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Antimony | Halides | Halides
Antimony forms two series of halides: and . The trihalides , , , and are all molecular compounds having trigonal pyramidal molecular geometry. The trifluoride is prepared by the reaction of antimony trioxide with hydrofluoric acid:Wiberg and Holleman, pp. 761–762
It is Lewis acidic and readily accepts fluoride ions to form the complex anions and . Molten antimony trifluoride is a weak electrical conductor. The trichloride is prepared by dissolving stibnite in hydrochloric acid:
Arsenic sulfides are not readily attacked by the hydrochloric acid, so this method offers a route to As-free Sb.
thumb|upright|left|Structure of gaseous
The pentahalides and have trigonal bipyramidal molecular geometry in the gas phase, but in the liquid phase, is polymeric, whereas is monomeric.Wiberg and Holleman, p. 761 Antimony pentafluoride is a powerful Lewis acid used to make the superacid fluoroantimonic acid ().
Oxyhalides are more common for antimony than for arsenic and phosphorus. Antimony trioxide dissolves in concentrated acid to form oxoantimonyl compounds such as SbOCl and .Wiberg and Holleman, p. 764 |
Antimony | Antimonides, hydrides, and organoantimony compounds | Antimonides, hydrides, and organoantimony compounds
Compounds in this class generally are described as derivatives of . Antimony forms antimonides with metals, such as indium antimonide (InSb) and silver antimonide ().Wiberg and Holleman, p. 760 The alkali metal and zinc antimonides, such as and , are more reactive. Treating these antimonides with acid produces the highly unstable gas stibine, :
Stibine can also be produced by treating salts with hydride reagents such as sodium borohydride. Stibine decomposes spontaneously at room temperature. Because stibine has a positive heat of formation, it is thermodynamically unstable and thus antimony does not react with hydrogen directly.Greenwood and Earnshaw, p. 558
Organoantimony compounds are typically prepared by alkylation of antimony halides with Grignard reagents.Elschenbroich, C. (2006) "Organometallics". Wiley-VCH: Weinheim. A large variety of compounds are known with both Sb(III) and Sb(V) centers, including mixed chloro-organic derivatives, anions, and cations. Examples include triphenylstibine () and pentaphenylantimony ().Greenwood and Earnshaw, p. 598 |
Antimony | History | History
upright=0.3|thumb|alt=An unshaded circle surmounted by a cross.|One of the alchemical symbols for antimony
Antimony(III) sulfide, , was recognized in predynastic Egypt as an eye cosmetic (kohl) as early as about 3100 BC, when the cosmetic palette was invented.
An artifact, said to be part of a vase, made of antimony dating to about 3000 BC was found at Telloh, Chaldea (part of present-day Iraq), and a copper object plated with antimony dating between 2500 BC and 2200 BC has been found in Egypt. Austen, at a lecture by Herbert Gladstone in 1892, commented that "we only know of antimony at the present day as a highly brittle and crystalline metal, which could hardly be fashioned into a useful vase, and therefore this remarkable 'find' (artifact mentioned above) must represent the lost art of rendering antimony malleable."
The British archaeologist Roger Moorey was unconvinced the artifact was indeed a vase, mentioning that Selimkhanov, after his analysis of the Tello object (published in 1975), "attempted to relate the metal to Transcaucasian natural antimony" (i.e. native metal) and that "the antimony objects from Transcaucasia are all small personal ornaments." This weakens the evidence for a lost art "of rendering antimony malleable".
The Roman scholar Pliny the Elder described several ways of preparing antimony sulfide for medical purposes in his treatise Natural History, around 77 AD. Pliny the Elder also made a distinction between "male" and "female" forms of antimony; the male form is probably the sulfide, while the female form, which is superior, heavier, and less friable, has been suspected to be native metallic antimony.Pliny, Natural history, 33.33; W.H.S. Jones, the Loeb Classical Library translator, supplies a note suggesting the identifications.
