Polonium
Polonium | ||||||||||||||||||||||||||||||
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Pronunciation | /pəˈloʊniəm/ | |||||||||||||||||||||||||||||
Allotropes | α, β | |||||||||||||||||||||||||||||
Appearance | silvery | |||||||||||||||||||||||||||||
Mass number | [209] | |||||||||||||||||||||||||||||
Polonium in the periodic table | ||||||||||||||||||||||||||||||
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kJ/mol | ||||||||||||||||||||||||||||||
Heat of vaporization | 102.91 kJ/mol | |||||||||||||||||||||||||||||
Molar heat capacity | 26.4 J/(mol·K) | |||||||||||||||||||||||||||||
Vapor pressure
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Atomic properties | ||||||||||||||||||||||||||||||
Discovery | Pierre and Marie Curie (1898) | |||||||||||||||||||||||||||||
First isolation | Willy Marckwald (1902) | |||||||||||||||||||||||||||||
Isotopes of polonium | ||||||||||||||||||||||||||||||
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Polonium is a
Polonium was discovered on July 18, 1898 by
Characteristics
210Po is an alpha emitter that has a half-life of 138.4 days; it decays directly to its stable daughter isotope, 206Pb. A milligram (5 curies) of 210Po emits about as many alpha particles per second as 5 grams of 226Ra,[3] which means it is 5,000 times more radioactive than radium. A few curies (1 curie equals 37 gigabecquerels, 1 Ci = 37 GBq) of 210Po emit a blue glow which is caused by ionisation of the surrounding air.
About one in 100,000 alpha emissions causes an excitation in the nucleus which then results in the emission of a gamma ray with a maximum energy of 803 keV.[4][5]
Solid state form
Polonium is a radioactive element that exists in two
210Po (in common with 238Pu[citation needed]) has the ability to become airborne with ease: if a sample is heated in air to 55 °C (131 °F), 50% of it is vaporized in 45 hours to form diatomic Po2 molecules, even though the melting point of polonium is 254 °C (489 °F) and its boiling point is 962 °C (1,764 °F).[12][13][1] 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.[14]
Chemistry
The chemistry of polonium is similar to that of tellurium, although it also shows some similarities to its neighbor bismuth due to its metallic character. Polonium dissolves readily in dilute acids but is only slightly soluble in alkalis. Polonium solutions are first colored in pink by the Po2+ ions, but then rapidly become yellow because alpha radiation from polonium ionizes the solvent and converts Po2+ into Po4+. As polonium also emits alpha-particles after disintegration so this process is accompanied by bubbling and emission of heat and light by glassware due to the absorbed alpha particles; as a result, polonium solutions are volatile and will evaporate within days unless sealed.[15][16] At pH about 1, polonium ions are readily hydrolyzed and complexed by acids such as oxalic acid, citric acid, and tartaric acid.[17]
Compounds
Polonium has no common compounds, and almost all of its compounds are synthetically created; more than 50 of those are known.
Polonium hydride (PoH
2) is a volatile liquid at room temperature prone to dissociation; it is thermally unstable.[19] Water is the only other known hydrogen chalcogenide which is a liquid at room temperature; however, this is due to hydrogen bonding. The three oxides, PoO, PoO2 and PoO3, are the products of oxidation of polonium.[21]
Halides of the structure PoX2, PoX4 and PoF6 are known. They are soluble in the corresponding hydrogen halides, i.e., PoClX in HCl, PoBrX in HBr and PoI4 in HI.[22] Polonium dihalides are formed by direct reaction of the elements or by reduction of PoCl4 with SO2 and with PoBr4 with H2S at room temperature. Tetrahalides can be obtained by reacting polonium dioxide with HCl, HBr or HI.[23]
Other polonium compounds include the
A limited
Formula | Color | m.p. (°C) | Sublimation temp. (°C) |
Symmetry | Pearson symbol | Space group | No | a (pm) | b(pm) | c(pm) | Z | ρ (g/cm3) | ref |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
PoO | black | ||||||||||||
PoO2 | pale yellow | 500 (dec.) | 885 | fcc |
cF12 | Fm3m | 225 | 563.7 | 563.7 | 563.7 | 4 | 8.94 | [28] |
PoH2 | -35.5 | ||||||||||||
PoCl2 | dark ruby red | 355 | 130 | orthorhombic |
oP3 | Pmmm | 47 | 367 | 435 | 450 | 1 | 6.47 | [29] |
PoBr2 | purple-brown | 270 (dec.) | [30] | ||||||||||
PoCl4 | yellow | 300 | 200 | monoclinic |
[29] | ||||||||
PoBr4 | red | 330 (dec.) | fcc |
cF100 | Fm3m | 225 | 560 | 560 | 560 | 4 | [30] | ||
PoI4 | black | [31] |
Isotopes
Polonium has 42 known isotopes, all of which are
History
Tentatively called "
This element was the first one discovered by the Curies while they were investigating the cause of
In the United States, polonium was produced as part of the
