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Americium
| 900 |
Synthesis and extraction
|
Most synthesis routines yield a mixture of different actinide isotopes in oxide forms, from which isotopes of americium can be separated. In a typical procedure, the spent reactor fuel (e.g. MOX fuel) is dissolved in nitric acid, and the bulk of uranium and plutonium is removed using a PUREX-type extraction (Plutonium–URanium EXtraction) with tributyl phosphate in a hydrocarbon. The lanthanides and remaining actinides are then separated from the aqueous residue (raffinate) by a diamide-based extraction, to give, after stripping, a mixture of trivalent actinides and lanthanides. Americium compounds are then selectively extracted using multi-step chromatographic and centrifugation techniques with an appropriate reagent. A large amount of work has been done on the solvent extraction of americium. For example, a 2003 EU-funded project codenamed "EUROPART" studied triazines and other compounds as potential extraction agents. A bis-triazinyl bipyridine complex was proposed in 2009 as such a reagent is highly selective to americium (and curium). Separation of americium from the highly similar curium can be achieved by treating a slurry of their hydroxides in aqueous sodium bicarbonate with ozone, at elevated temperatures. Both Am and Cm are mostly present in solutions in the +3 valence state; whereas curium remains unchanged, americium oxidizes to soluble Am(IV) complexes which can be washed away.
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Americium
| 900 |
Synthesis and extraction
|
Metallic americium is obtained by reduction from its compounds. Americium(III) fluoride was first used for this purpose. The reaction was conducted using elemental barium as reducing agent in a water- and oxygen-free environment inside an apparatus made of tantalum and tungsten.
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Americium
| 900 |
Synthesis and extraction
|
An alternative is the reduction of americium dioxide by metallic lanthanum or thorium:
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Americium
| 900 |
Physical properties
|
In the periodic table, americium is located to the right of plutonium, to the left of curium, and below the lanthanide europium, with which it shares many physical and chemical properties. Americium is a highly radioactive element. When freshly prepared, it has a silvery-white metallic lustre, but then slowly tarnishes in air. With a density of 12 g/cm, americium is less dense than both curium (13.52 g/cm) and plutonium (19.8 g/cm); but has a higher density than europium (5.264 g/cm)—mostly because of its higher atomic mass. Americium is relatively soft and easily deformable and has a significantly lower bulk modulus than the actinides before it: Th, Pa, U, Np and Pu. Its melting point of 1173 °C is significantly higher than that of plutonium (639 °C) and europium (826 °C), but lower than for curium (1340 °C).
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Americium
| 900 |
Physical properties
|
At ambient conditions, americium is present in its most stable α form which has a hexagonal crystal symmetry, and a space group P63/mmc with cell parameters a = 346.8 pm and c = 1124 pm, and four atoms per unit cell. The crystal consists of a double-hexagonal close packing with the layer sequence ABAC and so is isotypic with α-lanthanum and several actinides such as α-curium. The crystal structure of americium changes with pressure and temperature. When compressed at room temperature to 5 GPa, α-Am transforms to the β modification, which has a face-centered cubic (fcc) symmetry, space group Fm3m and lattice constant a = 489 pm. This fcc structure is equivalent to the closest packing with the sequence ABC. Upon further compression to 23 GPa, americium transforms to an orthorhombic γ-Am structure similar to that of α-uranium. There are no further transitions observed up to 52 GPa, except for an appearance of a monoclinic phase at pressures between 10 and 15 GPa. There is no consistency on the status of this phase in the literature, which also sometimes lists the α, β and γ phases as I, II and III. The β-γ transition is accompanied by a 6% decrease in the crystal volume; although theory also predicts a significant volume change for the α-β transition, it is not observed experimentally. The pressure of the α-β transition decreases with increasing temperature, and when α-americium is heated at ambient pressure, at 770 °C it changes into an fcc phase which is different from β-Am, and at 1075 °C it converts to a body-centered cubic structure. The pressure-temperature phase diagram of americium is thus rather similar to those of lanthanum, praseodymium and neodymium.
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Americium
| 900 |
Physical properties
|
As with many other actinides, self-damage of the crystal structure due to alpha-particle irradiation is intrinsic to americium. It is especially noticeable at low temperatures, where the mobility of the produced structure defects is relatively low, by broadening of X-ray diffraction peaks. This effect makes somewhat uncertain the temperature of americium and some of its properties, such as electrical resistivity. So for americium-241, the resistivity at 4.2 K increases with time from about 2 µOhm·cm to 10 µOhm·cm after 40 hours, and saturates at about 16 µOhm·cm after 140 hours. This effect is less pronounced at room temperature, due to annihilation of radiation defects; also heating to room temperature the sample which was kept for hours at low temperatures restores its resistivity. In fresh samples, the resistivity gradually increases with temperature from about 2 µOhm·cm at liquid helium to 69 µOhm·cm at room temperature; this behavior is similar to that of neptunium, uranium, thorium and protactinium, but is different from plutonium and curium which show a rapid rise up to 60 K followed by saturation. The room temperature value for americium is lower than that of neptunium, plutonium and curium, but higher than for uranium, thorium and protactinium.
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Americium
| 900 |
Physical properties
|
Americium is paramagnetic in a wide temperature range, from that of liquid helium, to room temperature and above. This behavior is markedly different from that of its neighbor curium which exhibits antiferromagnetic transition at 52 K. The thermal expansion coefficient of americium is slightly anisotropic and amounts to (7.5±0.2)×10 /°C along the shorter a axis and (6.2±0.4)×10 /°C for the longer c hexagonal axis. The enthalpy of dissolution of americium metal in hydrochloric acid at standard conditions is −620.6±1.3 kJ/mol, from which the standard enthalpy change of formation (ΔfH°) of aqueous Am ion is −621.2±2.0 kJ/mol. The standard potential Am/Am is −2.08±0.01 V.
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Americium
| 900 |
Chemical properties
|
Americium metal readily reacts with oxygen and dissolves in aqueous acids. The most stable oxidation state for americium is +3. The chemistry of americium(III) has many similarities to the chemistry of lanthanide(III) compounds. For example, trivalent americium forms insoluble fluoride, oxalate, iodate, hydroxide, phosphate and other salts. Compounds of americium in oxidation states 2, 4, 5, 6 and 7 have also been studied. This is the widest range that has been observed with actinide elements. The color of americium compounds in aqueous solution is as follows: Am (yellow-reddish), Am (yellow-reddish), AmO+2; (yellow), AmO2+2 (brown) and AmO5−6 (dark green). The absorption spectra have sharp peaks, due to f-f transitions' in the visible and near-infrared regions. Typically, Am(III) has absorption maxima at ca. 504 and 811 nm, Am(V) at ca. 514 and 715 nm, and Am(VI) at ca. 666 and 992 nm.
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Americium
| 900 |
Chemical properties
|
Americium compounds with oxidation state +4 and higher are strong oxidizing agents, comparable in strength to the permanganate ion (MnO−4) in acidic solutions. Whereas the Am ions are unstable in solutions and readily convert to Am, compounds such as americium dioxide (AmO2) and americium(IV) fluoride (AmF4) are stable in the solid state.