The Greek naturalist Pedanius Dioscorides mentioned that antimony sulfide could be roasted by heating by a current of air. It is thought that this produced metallic antimony.
thumb|right|upright=0.9|The Italian metallurgist Vannoccio Biringuccio described a procedure to isolate antimony in 1540
Antimony was frequently described in alchemical manuscripts, including the Summa Perfectionis of Pseudo-Geber, written around the 14th century. A description of a procedure for isolating antimony is later given in the 1540 book De la pirotechnia by Vannoccio Biringuccio,Vannoccio Biringuccio, De la Pirotechnia (Venice (Italy): Curtio Navo e fratelli, 1540), Book 2, chapter 3: Del antimonio & sua miniera, Capitolo terzo (On antimony and its ore, third chapter), pp. 27–28. [Note: Only every second page of this book is numbered, so the relevant passage is to be found on the 74th and 75th pages of the text.] (in Italian) predating the more famous 1556 book by Agricola, De re metallica. In this context Agricola has been often incorrectly credited with the discovery of metallic antimony. The book Currus Triumphalis Antimonii (The Triumphal Chariot of Antimony), describing the preparation of metallic antimony, was published in Germany in 1604. It was purported to be written by a Benedictine monk, writing under the name Basilius Valentinus in the 15th century; if it were authentic, which it is not, it would predate Biringuccio.
The metal antimony was known to German chemist Andreas Libavius in 1615 who obtained it by adding iron to a molten mixture of antimony sulfide, salt and potassium tartrate. This procedure produced antimony with a crystalline or starred surface.
With the advent of challenges to phlogiston theory, it was recognized that antimony is an element forming sulfides, oxides, and other compounds, as do other metals.
The first discovery of naturally occurring pure antimony in the Earth's crust was described by the Swedish scientist and local mine district engineer Anton von Swab in 1783; the type-sample was collected from the Sala Silver Mine in the Bergslagen mining district of Sala, Västmanland, Sweden. |
Antimony | Etymology | Etymology
The medieval Latin form, from which the modern languages and late Byzantine Greek take their names for antimony, is . The origin of that is uncertain, and all suggestions have some difficulty either of form or interpretation. The popular etymology, from ἀντίμοναχός anti-monachos or French , would mean "monk-killer", which is explained by the fact that many early alchemists were monks, and some antimony compounds were poisonous. Fernando connects the proposed etymology to the story of "Basil Valentine", although antimonium is found two centuries before Valentine's time.
Another popular etymology is the hypothetical Greek word ἀντίμόνος antimonos, "against aloneness", explained as "not found as metal", or "not found unalloyed"."Antimony" in Kirk-Othmer Encyclopedia of Chemical Technology, 5th ed. 2004. However, ancient Greek would more naturally express the pure negative as α- ("not")., which considers the derivation a "popular etymology". Edmund Oscar von Lippmann conjectured a hypothetical Greek word ανθήμόνιον anthemonion, which would mean "floret", and cites several examples of related Greek words (but not that one) which describe chemical or biological efflorescence.von Lippmann, Edmund Oscar (1919) Entstehung und Ausbreitung der Alchemie, teil 1. Berlin: Julius Springer (in German). pp. 642–5
The early uses of antimonium include the translations, in 1050–1100, by Constantine the African of Arabic medical treatises. Several authorities believe antimonium is a scribal corruption of some Arabic form; Meyerhof derives it from ithmid;Meyerhof as quoted in , asserts that ithmid or athmoud became corrupted in the medieval "traductions barbaro-latines". The OED asserts some Arabic form is the origin, and if ithmid is the root, posits athimodium, atimodium, atimonium as intermediates. other possibilities include athimar, the Arabic name of the metalloid, and a hypothetical as-stimmi, derived from or parallel to the Greek.
The standard chemical symbol for antimony (Sb) is credited to Jöns Jakob Berzelius, who derived the abbreviation from stibium.Jöns Jacob Berzelius, "Essay on the cause of chemical proportions, and on some circumstances relating to them: together with a short and easy method of expressing them," Annals of Philosophy, vol. 2, pages 443–454 (1813) and vol. 3, pages 51–62, 93–106, 244–255, 353–364 (1814). On [ p. 52], Berzelius lists the symbol for antimony as "St"; however, starting from [ p. 248], Berzelius consistently uses the symbol "Sb" instead.
The ancient words for antimony mostly have, as their chief meaning, kohl, the sulfide of antimony.
The Egyptians called antimony mśdmt or stm.