Much of the basic physics of polonium was classified until after the war. The fact that a polonium-beryllium (Po-Be) initiator was used in the gun-type nuclear weapons was classified until the 1960s.[42]
The
Occurrence and production
Polonium is a very rare element in nature because of the short
Polonium can be found in
Because it is present in small concentrations, isolation of polonium from natural sources is a tedious process. The largest batch of the element ever extracted, performed in the first half of the 20th century, contained only 40 Ci (1.5 TBq) (9 mg) of polonium-210 and was obtained by processing 37 tonnes of residues from radium production.[53] Polonium is now usually obtained by irradiating bismuth with high-energy neutrons or protons.[15][54]
In 1934, an experiment showed that when natural 209Bi is bombarded with neutrons, 210Bi is created, which then decays to 210Po via beta-minus decay. By irradiating certain bismuth salts containing light element nuclei such as beryllium, a cascading (α,n) reaction can also be induced to produce 210Po in large quantities.[55] The final purification is done pyrochemically followed by liquid-liquid extraction techniques.[56] Polonium may now be made in milligram amounts in this procedure which uses high neutron fluxes found in nuclear reactors.[54] Only about 100 grams are produced each year, practically all of it in Russia, making polonium exceedingly rare.[57][58]
This process can cause problems in lead-bismuth based liquid metal cooled nuclear reactors such as those used in the Soviet Navy's K-27. Measures must be taken in these reactors to deal with the unwanted possibility of 210Po being released from the coolant.[59][60]
The longer-lived isotopes of polonium, 208Po and 209Po, can be formed by
Applications
Polonium-based sources of alpha particles were produced in the former Soviet Union.[62] Such sources were applied for measuring the thickness of industrial coatings via attenuation of alpha radiation.[63]
Because of intense alpha radiation, a one-gram sample of 210Po will spontaneously heat up to above 500 °C (932 °F) generating about 140 watts of power. Therefore, 210Po is used as an atomic heat source to power
The alpha particles emitted by polonium can be converted to neutrons using beryllium oxide, at a rate of 93 neutrons per million alpha particles.
Polonium was also part of brushes or more complex tools that eliminate static charges in photographic plates, textile mills, paper rolls, sheet plastics, and on substrates (such as automotive) prior to the application of coatings.[70] Alpha particles emitted by polonium ionize air molecules that neutralize charges on the nearby surfaces.[71][72] Some anti-static brushes contain up to 500 microcuries (20 MBq) of 210Po as a source of charged particles for neutralizing static electricity.[73] In the US, devices with no more than 500 μCi (19 MBq) of (sealed) 210Po per unit can be bought in any amount under a "general license",[74] which means that a buyer need not be registered by any authorities. Polonium needs to be replaced in these devices nearly every year because of its short half-life; it is also highly radioactive and therefore has been mostly replaced by less dangerous beta particle sources.[3]
Tiny amounts of 210Po are sometimes used in the laboratory and for teaching purposes—typically of the order of 4–40 kBq (0.11–1.08 μCi), in the form of sealed sources, with the polonium deposited on a substrate or in a resin or polymer matrix—are often exempt from licensing by the NRC and similar authorities as they are not considered hazardous. Small amounts of 210Po are manufactured for sale to the public in the United States as "needle sources" for laboratory experimentation, and they are retailed by scientific supply companies. The polonium is a layer of plating which in turn is plated with a material such as gold, which allows the
Polonium spark plugs were marketed by Firestone from 1940 to 1953. While the amount of radiation from the plugs was minuscule and not a threat to the consumer, the benefits of such plugs quickly diminished after approximately a month because of polonium's short half-life and because buildup on the conductors would block the radiation that improved engine performance. (The premise behind the polonium spark plug, as well as Alfred Matthew Hubbard's prototype radium plug that preceded it, was that the radiation would improve ionization of the fuel in the cylinder and thus allow the motor to fire more quickly and efficiently.)[75][76]
Biology and toxicity
Overview
Polonium can be hazardous and has no biological role.
Polonium does not have toxic chemical properties.[79]
It has been reported that some
Acute effects
The
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.