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Americium
| 900 |
Chemical properties
|
The pentavalent oxidation state of americium was first observed in 1951. In acidic aqueous solution the AmO+2 ion is unstable with respect to disproportionation. The reaction
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Americium
| 900 |
Chemical properties
|
is typical. The chemistry of Am(V) and Am(VI) is comparable to the chemistry of uranium in those oxidation states. In particular, compounds like Li3AmO4 and Li6AmO6 are comparable to uranates and the ion AmO2+2 is comparable to the uranyl ion, UO2+2. Such compounds can be prepared by oxidation of Am(III) in dilute nitric acid with ammonium persulfate. Other oxidising agents that have been used include silver(I) oxide, ozone and sodium persulfate.
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Americium
| 900 |
Chemical compounds
|
Three americium oxides are known, with the oxidation states +2 (AmO), +3 (Am2O3) and +4 (AmO2). Americium(II) oxide was prepared in minute amounts and has not been characterized in detail. Americium(III) oxide is a red-brown solid with a melting point of 2205 °C. Americium(IV) oxide is the main form of solid americium which is used in nearly all its applications. As most other actinide dioxides, it is a black solid with a cubic (fluorite) crystal structure.
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Americium
| 900 |
Chemical compounds
|
The oxalate of americium(III), vacuum dried at room temperature, has the chemical formula Am2(C2O4)3·7H2O. Upon heating in vacuum, it loses water at 240 °C and starts decomposing into AmO2 at 300 °C, the decomposition completes at about 470 °C. The initial oxalate dissolves in nitric acid with the maximum solubility of 0.25 g/L.
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Americium
| 900 |
Chemical compounds
|
Halides of americium are known for the oxidation states +2, +3 and +4, where the +3 is most stable, especially in solutions.
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Americium
| 900 |
Chemical compounds
|
Reduction of Am(III) compounds with sodium amalgam yields Am(II) salts – the black halides AmCl2, AmBr2 and AmI2. They are very sensitive to oxygen and oxidize in water, releasing hydrogen and converting back to the Am(III) state. Specific lattice constants are:
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Americium
| 900 |
Chemical compounds
|
Americium(III) fluoride (AmF3) is poorly soluble and precipitates upon reaction of Am and fluoride ions in weak acidic solutions:
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Americium
| 900 |
Chemical compounds
|
The tetravalent americium(IV) fluoride (AmF4) is obtained by reacting solid americium(III) fluoride with molecular fluorine:
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Americium
| 900 |
Chemical compounds
|
Another known form of solid tetravalent americium fluoride is KAmF5. Tetravalent americium has also been observed in the aqueous phase. For this purpose, black Am(OH)4 was dissolved in 15-M NH4F with the americium concentration of 0.01 M. The resulting reddish solution had a characteristic optical absorption spectrum which is similar to that of AmF4 but differed from other oxidation states of americium. Heating the Am(IV) solution to 90 °C did not result in its disproportionation or reduction, however a slow reduction was observed to Am(III) and assigned to self-irradiation of americium by alpha particles.
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Americium
| 900 |
Chemical compounds
|
Most americium(III) halides form hexagonal crystals with slight variation of the color and exact structure between the halogens. So, chloride (AmCl3) is reddish and has a structure isotypic to uranium(III) chloride (space group P63/m) and the melting point of 715 °C. The fluoride is isotypic to LaF3 (space group P63/mmc) and the iodide to BiI3 (space group R3). The bromide is an exception with the orthorhombic PuBr3-type structure and space group Cmcm. Crystals of americium hexahydrate (AmCl3·6H2O) can be prepared by dissolving americium dioxide in hydrochloric acid and evaporating the liquid. Those crystals are hygroscopic and have yellow-reddish color and a monoclinic crystal structure.
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Americium
| 900 |
Chemical compounds
|
Oxyhalides of americium in the form AmO2X2, AmO2X, AmOX2 and AmOX can be obtained by reacting the corresponding americium halide with oxygen or Sb2O3, and AmOCl can also be produced by vapor phase hydrolysis:
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Americium
| 900 |
Chemical compounds
|
The known chalcogenides of americium include the sulfide AmS2, selenides AmSe2 and Am3Se4, and tellurides Am2Te3 and AmTe2. The pnictides of americium (Am) of the AmX type are known for the elements phosphorus, arsenic, antimony and bismuth. They crystallize in the rock-salt lattice.
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Americium
| 900 |
Chemical compounds
|
Americium monosilicide (AmSi) and "disilicide" (nominally AmSix with: 1.87 < x < 2.0) were obtained by reduction of americium(III) fluoride with elementary silicon in vacuum at 1050 °C (AmSi) and 1150−1200 °C (AmSix). AmSi is a black solid isomorphic with LaSi, it has an orthorhombic crystal symmetry. AmSix has a bright silvery lustre and a tetragonal crystal lattice (space group I41/amd), it is isomorphic with PuSi2 and ThSi2. Borides of americium include AmB4 and AmB6. The tetraboride can be obtained by heating an oxide or halide of americium with magnesium diboride in vacuum or inert atmosphere.
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Americium
| 900 |
Chemical compounds
|
Analogous to uranocene, americium forms the organometallic compound amerocene with two cyclooctatetraene ligands, with the chemical formula (η-C8H8)2Am. A cyclopentadienyl complex is also known that is likely to be stoichiometrically AmCp3.
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Americium
| 900 |
Chemical compounds
|
Formation of the complexes of the type Am(n-C3H7-BTP)3, where BTP stands for 2,6-di(1,2,4-triazin-3-yl)pyridine, in solutions containing n-C3H7-BTP and Am ions has been confirmed by EXAFS. Some of these BTP-type complexes selectively interact with americium and therefore are useful in its selective separation from lanthanides and another actinides.
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Americium
| 900 |
Biological aspects
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Americium is an artificial element of recent origin, and thus does not have a biological requirement. It is harmful to life. It has been proposed to use bacteria for removal of americium and other heavy metals from rivers and streams. Thus, Enterobacteriaceae of the genus Citrobacter precipitate americium ions from aqueous solutions, binding them into a metal-phosphate complex at their cell walls. Several studies have been reported on the biosorption and bioaccumulation of americium by bacteria and fungi.
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Americium
| 900 |
Fission
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The isotope Am (half-life 141 years) has the largest cross sections for absorption of thermal neutrons (5,700 barns), that results in a small critical mass for a sustained nuclear chain reaction. The critical mass for a bare Am sphere is about 9–14 kg (the uncertainty results from insufficient knowledge of its material properties). It can be lowered to 3–5 kg with a metal reflector and should become even smaller with a water reflector. Such small critical mass is favorable for portable nuclear weapons, but those based on Am are not known yet, probably because of its scarcity and high price. The critical masses of the two readily available isotopes, Am and Am, are relatively high – 57.6 to 75.6 kg for Am and 209 kg for Am. Scarcity and high price yet hinder application of americium as a nuclear fuel in nuclear reactors.