The Arabic word for the substance, as opposed to the cosmetic, can appear as ithmid, athmoud, othmod, or uthmod. Littré suggests the first form, which is the earliest, derives from stimmida, an accusative for stimmi. The Greek word στίμμι (stimmi) is used by Attic tragic poets of the 5th century BC, and is possibly a loan word from Arabic or from Egyptian stm. |
Antimony | Production | Production |
Antimony | Process | Process
The extraction of antimony from ores depends on the quality and composition of the ore. Most antimony is mined as the sulfide; lower-grade ores are concentrated by froth flotation, while higher-grade ores are heated to 500–600 °C, the temperature at which stibnite melts and separates from the gangue minerals. Antimony can be isolated from the crude antimony sulfide by reduction with scrap iron:
The sulfide is converted to an oxide by roasting. The product is further purified by vaporizing the volatile antimony(III) oxide, which is recovered. This sublimate is often used directly for the main applications, impurities being arsenic and sulfide., [ p. 45] Antimony is isolated from the oxide by a carbothermal reduction:
The lower-grade ores are reduced in blast furnaces while the higher-grade ores are reduced in reverberatory furnaces.
thumb|upright=1.6|World antimony output in 2010
thumb|upright=1.3|World production trend of antimony |
Antimony | Top producers and production volumes | Top producers and production volumes
In 2022, according to the US Geological Survey, China accounted for 54.5% of total antimony production, followed in second place by Russia with 18.2% and Tajikistan with 15.5%.
+Antimony mining in 2022 Country Tonnes % of total60,00054.520,00018.217,00015.54,0003.64,0003.6Top 5105,00095.5Total world110,000100.0
Chinese production of antimony is expected to decline in the future as mines and smelters are closed down by the government as part of pollution control. Especially due to an environmental protection law having gone into effect in January 2015 and revised "Emission Standards of Pollutants for Stanum, Antimony, and Mercury" having gone into effect, hurdles for economic production are higher.
Reported production of antimony in China has fallen and is unlikely to increase in the coming years, according to the Roskill report. No significant antimony deposits in China have been developed for about ten years, and the remaining economic reserves are being rapidly depleted. |
Antimony | Reserves | Reserves
+World antimony reserves in 2022 Country Reserves (tonnes) 350,000350,000310,000260,000140,000120,000100,00078,00060,00060,00050,000Total world>1,800,000 |
Antimony | Supply risk | Supply risk
For antimony-importing regions, such as Europe and the U.S., antimony is considered to be a critical mineral for industrial manufacturing that is at risk of supply chain disruption. With global production coming mainly from China (74%), Tajikistan (8%), and Russia (4%), these sources are critical to supply.
European Union: Antimony is considered a critical raw material for defense, automotive, construction and textiles. The E.U. sources are 100% imported, coming mainly from Turkey (62%), Bolivia (20%) and Guatemala (7%).
United Kingdom: The British Geological Survey's 2015 risk list ranks antimony second highest (after rare earth elements) on the relative supply risk index.
United States: Antimony is a mineral commodity considered critical to the economic and national security. In 2022, no antimony was mined in the U.S. |
Antimony | Applications | Applications
Approximately 48% of antimony is consumed in flame retardants, 33% in lead–acid batteries, and 8% in plastics. |
Antimony | Flame retardants | Flame retardants
Antimony is mainly used as the trioxide for flame-proofing compounds, always in combination with halogenated flame retardants except in halogen-containing polymers. The flame retarding effect of antimony trioxide is produced by the formation of halogenated antimony compounds, which react with hydrogen atoms, and probably also with oxygen atoms and OH radicals, thus inhibiting fire. Markets for these flame-retardants include children's clothing, toys, aircraft, and automobile seat covers. They are also added to polyester resins in fiberglass composites for such items as light aircraft engine covers. The resin will burn in the presence of an externally generated flame, but will extinguish when the external flame is removed.Grund, Sabina C.; Hanusch, Kunibert; Breunig, Hans J.; Wolf, Hans Uwe (2006) "Antimony and Antimony Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. |
Antimony | Alloys | Alloys
Antimony forms a highly useful alloy with lead, increasing its hardness and mechanical strength. When casting it increases fluidity of the melt and reduces shrinkage during cooling. For most applications involving lead, varying amounts of antimony are used as alloying metal. In lead–acid batteries, this addition improves plate strength and charging characteristics. For sailboats, lead keels are used to provide righting moment, ranging from 600 lbs to over 200 tons for the largest sailing superyachts; to improve hardness and tensile strength of the lead keel, antimony is mixed with lead between 2% and 5% by volume. Antimony is used in antifriction alloys (such as Babbitt metal), in bullets and lead shot, electrical cable sheathing, type metal (for example, for linotype printing machines), solder (some "lead-free" solders contain 5% Sb), in pewter, and in hardening alloys with low tin content in the manufacturing of organ pipes. |
Antimony | Other applications | Other applications
thumb|upright|InSb infrared detector manufactured by Mullard in the 1960s
Three other applications consume nearly all the rest of the world's supply. One application is as a stabilizer and catalyst for the production of polyethylene terephthalate. Another is as a fining agent to remove microscopic bubbles in glass, mostly for TV screens antimony ions interact with oxygen, suppressing the tendency of the latter to form bubbles. The third application is pigments.