Regulatory exposure limits and handling
The maximum allowable body burden for ingested 210Po is only 1.1 kBq (30 nCi), which is equivalent to a particle massing only 6.8 picograms. The maximum permissible workplace concentration of airborne 210Po is about 10 Bq/m3 (3×10−10 µCi/cm3).[92] The target organs for polonium in humans are the spleen and liver.[93] 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).[citation needed]
210Po is widely used in industry, and readily available with little regulation or restriction.[94]}[95] In the US, a tracking system run by the Nuclear Regulatory Commission was implemented in 2007 to register purchases of more than 16 curies (590 GBq) 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 (59 GBq)."[96] As of 2013, this is still the only alpha emitting byproduct material available, as a NRC Exempt Quantity, which may be held without a radioactive material license.[citation needed]
Polonium and its compounds must be handled with caution inside special alpha
Cases of poisoning
Despite the element's highly hazardous properties, circumstances in which polonium poisoning can occur are rare. Its extreme scarcity in nature, the short half-lives of all its isotopes, the specialised facilities and equipment needed to obtain any significant quantity, and safety precautions against laboratory accidents all make harmful exposure events unlikely. As such, only a handful of cases of radiation poisoning specifically attributable to polonium exposure have been confirmed.[citation needed]
20th century
In response to concerns about the risks of occupational polonium exposure, quantities of 210Po were administered to five human volunteers at the University of Rochester from 1944 to 1947, in order to study its biological behaviour. These studies were funded by the Manhattan Project and the AEC. Four men and a woman participated, all suffering from terminal cancers, and ranged in age from their early thirties to early forties; all were chosen because experimenters wanted subjects who had not been exposed to polonium either through work or accident.[98] 210Po was injected into four hospitalised patients, and orally given to a fifth. None of the administered doses (all ranging from 0.17 to 0.30 μCi kg−1) approached fatal quantities.[99][98]
The first documented death directly resulting from polonium poisoning occurred in the Soviet Union, on 10 July 1954.[100][101] An unidentified 41-year-old man presented for medical treatment on 29 June, with severe vomiting and fever; the previous day, he had been working for five hours in an area in which, unknown to him, a capsule containing 210Po had depressurised and begun to disperse in aerosol form. Over this period, his total intake of airborne 210Po was estimated at 0.11 GBq (almost 25 times the estimated LD50 by inhalation of 4.5 MBq). Despite treatment, his condition continued to worsen and he died 13 days after the exposure event.[100]
From 1955 to 1957 the Windscale Piles had been releasing Polonium-210. The Windscale fire brought the need for testing of the land downwind for radioactive material contamination, and this is how it was found. An estimate of 8.8 terabecquerels (240 Ci) of polonium-210 has been made.
It has also been suggested that Irène Joliot-Curie's 1956 death from leukaemia was owed to the radiation effects of polonium. She was accidentally exposed in 1946 when a sealed capsule of the element exploded on her laboratory bench.[102]
As well, several deaths in Israel during 1957–1969 have been alleged to have resulted from 210Po exposure.
The Church Rock uranium mill spill July 16, 1979 is reported to have released polonium-210. The report states animals had higher concentrations of lead-210, polonium-210 and radium-226 than the tissues from control animals.[105]
21st century
The cause of the 2006 death of Alexander Litvinenko, a former Russian FSB agent who had defected to the United Kingdom in 2001, was identified to be poisoning with a lethal dose of 210Po;[106][107] it was subsequently determined that the 210Po had probably been deliberately administered to him by two Russian ex-security agents, Andrey Lugovoy and Dmitry Kovtun.[108][109] As such, Litvinenko's death was the first (and, to date, only) confirmed instance in which polonium's extreme toxicity has been used with malicious intent.[110][111][112]
In 2011, an allegation surfaced that the death of Palestinian leader Yasser Arafat, who died on 11 November 2004 of uncertain causes, also resulted from deliberate polonium poisoning,[113][114] and in July 2012, concentrations of 210Po many times more than normal were detected in Arafat's clothes and personal belongings by the Institut de Radiophysique in Lausanne, Switzerland.[115][116] Even though Arafat's symptoms were acute gastroenteritis with diarrhoea and vomiting,[117] the institute's spokesman said that despite the tests the symptoms described in Arafat's medical reports were not consistent with 210Po poisoning, and conclusions could not be drawn.[116] In 2013 the team found levels of polonium in Arafat's ribs and pelvis 18 to 36 times the average,[118][119] even though by this point in time the amount had diminished by a factor of 2 million.[120] Forensic scientist Dave Barclay stated, "In my opinion, it is absolutely certain that the cause of his illness was polonium poisoning. ... What we have got is the smoking gun - the thing that caused his illness and was given to him with malice."[117][118] Subsequently, French and Russian teams claimed that the elevated 210Po levels were not the result of deliberate poisoning, and did not cause Arafat's death.[121][122]
It has also been suspected that Russian businessman Roman Tsepov was killed with polonium. He had symptoms similar to Aleksander Litvinenko.[123]
Treatment
It has been suggested that chelation agents, such as British anti-Lewisite (dimercaprol), can be used to decontaminate humans.[124] 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 for five months.[125]
Detection in biological specimens
Polonium-210 may be quantified in biological specimens by alpha particle spectrometry to confirm a diagnosis of poisoning in hospitalized patients or to provide evidence in a medicolegal death investigation. The baseline urinary excretion of polonium-210 in healthy persons due to routine exposure to environmental sources is normally in a range of 5–15 mBq/day. Levels in excess of 30 mBq/day are suggestive of excessive exposure to the radionuclide.[126]
Occurrence in humans and the biosphere
Polonium-210 is widespread in the
As early as the 1920s, French biologist
Tobacco
The presence of polonium in tobacco smoke has been known since the early 1960s.[138][139] Some of the world's biggest tobacco firms researched ways to remove the substance—to no avail—over a 40-year period. The results were never published.[52]
Food
Polonium is found in the food chain, especially in seafood.[140][141]
See also
- Polonium halo
- Poisoning of Alexander Litvinenko
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External links
- Polonium at The Periodic Table of Videos(University of Nottingham)