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Americium
| 900 |
Fission
|
There are proposals of very compact 10-kW high-flux reactors using as little as 20 grams of Am. Such low-power reactors would be relatively safe to use as neutron sources for radiation therapy in hospitals.
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Americium
| 900 |
Isotopes
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About 19 isotopes and 11 nuclear isomers are known for americium, including mass numbers 223, 229, 230, and 232 through 247. There are two long-lived alpha-emitters; Am has a half-life of 7,370 years and is the most stable isotope, and Am has a half-life of 432.2 years. The most stable nuclear isomer is Am; it has a long half-life of 141 years. The half-lives of other isotopes and isomers range from 0.64 microseconds for Am to 50.8 hours for Am. As with most other actinides, the isotopes of americium with odd number of neutrons have relatively high rate of nuclear fission and low critical mass.
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Americium
| 900 |
Isotopes
|
Americium-241 decays to Np emitting alpha particles of 5 different energies, mostly at 5.486 MeV (85.2%) and 5.443 MeV (12.8%). Because many of the resulting states are metastable, they also emit gamma rays with the discrete energies between 26.3 and 158.5 keV.
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Americium
| 900 |
Isotopes
|
Americium-242 is a short-lived isotope with a half-life of 16.02 h. It mostly (82.7%) converts by β-decay to Cm, but also by electron capture to Pu (17.3%). Both Cm and Pu transform via nearly the same decay chain through Pu down to U.
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Americium
| 900 |
Isotopes
|
Nearly all (99.541%) of Am decays by internal conversion to Am and the remaining 0.459% by α-decay to Np. The latter subsequently decays to Pu and then to U.
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Americium
| 900 |
Isotopes
|
Americium-243 transforms by α-emission into Np, which converts by β-decay to Pu, and the Pu changes into U by emitting an α-particle.
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Americium
| 900 |
Applications
|
Americium is used in the most common type of household smoke detector, which uses Am in the form of americium dioxide as its source of ionizing radiation. This isotope is preferred over Ra because it emits 5 times more alpha particles and relatively little harmful gamma radiation.
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Americium
| 900 |
Applications
|
The amount of americium in a typical new smoke detector is 1 microcurie (37 kBq) or 0.29 microgram. This amount declines slowly as the americium decays into neptunium-237, a different transuranic element with a much longer half-life (about 2.14 million years). With its half-life of 432.2 years, the americium in a smoke detector includes about 3% neptunium after 19 years, and about 5% after 32 years. The radiation passes through an ionization chamber, an air-filled space between two electrodes, and permits a small, constant current between the electrodes. Any smoke that enters the chamber absorbs the alpha particles, which reduces the ionization and affects this current, triggering the alarm. Compared to the alternative optical smoke detector, the ionization smoke detector is cheaper and can detect particles which are too small to produce significant light scattering; however, it is more prone to false alarms.
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Americium
| 900 |
Applications
|
As Am has a roughly similar half-life to Pu (432.2 years vs. 87 years), it has been proposed as an active element of radioisotope thermoelectric generators, for example in spacecraft. Although americium produces less heat and electricity – the power yield is 114.7 mW/g for Am and 6.31 mW/g for Am (cf. 390 mW/g for Pu) – and its radiation poses more threat to humans owing to neutron emission, the European Space Agency is considering using americium for its space probes.
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Americium
| 900 |
Applications
|
Another proposed space-related application of americium is a fuel for space ships with nuclear propulsion. It relies on the very high rate of nuclear fission of Am, which can be maintained even in a micrometer-thick foil. Small thickness avoids the problem of self-absorption of emitted radiation. This problem is pertinent to uranium or plutonium rods, in which only surface layers provide alpha-particles. The fission products of Am can either directly propel the spaceship or they can heat a thrusting gas. They can also transfer their energy to a fluid and generate electricity through a magnetohydrodynamic generator.
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Americium
| 900 |
Applications
|
One more proposal which utilizes the high nuclear fission rate of Am is a nuclear battery. Its design relies not on the energy of the emitted by americium alpha particles, but on their charge, that is the americium acts as the self-sustaining "cathode". A single 3.2 kg Am charge of such battery could provide about 140 kW of power over a period of 80 days. Even with all the potential benefits, the current applications of Am are as yet hindered by the scarcity and high price of this particular nuclear isomer.
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Americium
| 900 |
Applications
|
In 2019, researchers at the UK National Nuclear Laboratory and the University of Leicester demonstrated the use of heat generated by americium to illuminate a small light bulb. This technology could lead to systems to power missions with durations up to 400 years into interstellar space, where solar panels do not function.
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Americium
| 900 |
Applications
|
The oxide of Am pressed with beryllium is an efficient neutron source. Here americium acts as the alpha source, and beryllium produces neutrons owing to its large cross-section for the (α,n) nuclear reaction:
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Americium
| 900 |
Applications
|
The most widespread use of AmBe neutron sources is a neutron probe – a device used to measure the quantity of water present in soil, as well as moisture/density for quality control in highway construction. Am neutron sources are also used in well logging applications, as well as in neutron radiography, tomography and other radiochemical investigations.
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Americium
| 900 |
Applications
|
Americium is a starting material for the production of other transuranic elements and transactinides – for example, 82.7% of Am decays to Cm and 17.3% to Pu. In the nuclear reactor, Am is also up-converted by neutron capture to Am and Am, which transforms by β-decay to Cm:
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Americium
| 900 |
Applications
|
Irradiation of Am by C or Ne ions yields the isotopes Es (einsteinium) or Db (dubnium), respectively. Furthermore, the element berkelium (Bk isotope) had been first intentionally produced and identified by bombarding Am with alpha particles, in 1949, by the same Berkeley group, using the same 60-inch cyclotron. Similarly, nobelium was produced at the Joint Institute for Nuclear Research, Dubna, Russia, in 1965 in several reactions, one of which included irradiation of Am with N ions. Besides, one of the synthesis reactions for lawrencium, discovered by scientists at Berkeley and Dubna, included bombardment of Am with O.
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Americium
| 900 |
Applications
|
Americium-241 has been used as a portable source of both gamma rays and alpha particles for a number of medical and industrial uses. The 59.5409 keV gamma ray emissions from Am in such sources can be used for indirect analysis of materials in radiography and X-ray fluorescence spectroscopy, as well as for quality control in fixed nuclear density gauges and nuclear densometers. For example, the element has been employed to gauge glass thickness to help create flat glass. Americium-241 is also suitable for calibration of gamma-ray spectrometers in the low-energy range, since its spectrum consists of nearly a single peak and negligible Compton continuum (at least three orders of magnitude lower intensity). Americium-241 gamma rays were also used to provide passive diagnosis of thyroid function. This medical application is however obsolete.
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Americium
| 900 |
Health concerns
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As a highly radioactive element, americium and its compounds must be handled only in an appropriate laboratory under special arrangements. Although most americium isotopes predominantly emit alpha particles which can be blocked by thin layers of common materials, many of the daughter products emit gamma-rays and neutrons which have a long penetration depth.