In the 1990s antimony was increasingly being used in semiconductors as a dopant in n-type silicon wafers for diodes, infrared detectors, and Hall-effect devices. In the 1950s, the emitters and collectors of n-p-n alloy junction transistors were doped with tiny beads of a lead-antimony alloy. Indium antimonide (InSb) is used as a material for mid-infrared detectors.
The material is used as for phase-change memory, a type of computer memory.
Biology and medicine have few uses for antimony. Treatments containing antimony, known as antimonials, are used as emetics. Antimony compounds are used as antiprotozoan drugs. Potassium antimonyl tartrate, or tartar emetic, was once used as an anti-schistosomal drug from 1919 on. It was subsequently replaced by praziquantel. Antimony and its compounds are used in several veterinary preparations, such as anthiomaline and lithium antimony thiomalate, as a skin conditioner in ruminants. Antimony has a nourishing or conditioning effect on keratinized tissues in animals.
Antimony-based drugs, such as meglumine antimoniate, are also considered the drugs of choice for treatment of leishmaniasis. Early treatments used antimony(III) species (trivalent antimonials), but in 1922 Upendranath Brahmachari invented a much safer antimony(V) drug, and since then so-called pentavalent antimonials have been the standard first-line treatment. However, Leishmania strains in Bihar and neighboring regions have developed resistance to antimony. Elemental antimony as an antimony pill was once used as a medicine. It could be reused by others after ingestion and elimination.
Antimony(III) sulfide is used in the heads of some safety matches. Antimony sulfides help to stabilize the friction coefficient in automotive brake pad materials. Antimony is used in bullets, bullet tracers, paint, glass art, and as an opacifier in enamel. Antimony-124 is used together with beryllium in neutron sources; the gamma rays emitted by antimony-124 initiate the photodisintegration of beryllium. The emitted neutrons have an average energy of 24 keV. Natural antimony is used in startup neutron sources.
The powder derived from crushed antimony sulfide (kohl) has been used for millennia as an eye cosmetic. Historically it was applied to the eyes with a metal rod and with one's spittle, and was thought by the ancients to aid in curing eye infections. The practice is still seen in Yemen and in other Muslim countries. |
Antimony | Precautions | Precautions
Antimony and many of its compounds are toxic, and the effects of antimony poisoning are similar to arsenic poisoning. The toxicity of antimony is far lower than that of arsenic; this might be caused by the significant differences of uptake, metabolism and excretion between arsenic and antimony. The uptake of antimony(III) or antimony(V) in the gastrointestinal tract is at most 20%. Antimony(V) is not quantitatively reduced to antimony(III) in the cell (in fact antimony(III) is oxidised to antimony(V) instead).
Since methylation of antimony does not occur, the excretion of antimony(V) in urine is the main way of elimination. Like arsenic, the most serious effect of acute antimony poisoning is cardiotoxicity and the resulting myocarditis; however, it can also manifest as Adams–Stokes syndrome, which arsenic does not. Reported cases of intoxication by antimony equivalent to 90 mg antimony potassium tartrate dissolved from enamel has been reported to show only short term effects. An intoxication with 6 g of antimony potassium tartrate was reported to result in death after three days.
