. This corresponds to ingestion of 1–3 GBq or more, assuming 10% absorption to blood".
  35. ^ National Academy of Sciences 1988 report Health Risks of Radon and Other Internally Deposited Alpha-Emitters: BEIR IV, page 5
  36. ^ National Academy of Sciences 1999 report Health Effects Of Exposure To Indoor Radon
  37. ^ The Straight Dope Does smoking organically grown tobacco lower the chance of lung cancer?
  38. ^ Nuclear Regulatory Commission limits for 210Po
  39. ^ PilgrimWatch - Pilgrim Nuclear - Health Impact
  40. ^ Peter D. Zimmerman (2006). "The Smoky Bomb Threat". The New York Times. Retrieved 2006-12-19.
  41. ^ "The mystery of Litvinenko's death". BBC News. 24 November 2006.
  42. ^ UK requests Lugovoi extradition BBC News
  43. ^ "Focus: Cracking the code of the nuclear assassin".
  44. ^ Innocent chemical a killer - The Daily Telegraph (of Australia), December 4, 2006 [1]
  45. ^ Karpin, Michael (2006). The bomb in the basement: How Israel went nuclear and what that means for the world. Simon and Schuster. ISBN 0743265947.
  46. ^ [2]9 also see NRCP Report No. 65: Management of Persons Accidentally Contaminated With Radionuclides
  47. ^ http://www.fda.gov/cder/Guidance/6983fnl.pdf
  48. ^ Rencováa J., Svoboda V., Holuša R., Volf V., Jones M. M., Singh P. K. (1997). "Reduction of subacute lethal radiotoxicity of polonium-210 in rats by chelating agents". International Journal of Radiation Biology. 72 (3): 247–249. doi:10.1080/095530097143338.{{cite journal}}: CS1 maint: multiple names: authors list (link)
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References and External links verified 2006-11-25 unless noted.

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