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Americium
| 900 |
Health concerns
|
If consumed, most of the americium is excreted within a few days, with only 0.05% absorbed in the blood, of which roughly 45% goes to the liver and 45% to the bones, and the remaining 10% is excreted. The uptake to the liver depends on the individual and increases with age. In the bones, americium is first deposited over cortical and trabecular surfaces and slowly redistributes over the bone with time. The biological half-life of Am is 50 years in the bones and 20 years in the liver, whereas in the gonads (testicles and ovaries) it remains permanently; in all these organs, americium promotes formation of cancer cells as a result of its radioactivity.
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Americium
| 900 |
Health concerns
|
Americium often enters landfills from discarded smoke detectors. The rules associated with the disposal of smoke detectors are relaxed in most jurisdictions. In 1994, 17-year-old David Hahn extracted the americium from about 100 smoke detectors in an attempt to build a breeder nuclear reactor. There have been a few cases of exposure to americium, the worst case being that of chemical operations technician Harold McCluskey, who at the age of 64 was exposed to 500 times the occupational standard for americium-241 as a result of an explosion in his lab. McCluskey died at the age of 75 of unrelated pre-existing disease.
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Astatine
| 901 |
Astatine is a chemical element; it has symbol At and atomic number 85. It is the rarest naturally occurring element in the Earth's crust, occurring only as the decay product of various heavier elements. All of astatine's isotopes are short-lived; the most stable is astatine-210, with a half-life of 8.1 hours. Consequently, a solid sample of the element has never been seen, because any macroscopic specimen would be immediately vaporized by the heat of its radioactivity.
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Astatine
| 901 |
The bulk properties of astatine are not known with certainty. Many of them have been estimated from its position on the periodic table as a heavier analog of fluorine, chlorine, bromine, and iodine, the four stable halogens. However, astatine also falls roughly along the dividing line between metals and nonmetals, and some metallic behavior has also been observed and predicted for it. Astatine is likely to have a dark or lustrous appearance and may be a semiconductor or possibly a metal. Chemically, several anionic species of astatine are known and most of its compounds resemble those of iodine, but it also sometimes displays metallic characteristics and shows some similarities to silver.
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Astatine
| 901 |
The first synthesis of astatine was in 1940 by Dale R. Corson, Kenneth Ross MacKenzie, and Emilio G. Segrè at the University of California, Berkeley. They named it from the Ancient Greek ἄστατος (astatos) 'unstable'. Four isotopes of astatine were subsequently found to be naturally occurring, although much less than one gram is present at any given time in the Earth's crust. Neither the most stable isotope, astatine-210, nor the medically useful astatine-211 occur naturally; they are usually produced by bombarding bismuth-209 with alpha particles.
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Astatine
| 901 |
Characteristics
|
Astatine is an extremely radioactive element; all its isotopes have half-lives of 8.1 hours or less, decaying into other astatine isotopes, bismuth, polonium, or radon. Most of its isotopes are very unstable, with half-lives of seconds or less. Of the first 101 elements in the periodic table, only francium is less stable, and all the astatine isotopes more stable than the longest-lived francium isotopes (At) are in any case synthetic and do not occur in nature.
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Astatine
| 901 |
Characteristics
|
The bulk properties of astatine are not known with any certainty. Research is limited by its short half-life, which prevents the creation of weighable quantities. A visible piece of astatine would immediately vaporize itself because of the heat generated by its intense radioactivity. It remains to be seen if, with sufficient cooling, a macroscopic quantity of astatine could be deposited as a thin film. Astatine is usually classified as either a nonmetal or a metalloid; metal formation has also been predicted.
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Astatine
| 901 |
Characteristics
|
Most of the physical properties of astatine have been estimated (by interpolation or extrapolation), using theoretically or empirically derived methods. For example, halogens get darker with increasing atomic weight – fluorine is nearly colorless, chlorine is yellow-green, bromine is red-brown, and iodine is dark gray/violet. Astatine is sometimes described as probably being a black solid (assuming it follows this trend), or as having a metallic appearance (if it is a metalloid or a metal).
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Astatine
| 901 |
Characteristics
|
Astatine sublimes less readily than does iodine, having a lower vapor pressure. Even so, half of a given quantity of astatine will vaporize in approximately an hour if put on a clean glass surface at room temperature. The absorption spectrum of astatine in the middle ultraviolet region has lines at 224.401 and 216.225 nm, suggestive of 6p to 7s transitions.
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Astatine
| 901 |
Characteristics
|
The structure of solid astatine is unknown. As an analog of iodine it may have an orthorhombic crystalline structure composed of diatomic astatine molecules, and be a semiconductor (with a band gap of 0.7 eV). Alternatively, if condensed astatine forms a metallic phase, as has been predicted, it may have a monatomic face-centered cubic structure; in this structure, it may well be a superconductor, like the similar high-pressure phase of iodine. Metallic astatine is expected to have a density of 8.91–8.95 g/cm.
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Astatine
| 901 |
Characteristics
|
Evidence for (or against) the existence of diatomic astatine (At2) is sparse and inconclusive. Some sources state that it does not exist, or at least has never been observed, while other sources assert or imply its existence. Despite this controversy, many properties of diatomic astatine have been predicted; for example, its bond length would be 300±10 pm, dissociation energy 83.7±12.5 kJ/mol, and heat of vaporization (∆Hvap) 54.39 kJ/mol. Many values have been predicted for the melting and boiling points of astatine, but only for At2.
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Astatine
| 901 |
Characteristics
|
The chemistry of astatine is "clouded by the extremely low concentrations at which astatine experiments have been conducted, and the possibility of reactions with impurities, walls and filters, or radioactivity by-products, and other unwanted nano-scale interactions". Many of its apparent chemical properties have been observed using tracer studies on extremely dilute astatine solutions, typically less than 10 mol·L. Some properties, such as anion formation, align with other halogens. Astatine has some metallic characteristics as well, such as plating onto a cathode, and coprecipitating with metal sulfides in hydrochloric acid. It forms complexes with EDTA, a metal chelating agent, and is capable of acting as a metal in antibody radiolabeling; in some respects, astatine in the +1 state is akin to silver in the same state. Most of the organic chemistry of astatine is, however, analogous to that of iodine. It has been suggested that astatine can form a stable monatomic cation in aqueous solution.
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Astatine
| 901 |
Characteristics
|
Astatine has an electronegativity of 2.2 on the revised Pauling scale – lower than that of iodine (2.66) and the same as hydrogen. In hydrogen astatide (HAt), the negative charge is predicted to be on the hydrogen atom, implying that this compound could be referred to as astatine hydride according to certain nomenclatures. That would be consistent with the electronegativity of astatine on the Allred–Rochow scale (1.9) being less than that of hydrogen (2.2). However, official IUPAC stoichiometric nomenclature is based on an idealized convention of determining the relative electronegativities of the elements by the mere virtue of their position within the periodic table. According to this convention, astatine is handled as though it is more electronegative than hydrogen, irrespective of its true electronegativity. The electron affinity of astatine, at 233 kJ mol, is 21% less than that of iodine. In comparison, the value of Cl (349) is 6.4% higher than F (328); Br (325) is 6.9% less than Cl; and I (295) is 9.2% less than Br. The marked reduction for At was predicted as being due to spin–orbit interactions. The first ionization energy of astatine is about 899 kJ mol, which continues the trend of decreasing first ionization energies down the halogen group (fluorine, 1681; chlorine, 1251; bromine, 1140; iodine, 1008).