Inhalation of antimony dust is harmful and in certain cases may be fatal; in small doses, antimony causes headaches, dizziness, and depression. Larger doses such as prolonged skin contact may cause dermatitis, or damage the kidneys and the liver, causing violent and frequent vomiting, leading to death in a few days.
Antimony is incompatible with strong oxidizing agents, strong acids, halogen acids, chlorine, or fluorine. It should be kept away from heat.Antimony MSDS. Baker
Antimony leaches from polyethylene terephthalate (PET) bottles into liquids. While levels observed for bottled water are below drinking water guidelines, fruit juice concentrates (for which no guidelines are established) produced in the UK were found to contain up to 44.7 μg/L of antimony, well above the EU limits for tap water of 5 μg/L. The guidelines are:
World Health Organization: 20 μg/L
Japan: 15 μg/LWakayama, Hiroshi (2003) "Revision of Drinking Water Standards in Japan", Ministry of Health, Labor and Welfare (Japan); Table 2, p. 84
United States Environmental Protection Agency, Health Canada and the Ontario Ministry of Environment: 6 μg/LScreening assessment antimony-containing substances. Health Canada. July 2020.
EU and German Federal Ministry of Environment: 5 μg/L
The tolerable daily intake (TDI) proposed by WHO is 6 μg antimony per kilogram of body weight. The immediately dangerous to life or health (IDLH) value for antimony is 50 mg/m3. |
Antimony | Toxicity | Toxicity
Certain compounds of antimony appear to be toxic, particularly antimony trioxide and antimony potassium tartrate. Effects may be similar to arsenic poisoning. Occupational exposure may cause respiratory irritation, pneumoconiosis, antimony spots on the skin, gastrointestinal symptoms, and cardiac arrhythmias. In addition, antimony trioxide is potentially carcinogenic to humans.
Adverse health effects have been observed in humans and animals following inhalation, oral, or dermal exposure to antimony and antimony compounds. Antimony toxicity typically occurs either due to occupational exposure, during therapy or from accidental ingestion. It is unclear if antimony can enter the body through the skin. The presence of low levels of antimony in saliva may also be associated with dental decay. |
Antimony | Notes | Notes |
Antimony | References | References |
Antimony | Cited sources | Cited sources |
Antimony | External links | External links
Public Health Statement for Antimony
International Antimony Association vzw (i2a)
Chemistry in its element podcast (MP3) from the Royal Society of Chemistry's Chemistry World: Antimony
Antimony at The Periodic Table of Videos (University of Nottingham)
CDC – NIOSH Pocket Guide to Chemical Hazards – Antimony
Antimony Mineral data and specimen images
Category:Chemical elements
Category:Metalloids
Category:Native element minerals
Category:Nuclear materials
Category:Pnictogens
Category:Trigonal minerals
Category:Minerals in space group 166
Category:Chemical elements with rhombohedral structure |
Antimony | Table of Content | distinguish, Characteristics, Properties, Isotopes, Occurrence, Compounds, Oxides and hydroxides, Halides, Antimonides, hydrides, and organoantimony compounds, History, Etymology, Production, Process, Top producers and production volumes, Reserves, Supply risk, Applications, Flame retardants, Alloys, Other applications, Precautions, Toxicity, Notes, References, Cited sources, External links |
Actinium | Distinguish | Actinium is a chemical element; it has symbol Ac and atomic number 89. It was discovered by Friedrich Oskar Giesel in 1902, who gave it the name emanium; the element got its name by being wrongly identified with a substance André-Louis Debierne found in 1899 and called actinium. The actinide series, a set of 15 elements between actinium and lawrencium in the periodic table, are named for actinium. Together with polonium, radium, and radon, actinium was one of the first non-primordial radioactive elements to be discovered.
A soft, silvery-white radioactive metal, actinium reacts rapidly with oxygen and moisture in air forming a white coating of actinium oxide that prevents further oxidation. As with most lanthanides and many actinides, actinium assumes oxidation state +3 in nearly all its chemical compounds. Actinium is found only in traces in uranium and thorium ores as the isotope 227Ac, which decays with a half-life of 21.772 years, predominantly emitting beta and sometimes alpha particles, and 228Ac, which is beta active with a half-life of 6.15 hours. One tonne of natural uranium in ore contains about 0.2 milligrams of actinium-227, and one tonne of thorium contains about 5 nanograms of actinium-228. The close similarity of physical and chemical properties of actinium and lanthanum makes separation of actinium from the ore impractical. Instead, the element is prepared, in milligram amounts, by the neutron irradiation of in a nuclear reactor. Owing to its scarcity, high price and radioactivity, actinium has no significant industrial use. Its current applications include a neutron source and an agent for radiation therapy. |
Actinium | History | History
André-Louis Debierne, a French chemist, announced the discovery of a new element in 1899. He separated it from pitchblende residues left by Marie and Pierre Curie after they had extracted radium. In 1899, Debierne described the substance as similar to titanium and (in 1900) as similar to thorium. Friedrich Oskar Giesel found in 1902 a substance similar to lanthanum and called it "emanium" in 1904. After a comparison of the substances' half-lives determined by Debierne, Harriet Brooks in 1904, and Otto Hahn and Otto Sackur in 1905, Debierne's chosen name for the new element was retained because it had seniority, despite the contradicting chemical properties he claimed for the element at different times.
Articles published in the 1970s and later suggest that Debierne's results published in 1904 conflict with those reported in 1899 and 1900. Furthermore, the now-known chemistry of actinium precludes its presence as anything other than a minor constituent of Debierne's 1899 and 1900 results; in fact, the chemical properties he reported make it likely that he had, instead, accidentally identified protactinium, which would not be discovered for another fourteen years, only to have it disappear due to its hydrolysis and adsorption onto his laboratory equipment. This has led some authors to advocate that Giesel alone should be credited with the discovery. A less confrontational vision of scientific discovery is proposed by Adloff. He suggests that hindsight criticism of the early publications should be mitigated by the then nascent state of radiochemistry: highlighting the prudence of Debierne's claims in the original papers, he notes that nobody can contend that Debierne's substance did not contain actinium. Debierne, who is now considered by the vast majority of historians as the discoverer, lost interest in the element and left the topic. Giesel, on the other hand, can rightfully be credited with the first preparation of radiochemically pure actinium and with the identification of its atomic number 89.
The name actinium originates from the Ancient Greek aktis, aktinos (ακτίς, ακτίνος), meaning beam or ray. Its symbol Ac is also used in abbreviations of other compounds that have nothing to do with actinium, such as acetyl, acetate and sometimes acetaldehyde. |
Actinium | Properties | Properties
Actinium is a soft, silvery-white,Actinium, in Encyclopædia Britannica, 15th edition, 1995, p. 70 radioactive, metallic element. Its estimated shear modulus is similar to that of lead.Seitz, Frederick and Turnbull, David (1964) Solid state physics: advances in research and applications. Academic Press. pp. 289–291 Owing to its strong radioactivity, actinium glows in the dark with a pale blue light, which originates from the surrounding air ionized by the emitted energetic particles. Actinium has similar chemical properties to lanthanum and other lanthanides, and therefore these elements are difficult to separate when extracting from uranium ores. Solvent extraction and ion chromatography are commonly used for the separation.
The first element of the actinides, actinium gave the set its name, much as lanthanum had done for the lanthanides. The actinides are much more diverse than the lanthanides and therefore it was not until 1945 that the most significant change to Dmitri Mendeleev's periodic table since the recognition of the lanthanides, the introduction of the actinides, was generally accepted after Glenn T. Seaborg's research on the transuranium elements (although it had been proposed as early as 1892 by British chemist Henry Bassett).