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Astatine
| 901 |
Compounds
|
Less reactive than iodine, astatine is the least reactive of the halogens; the chemical properties of tennessine, the next-heavier group 17 element, have not yet been investigated, however. Astatine compounds have been synthesized in nano-scale amounts and studied as intensively as possible before their radioactive disintegration. The reactions involved have been typically tested with dilute solutions of astatine mixed with larger amounts of iodine. Acting as a carrier, the iodine ensures there is sufficient material for laboratory techniques (such as filtration and precipitation) to work. Like iodine, astatine has been shown to adopt odd-numbered oxidation states ranging from −1 to +7.
|
Astatine
| 901 |
Compounds
|
Only a few compounds with metals have been reported, in the form of astatides of sodium, palladium, silver, thallium, and lead. Some characteristic properties of silver and sodium astatide, and the other hypothetical alkali and alkaline earth astatides, have been estimated by extrapolation from other metal halides.
|
Astatine
| 901 |
Compounds
|
The formation of an astatine compound with hydrogen – usually referred to as hydrogen astatide – was noted by the pioneers of astatine chemistry. As mentioned, there are grounds for instead referring to this compound as astatine hydride. It is easily oxidized; acidification by dilute nitric acid gives the At or At forms, and the subsequent addition of silver(I) may only partially, at best, precipitate astatine as silver(I) astatide (AgAt). Iodine, in contrast, is not oxidized, and precipitates readily as silver(I) iodide.
|
Astatine
| 901 |
Compounds
|
Astatine is known to bind to boron, carbon, and nitrogen. Various boron cage compounds have been prepared with At–B bonds, these being more stable than At–C bonds. Astatine can replace a hydrogen atom in benzene to form astatobenzene C6H5At; this may be oxidized to C6H5AtCl2 by chlorine. By treating this compound with an alkaline solution of hypochlorite, C6H5AtO2 can be produced. The dipyridine-astatine(I) cation, [At(C5H5N)2], forms ionic compounds with perchlorate (a non-coordinating anion) and with nitrate, [At(C5H5N)2]NO3. This cation exists as a coordination complex in which two dative covalent bonds separately link the astatine(I) centre with each of the pyridine rings via their nitrogen atoms.
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Astatine
| 901 |
Compounds
|
With oxygen, there is evidence of the species AtO and AtO in aqueous solution, formed by the reaction of astatine with an oxidant such as elemental bromine or (in the last case) by sodium persulfate in a solution of perchloric acid. The species previously thought to be AtO−2 has since been determined to be AtO(OH)−2, a hydrolysis product of AtO (another such hydrolysis product being AtOOH). The well characterized AtO−3 anion can be obtained by, for example, the oxidation of astatine with potassium hypochlorite in a solution of potassium hydroxide. Preparation of lanthanum triastatate La(AtO3)3, following the oxidation of astatine by a hot Na2S2O8 solution, has been reported. Further oxidation of AtO−3, such as by xenon difluoride (in a hot alkaline solution) or periodate (in a neutral or alkaline solution), yields the perastatate ion AtO−4; this is only stable in neutral or alkaline solutions. Astatine is also thought to be capable of forming cations in salts with oxyanions such as iodate or dichromate; this is based on the observation that, in acidic solutions, monovalent or intermediate positive states of astatine coprecipitate with the insoluble salts of metal cations such as silver(I) iodate or thallium(I) dichromate.
|
Astatine
| 901 |
Compounds
|
Astatine may form bonds to the other chalcogens; these include S7At and At(CSN)−2 with sulfur, a coordination selenourea compound with selenium, and an astatine–tellurium colloid with tellurium.
|
Astatine
| 901 |
Compounds
|
Astatine is known to react with its lighter homologs iodine, bromine, and chlorine in the vapor state; these reactions produce diatomic interhalogen compounds with formulas AtI, AtBr, and AtCl. The first two compounds may also be produced in water – astatine reacts with iodine/iodide solution to form AtI, whereas AtBr requires (aside from astatine) an iodine/iodine monobromide/bromide solution. The excess of iodides or bromides may lead to AtBr−2 and AtI−2 ions, or in a chloride solution, they may produce species like AtCl−2 or AtBrCl via equilibrium reactions with the chlorides. Oxidation of the element with dichromate (in nitric acid solution) showed that adding chloride turned the astatine into a molecule likely to be either AtCl or AtOCl. Similarly, AtOCl−2 or AtCl−2 may be produced. The polyhalides PdAtI2, CsAtI2, TlAtI2, and PbAtI are known or presumed to have been precipitated. In a plasma ion source mass spectrometer, the ions [AtI], [AtBr], and [AtCl] have been formed by introducing lighter halogen vapors into a helium-filled cell containing astatine, supporting the existence of stable neutral molecules in the plasma ion state. No astatine fluorides have been discovered yet. Their absence has been speculatively attributed to the extreme reactivity of such compounds, including the reaction of an initially formed fluoride with the walls of the glass container to form a non-volatile product. Thus, although the synthesis of an astatine fluoride is thought to be possible, it may require a liquid halogen fluoride solvent, as has already been used for the characterization of radon fluoride.
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Astatine
| 901 |
History
|
In 1869, when Dmitri Mendeleev published his periodic table, the space under iodine was empty; after Niels Bohr established the physical basis of the classification of chemical elements, it was suggested that the fifth halogen belonged there. Before its officially recognized discovery, it was called "eka-iodine" (from Sanskrit eka – "one") to imply it was one space under iodine (in the same manner as eka-silicon, eka-boron, and others). Scientists tried to find it in nature; given its extreme rarity, these attempts resulted in several false discoveries.
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Astatine
| 901 |
History
|
The first claimed discovery of eka-iodine was made by Fred Allison and his associates at the Alabama Polytechnic Institute (now Auburn University) in 1931. The discoverers named element 85 "alabamine", and assigned it the symbol Ab, designations that were used for a few years. In 1934, H. G. MacPherson of University of California, Berkeley disproved Allison's method and the validity of his discovery. There was another claim in 1937, by the chemist Rajendralal De. Working in Dacca in British India (now Dhaka in Bangladesh), he chose the name "dakin" for element 85, which he claimed to have isolated as the thorium series equivalent of radium F (polonium-210) in the radium series. The properties he reported for dakin do not correspond to those of astatine, and astatine's radioactivity would have prevented him from handling it in the quantities he claimed. Moreover, astatine is not found in the thorium series, and the true identity of dakin is not known.