Actinium reacts rapidly with oxygen and moisture in air forming a white coating of actinium oxide that impedes further oxidation. As with most lanthanides and actinides, actinium exists in the oxidation state +3, and the Ac3+ ions are colorless in solutions. The oxidation state +3 originates from the [Rn] 6d17s2 electronic configuration of actinium, with three valence electrons that are easily donated to give the stable closed-shell structure of the noble gas radon. Although the 5f orbitals are unoccupied in an actinium atom, it can be used as a valence orbital in actinium complexes and hence it is generally considered the first 5f element by authors working on it. Ac3+ is the largest of all known tripositive ions and its first coordination sphere contains approximately 10.9 ± 0.5 water molecules. |
Actinium | Chemical compounds | Chemical compounds
Due to actinium's intense radioactivity, only a limited number of actinium compounds are known. These include: AcF3, AcCl3, AcBr3, AcOF, AcOCl, AcOBr, Ac2S3, Ac2O3, AcPO4 and Ac(NO3)3. They all contain actinium in the oxidation state +3. In particular, the lattice constants of the analogous lanthanum and actinium compounds differ by only a few percent.
Formula color symmetry space group No Pearson symbol a (pm) b (pm) c (pm) Z density, g/cm3 Ac silvery fcc Fmm 225 cF4 531.1 531.1 531.1 4 10.07 AcH2unknown cubic Fmm 225 cF12 567 567 567 4 8.35 Ac2O3 white trigonal Pm1 164 hP5 408 408 630 1 9.18 Ac2S3 black cubic I3d 220 cI28 778.56 778.56 778.56 4 6.71 AcF3 whiteMeyer, p. 71 hexagonal Pc1 165 hP24 741 741 755 6 7.88 AcCl3white hexagonal P63/m 165 hP8 764 764 456 2 4.8 AcBr3 white hexagonal P63/m 165 hP8 764 764 456 2 5.85 AcOF white cubic Fmm 593.1 8.28 AcOClwhite tetragonal 424 424 707 7.23 AcOBrwhite tetragonal 427 427 740 7.89 AcPO4·0.5H2Ounknown hexagonal 721 721 664 5.48
Here a, b and c are lattice constants, No is space group number and Z is the number of formula units per unit cell. Density was not measured directly but calculated from the lattice parameters. |
Actinium | Oxides | Oxides
Actinium oxide (Ac2O3) can be obtained by heating the hydroxide at or the oxalate at , in vacuum. Its crystal lattice is isotypic with the oxides of most trivalent rare-earth metals. |
Actinium | Halides | Halides
Actinium trifluoride can be produced either in solution or in solid reaction. The former reaction is carried out at room temperature, by adding hydrofluoric acid to a solution containing actinium ions. In the latter method, actinium metal is treated with hydrogen fluoride vapors at in an all-platinum setup. Treating actinium trifluoride with ammonium hydroxide at yields oxyfluoride AcOF. Whereas lanthanum oxyfluoride can be easily obtained by burning lanthanum trifluoride in air at for an hour, similar treatment of actinium trifluoride yields no AcOF and only results in melting of the initial product.Meyer, pp. 87–88
AcF3 + 2 NH3 + H2O → AcOF + 2 NH4F
Actinium trichloride is obtained by reacting actinium hydroxide or oxalate with carbon tetrachloride vapors at temperatures above . Similarly to the oxyfluoride, actinium oxychloride can be prepared by hydrolyzing actinium trichloride with ammonium hydroxide at . However, in contrast to the oxyfluoride, the oxychloride could well be synthesized by igniting a solution of actinium trichloride in hydrochloric acid with ammonia.
Reaction of aluminium bromide and actinium oxide yields actinium tribromide:
Ac2O3 + 2 AlBr3 → 2 AcBr3 + Al2O3
and treating it with ammonium hydroxide at results in the oxybromide AcOBr. |
Actinium | Other compounds | Other compounds
Actinium hydride was obtained by reduction of actinium trichloride with potassium at , and its structure was deduced by analogy with the corresponding LaH2 hydride. The source of hydrogen in the reaction was uncertain.Meyer, p. 43
Mixing monosodium phosphate (NaH2PO4) with a solution of actinium in hydrochloric acid yields white-colored actinium phosphate hemihydrate (AcPO4·0.5H2O), and heating actinium oxalate with hydrogen sulfide vapors at for a few minutes results in a black actinium sulfide Ac2S3. It may possibly be produced by acting with a mixture of hydrogen sulfide and carbon disulfide on actinium oxide at . |
Actinium | Isotopes | Isotopes
Naturally occurring actinium is principally composed of two radioactive isotopes; (from the radioactive family of ) and (a granddaughter of ). decays mainly as a beta emitter with a very small energy, but in 1.38% of cases it emits an alpha particle, so it can readily be identified through alpha spectrometry. Thirty-three radioisotopes have been identified, the most stable being with a half-life of 21.772 years, with a half-life of 10.0 days and with a half-life of 29.37 hours. All remaining radioactive isotopes have half-lives that are less than 10 hours and the majority of them have half-lives shorter than one minute. The shortest-lived known isotope of actinium is (half-life of 69 nanoseconds) which decays through alpha decay. Actinium also has two known meta states. The most significant isotopes for chemistry are 225Ac, 227Ac, and 228Ac.