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Astatine
| 901 |
History
|
In 1936, the team of Romanian physicist Horia Hulubei and French physicist Yvette Cauchois claimed to have discovered element 85 by observing its X-ray emission lines. In 1939, they published another paper which supported and extended previous data. In 1944, Hulubei published a summary of data he had obtained up to that time, claiming it was supported by the work of other researchers. He chose the name "dor", presumably from the Romanian for "longing" [for peace], as World War II had started five years earlier. As Hulubei was writing in French, a language which does not accommodate the "ine" suffix, dor would likely have been rendered in English as "dorine", had it been adopted. In 1947, Hulubei's claim was effectively rejected by the Austrian chemist Friedrich Paneth, who would later chair the IUPAC committee responsible for recognition of new elements. Even though Hulubei's samples did contain astatine-218, his means to detect it were too weak, by current standards, to enable correct identification; moreover, he could not perform chemical tests on the element. He had also been involved in an earlier false claim as to the discovery of element 87 (francium) and this is thought to have caused other researchers to downplay his work.
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Astatine
| 901 |
History
|
In 1940, the Swiss chemist Walter Minder announced the discovery of element 85 as the beta decay product of radium A (polonium-218), choosing the name "helvetium" (from Helvetia, the Latin name of Switzerland). Berta Karlik and Traude Bernert were unsuccessful in reproducing his experiments, and subsequently attributed Minder's results to contamination of his radon stream (radon-222 is the parent isotope of polonium-218). In 1942, Minder, in collaboration with the English scientist Alice Leigh-Smith, announced the discovery of another isotope of element 85, presumed to be the product of thorium A (polonium-216) beta decay. They named this substance "anglo-helvetium", but Karlik and Bernert were again unable to reproduce these results.
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Astatine
| 901 |
History
|
Later in 1940, Dale R. Corson, Kenneth Ross MacKenzie, and Emilio Segrè isolated the element at the University of California, Berkeley. Instead of searching for the element in nature, the scientists created it by bombarding bismuth-209 with alpha particles in a cyclotron (particle accelerator) to produce, after emission of two neutrons, astatine-211. The discoverers, however, did not immediately suggest a name for the element. The reason for this was that at the time, an element created synthetically in "invisible quantities" that had not yet been discovered in nature was not seen as a completely valid one; in addition, chemists were reluctant to recognize radioactive isotopes as legitimately as stable ones. In 1943, astatine was found as a product of two naturally occurring decay chains by Berta Karlik and Traude Bernert, first in the so-called uranium series, and then in the actinium series. (Since then, astatine was also found in a third decay chain, the neptunium series.) Friedrich Paneth in 1946 called to finally recognize synthetic elements, quoting, among other reasons, recent confirmation of their natural occurrence, and proposed that the discoverers of the newly discovered unnamed elements name these elements. In early 1947, Nature published the discoverers' suggestions; a letter from Corson, MacKenzie, and Segrè suggested the name "astatine" coming from the Ancient Greek αστατος (astatos) meaning 'unstable', because of its propensity for radioactive decay, with the ending "-ine", found in the names of the four previously discovered halogens. The name was also chosen to continue the tradition of the four stable halogens, where the name referred to a property of the element.
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Astatine
| 901 |
History
|
Corson and his colleagues classified astatine as a metal on the basis of its analytical chemistry. Subsequent investigators reported iodine-like, cationic, or amphoteric behavior. In a 2003 retrospective, Corson wrote that "some of the properties [of astatine] are similar to iodine ... it also exhibits metallic properties, more like its metallic neighbors Po and Bi."
|
Astatine
| 901 |
Isotopes
|
There are 41 known isotopes of astatine, with mass numbers of 188 and 190–229. Theoretical modeling suggests that about 37 more isotopes could exist. No stable or long-lived astatine isotope has been observed, nor is one expected to exist.
|
Astatine
| 901 |
Isotopes
|
Astatine's alpha decay energies follow the same trend as for other heavy elements. Lighter astatine isotopes have quite high energies of alpha decay, which become lower as the nuclei become heavier. Astatine-211 has a significantly higher energy than the previous isotope, because it has a nucleus with 126 neutrons, and 126 is a magic number corresponding to a filled neutron shell. Despite having a similar half-life to the previous isotope (8.1 hours for astatine-210 and 7.2 hours for astatine-211), the alpha decay probability is much higher for the latter: 41.81% against only 0.18%. The two following isotopes release even more energy, with astatine-213 releasing the most energy. For this reason, it is the shortest-lived astatine isotope. Even though heavier astatine isotopes release less energy, no long-lived astatine isotope exists, because of the increasing role of beta decay (electron emission). This decay mode is especially important for astatine; as early as 1950 it was postulated that all isotopes of the element undergo beta decay, though nuclear mass measurements indicate that At is in fact beta-stable, as it has the lowest mass of all isobars with A = 215. A beta decay mode has been found for all other astatine isotopes except for astatine-213, astatine-214, and astatine-216m. Astatine-210 and lighter isotopes exhibit beta plus decay (positron emission), astatine-216 and heavier isotopes exhibit beta minus decay, and astatine-212 decays via both modes, while astatine-211 undergoes electron capture.
|
Astatine
| 901 |
Isotopes
|
The most stable isotope is astatine-210, which has a half-life of 8.1 hours. The primary decay mode is beta plus, to the relatively long-lived (in comparison to astatine isotopes) alpha emitter polonium-210. In total, only five isotopes have half-lives exceeding one hour (astatine-207 to -211). The least stable ground state isotope is astatine-213, with a half-life of 125 nanoseconds. It undergoes alpha decay to the extremely long-lived bismuth-209.
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Astatine
| 901 |
Isotopes
|
Astatine has 24 known nuclear isomers, which are nuclei with one or more nucleons (protons or neutrons) in an excited state. A nuclear isomer may also be called a "meta-state", meaning the system has more internal energy than the "ground state" (the state with the lowest possible internal energy), making the former likely to decay into the latter. There may be more than one isomer for each isotope. The most stable of these nuclear isomers is astatine-202m1, which has a half-life of about 3 minutes, longer than those of all the ground states bar those of isotopes 203–211 and 220. The least stable is astatine-214m1; its half-life of 265 nanoseconds is shorter than those of all ground states except that of astatine-213.
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Astatine
| 901 |
Natural occurrence
|
Astatine is the rarest naturally occurring element. The total amount of astatine in the Earth's crust (quoted mass 2.36 × 10 grams) is estimated by some to be less than one gram at any given time. Other sources estimate the amount of ephemeral astatine, present on earth at any given moment, to be up to one ounce (about 28 grams).
|
Astatine
| 901 |
Natural occurrence
|
Any astatine present at the formation of the Earth has long since disappeared; the four naturally occurring isotopes (astatine-215, -217, -218 and -219) are instead continuously produced as a result of the decay of radioactive thorium and uranium ores, and trace quantities of neptunium-237. The landmass of North and South America combined, to a depth of 16 kilometers (10 miles), contains only about one trillion astatine-215 atoms at any given time (around 3.5 × 10 grams). Astatine-217 is produced via the radioactive decay of neptunium-237. Primordial remnants of the latter isotope—due to its relatively short half-life of 2.14 million years—are no longer present on Earth. However, trace amounts occur naturally as a product of transmutation reactions in uranium ores. Astatine-218 was the first astatine isotope discovered in nature. Astatine-219, with a half-life of 56 seconds, is the longest lived of the naturally occurring isotopes.
|
Astatine
| 901 |
Natural occurrence
|
Isotopes of astatine are sometimes not listed as naturally occurring because of misconceptions that there are no such isotopes, or discrepancies in the literature. Astatine-216 has been counted as a naturally occurring isotope but reports of its observation (which were described as doubtful) have not been confirmed.
|
Astatine
| 901 |
Synthesis
|
Astatine was first produced by bombarding bismuth-209 with energetic alpha particles, and this is still the major route used to create the relatively long-lived isotopes astatine-209 through astatine-211. Astatine is only produced in minuscule quantities, with modern techniques allowing production runs of up to 6.6 gigabecquerels (about 86 nanograms or 2.47×10 atoms). Synthesis of greater quantities of astatine using this method is constrained by the limited availability of suitable cyclotrons and the prospect of melting the target. Solvent radiolysis due to the cumulative effect of astatine decay is a related problem. With cryogenic technology, microgram quantities of astatine might be able to be generated via proton irradiation of thorium or uranium to yield radon-211, in turn decaying to astatine-211. Contamination with astatine-210 is expected to be a drawback of this method.
|
Astatine
| 901 |
Synthesis
|
The most important isotope is astatine-211, the only one in commercial use. To produce the bismuth target, the metal is sputtered onto a gold, copper, or aluminium surface at 50 to 100 milligrams per square centimeter. Bismuth oxide can be used instead; this is forcibly fused with a copper plate. The target is kept under a chemically neutral nitrogen atmosphere, and is cooled with water to prevent premature astatine vaporization. In a particle accelerator, such as a cyclotron, alpha particles are collided with the bismuth. Even though only one bismuth isotope is used (bismuth-209), the reaction may occur in three possible ways, producing astatine-209, astatine-210, or astatine-211. In order to eliminate undesired nuclides, the maximum energy of the particle accelerator is set to a value (optimally 29.17 MeV) above that for the reaction producing astatine-211 (to produce the desired isotope) and below the one producing astatine-210 (to avoid producing other astatine isotopes).
|
Astatine
| 901 |
Synthesis
|
Since astatine is the main product of the synthesis, after its formation it must only be separated from the target and any significant contaminants. Several methods are available, "but they generally follow one of two approaches—dry distillation or [wet] acid treatment of the target followed by solvent extraction." The methods summarized below are modern adaptations of older procedures, as reviewed by Kugler and Keller. Pre-1985 techniques more often addressed the elimination of co-produced toxic polonium; this requirement is now mitigated by capping the energy of the cyclotron irradiation beam.
|
Astatine
| 901 |
Synthesis
|
The astatine-containing cyclotron target is heated to a temperature of around 650 °C. The astatine volatilizes and is condensed in (typically) a cold trap. Higher temperatures of up to around 850 °C may increase the yield, at the risk of bismuth contamination from concurrent volatilization. Redistilling the condensate may be required to minimize the presence of bismuth (as bismuth can interfere with astatine labeling reactions). The astatine is recovered from the trap using one or more low concentration solvents such as sodium hydroxide, methanol or chloroform. Astatine yields of up to around 80% may be achieved. Dry separation is the method most commonly used to produce a chemically useful form of astatine.
|
Astatine
| 901 |
Synthesis
|
The irradiated bismuth (or sometimes bismuth trioxide) target is first dissolved in, for example, concentrated nitric or perchloric acid. Following this first step, the acid can be distilled away to leave behind a white residue that contains both bismuth and the desired astatine product. This residue is then dissolved in a concentrated acid, such as hydrochloric acid. Astatine is extracted from this acid using an organic solvent such as dibutyl ether, diisopropyl ether (DIPE), or thiosemicarbazide. Using liquid-liquid extraction, the astatine product can be repeatedly washed with an acid, such as HCl, and extracted into the organic solvent layer. A separation yield of 93% using nitric acid has been reported, falling to 72% by the time purification procedures were completed (distillation of nitric acid, purging residual nitrogen oxides, and redissolving bismuth nitrate to enable liquid–liquid extraction). Wet methods involve "multiple radioactivity handling steps" and have not been considered well suited for isolating larger quantities of astatine. However, wet extraction methods are being examined for use in production of larger quantities of astatine-211, as it is thought that wet extraction methods can provide more consistency. They can enable the production of astatine in a specific oxidation state and may have greater applicability in experimental radiochemistry.
|
Astatine
| 901 |
Uses and precautions
|
Newly formed astatine-211 is the subject of ongoing research in nuclear medicine. It must be used quickly as it decays with a half-life of 7.2 hours; this is long enough to permit multistep labeling strategies. Astatine-211 has potential for targeted alpha-particle therapy, since it decays either via emission of an alpha particle (to bismuth-207), or via electron capture (to an extremely short-lived nuclide, polonium-211, which undergoes further alpha decay), very quickly reaching its stable granddaughter lead-207. Polonium X-rays emitted as a result of the electron capture branch, in the range of 77–92 keV, enable the tracking of astatine in animals and patients. Although astatine-210 has a slightly longer half-life, it is wholly unsuitable because it usually undergoes beta plus decay to the extremely toxic polonium-210.
|
Astatine
| 901 |
Uses and precautions
|
The principal medicinal difference between astatine-211 and iodine-131 (a radioactive iodine isotope also used in medicine) is that iodine-131 emits high-energy beta particles, and astatine does not. Beta particles have much greater penetrating power through tissues than do the much heavier alpha particles. An average alpha particle released by astatine-211 can travel up to 70 µm through surrounding tissues; an average-energy beta particle emitted by iodine-131 can travel nearly 30 times as far, to about 2 mm. The short half-life and limited penetrating power of alpha radiation through tissues offers advantages in situations where the "tumor burden is low and/or malignant cell populations are located in close proximity to essential normal tissues." Significant morbidity in cell culture models of human cancers has been achieved with from one to ten astatine-211 atoms bound per cell.
|
Astatine
| 901 |
Uses and precautions
|
Astatine ... [is] miserable to make and hell to work with.
|
Astatine
| 901 |
Uses and precautions
|
P Durbin, Human Radiation Studies: Remembering the Early Years, 1995
|
Astatine
| 901 |
Uses and precautions
|
Several obstacles have been encountered in the development of astatine-based radiopharmaceuticals for cancer treatment. World War II delayed research for close to a decade. Results of early experiments indicated that a cancer-selective carrier would need to be developed and it was not until the 1970s that monoclonal antibodies became available for this purpose. Unlike iodine, astatine shows a tendency to dehalogenate from molecular carriers such as these, particularly at sp carbon sites (less so from sp sites). Given the toxicity of astatine accumulated and retained in the body, this emphasized the need to ensure it remained attached to its host molecule. While astatine carriers that are slowly metabolized can be assessed for their efficacy, more rapidly metabolized carriers remain a significant obstacle to the evaluation of astatine in nuclear medicine. Mitigating the effects of astatine-induced radiolysis of labeling chemistry and carrier molecules is another area requiring further development. A practical application for astatine as a cancer treatment would potentially be suitable for a "staggering" number of patients; production of astatine in the quantities that would be required remains an issue.
|
Astatine
| 901 |
Uses and precautions
|
Animal studies show that astatine, similarly to iodine—although to a lesser extent, perhaps because of its slightly more metallic nature—is preferentially (and dangerously) concentrated in the thyroid gland. Unlike iodine, astatine also shows a tendency to be taken up by the lungs and spleen, possibly because of in-body oxidation of At to At. If administered in the form of a radiocolloid it tends to concentrate in the liver. Experiments in rats and monkeys suggest that astatine-211 causes much greater damage to the thyroid gland than does iodine-131, with repetitive injection of the nuclide resulting in necrosis and cell dysplasia within the gland. Early research suggested that injection of astatine into female rodents caused morphological changes in breast tissue; this conclusion remained controversial for many years. General agreement was later reached that this was likely caused by the effect of breast tissue irradiation combined with hormonal changes due to irradiation of the ovaries. Trace amounts of astatine can be handled safely in fume hoods if they are well-aerated; biological uptake of the element must be avoided.
|
Atom
| 902 |
The atom is the basic particle of the chemical elements. An atom consists of a nucleus of protons and generally neutrons, surrounded by an electromagnetically-bound swarm of electrons. The chemical elements are distinguished from each other by the number of protons that are in their atoms. For example, any atom that contains 11 protons is sodium, and any atom that contains 29 protons is copper. Atoms with the same number of protons but a different number of neutrons are called isotopes of the same element.
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|
Atom
| 902 |
Atoms are extremely small, typically around 100 picometers across. A human hair is about a million carbon atoms wide. This is smaller than the shortest wavelength of visible light, which means humans cannot see atoms with conventional microscopes. Atoms are so small that accurately predicting their behavior using classical physics is not possible due to quantum effects.
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Atom
| 902 |
More than 99.94% of an atom's mass is in the nucleus. Protons have a positive electric charge and neutrons have no charge, so the nucleus is positively charged. The electrons are negatively charged, and this opposing charge is what binds them to the nucleus. If the numbers of protons and electrons are equal, as they normally are, then the atom is electrically neutral as a whole. If an atom has more electrons than protons, then it has an overall negative charge, and is called a negative ion (or anion). Conversely, if it has more protons than electrons, it has a positive charge, and is called a positive ion (or cation).
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|
Atom
| 902 |
The electrons of an atom are attracted to the protons in an atomic nucleus by the electromagnetic force. The protons and neutrons in the nucleus are attracted to each other by the nuclear force. This force is usually stronger than the electromagnetic force that repels the positively charged protons from one another. Under certain circumstances, the repelling electromagnetic force becomes stronger than the nuclear force. In this case, the nucleus splits and leaves behind different elements. This is a form of nuclear decay.
|
|
Atom
| 902 |
Atoms can attach to one or more other atoms by chemical bonds to form chemical compounds such as molecules or crystals. The ability of atoms to attach and detach from each other is responsible for most of the physical changes observed in nature. Chemistry is the science that studies these changes.
|
|
Atom
| 902 |
History of atomic theory
|
The basic idea that matter is made up of tiny indivisible particles is an old idea that appeared in many ancient cultures. The word atom is derived from the ancient Greek word atomos, which means "uncuttable". This ancient idea was based in philosophical reasoning rather than scientific reasoning. Modern atomic theory is not based on these old concepts. In the early 19th century, the scientist John Dalton noticed that chemical elements seemed to combine with each other by discrete units of weight, and he decided to use the word "atom" to refer to these units, as he thought these were the fundamental units of matter. About a century later it was discovered that Dalton's atoms are not actually indivisible, but the term stuck.
|
Atom
| 902 |
History of atomic theory
|
In the early 1800s, the English chemist John Dalton compiled experimental data gathered by him and other scientists and discovered a pattern now known as the "law of multiple proportions". He noticed that in chemical compounds which contain a particular chemical element, the content of that element in these compounds will differ in weight by ratios of small whole numbers. This pattern suggested that each chemical element combines with other elements by a basic unit of weight, and Dalton decided to call these units "atoms".
|
Atom
| 902 |
History of atomic theory
|
For example, there are two types of tin oxide: one is a grey powder that is 88.1% tin and 11.9% oxygen, and the other is a white powder that is 78.7% tin and 21.3% oxygen. Adjusting these figures, in the grey powder there is about 13.5 g of oxygen for every 100 g of tin, and in the white powder there is about 27 g of oxygen for every 100 g of tin. 13.5 and 27 form a ratio of 1:2. Dalton concluded that in these oxides, for every tin atom there are one or two oxygen atoms respectively (SnO and SnO2).
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Atom
| 902 |
History of atomic theory
|
Dalton also analyzed iron oxides. There is one type of iron oxide that is a black powder which is 78.1% iron and 21.9% oxygen; and there is another iron oxide that is a red powder which is 70.4% iron and 29.6% oxygen. Adjusting these figures, in the black powder there is about 28 g of oxygen for every 100 g of iron, and in the red powder there is about 42 g of oxygen for every 100 g of iron. 28 and 42 form a ratio of 2:3. Dalton concluded that in these oxides, for every two atoms of iron, there are two or three atoms of oxygen respectively (Fe2O2 and Fe2O3).
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Atom
| 902 |
History of atomic theory
|
As a final example: nitrous oxide is 63.3% nitrogen and 36.7% oxygen, nitric oxide is 44.05% nitrogen and 55.95% oxygen, and nitrogen dioxide is 29.5% nitrogen and 70.5% oxygen. Adjusting these figures, in nitrous oxide there is 80 g of oxygen for every 140 g of nitrogen, in nitric oxide there is about 160 g of oxygen for every 140 g of nitrogen, and in nitrogen dioxide there is 320 g of oxygen for every 140 g of nitrogen. 80, 160, and 320 form a ratio of 1:2:4. The respective formulas for these oxides are N2O, NO, and NO2.
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Atom
| 902 |
History of atomic theory
|
Scientists discovered some substances have the exact same chemical content but different properties. For instance, in 1827, Friedrich Wöhler discovered that silver fulminate and silver cyanate are both 107 parts silver, 12 parts carbon, 14 parts nitrogen, and 12 parts oxygen (we now know their formulas as both AgCNO). In 1830 Jöns Jacob Berzelius introduced the term isomerism to describe the phenomenon. In 1860, Louis Pasteur hypothesized that the molecules of isomers might have the same set of atoms but in different arrangements.
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Atom
| 902 |
History of atomic theory
|
In 1874, Jacobus Henricus van 't Hoff proposed that the carbon atom bonds to other atoms in a tetrahedral arrangement. Working from this, he explained the structures of organic molecules in such a way that he could predict how many isomers a compound could have. Consider, for example, pentane (C5H12). In van 't Hoff's way of modelling molecules, there are three possible configurations for pentane, and scientists did go on to discover three and only three isomers of pentane.
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