Purified comes into equilibrium with its decay products after about a half of year. It decays according to its 21.772-year half-life emitting mostly beta (98.62%) and some alpha particles (1.38%); the successive decay products are part of the actinium series. Owing to the low available amounts, low energy of its beta particles (maximum 44.8 keV) and low intensity of alpha radiation, is difficult to detect directly by its emission and it is therefore traced via its decay products.Actinium, Great Soviet Encyclopedia (in Russian) The isotopes of actinium range in atomic weight from 203 u () to 236 u ().
Isotope
Production
Decay
Half-life
221Ac
232Th(d,9n)→225Pa(α)→221Ac
α
52 ms
222Ac
232Th(d,8n)→226Pa(α)→222Ac
α
5.0 s
223Ac
232Th(d,7n)→227Pa(α)→223Ac
α
2.1 min
224Ac
232Th(d,6n)→228Pa(α)→224Ac
α
2.78 hours
225Ac
232Th(n,γ)→233Th(β−)→233Pa(β−)→233U(α)→229Th(α)→225Ra(β−)→225Ac
α
10 days
226Ac
226Ra(d,2n)→226Ac
α, β− electron capture
29.37 hours
227Ac
235U(α)→231Th(β−)→231Pa(α)→227Ac
α, β−
21.77 years
228Ac
232Th(α)→228Ra(β−)→228Ac
β−
6.15 hours
229Ac
228Ra(n,γ)→229Ra(β−)→229Ac
β−
62.7 min
230Ac
232Th(d,α)→230Ac
β−
122 s
231Ac
232Th(γ,p)→231Ac
β−
7.5 min
232Ac
232Th(n,p)→232Ac
β−
119 s
|
Actinium | Occurrence and synthesis | Occurrence and synthesis
upright=0.70|thumb|Uraninite ores have elevated concentrations of actinium.
Actinium is found only in traces in uranium ores – one tonne of uranium in ore contains about 0.2 milligrams of 227Ac – and in thorium ores, which contain about 5 nanograms of 228Ac per one tonne of thorium. The actinium isotope 227Ac is a transient member of the uranium-actinium series decay chain, which begins with the parent isotope 235U (or 239Pu) and ends with the stable lead isotope 207Pb. The isotope 228Ac is a transient member of the thorium series decay chain, which begins with the parent isotope 232Th and ends with the stable lead isotope 208Pb. Another actinium isotope (225Ac) is transiently present in the neptunium series decay chain, beginning with 237Np (or 233U) and ending with thallium (205Tl) and near-stable bismuth (209Bi); even though all primordial 237Np has decayed away, it is continuously produced by neutron knock-out reactions on natural 238U.
The low natural concentration, and the close similarity of physical and chemical properties to those of lanthanum and other lanthanides, which are always abundant in actinium-bearing ores, render separation of actinium from the ore impractical. The most concentrated actinium sample prepared from raw material consisted of 7 micrograms of 227Ac in less than 0.1 milligrams of La2O3, and complete separation was never achieved. Instead, actinium is prepared, in milligram amounts, by the neutron irradiation of in a nuclear reactor.
^{226}_{88}Ra + ^{1}_{0}n -> ^{227}_{88}Ra ->[\beta^-][42.2 \ \ce{min}] ^{227}_{89}Ac
The reaction yield is about 2% of the radium weight. 227Ac can further capture neutrons resulting in small amounts of 228Ac. After the synthesis, actinium is separated from radium and from the products of decay and nuclear fusion, such as thorium, polonium, lead and bismuth. The extraction can be performed with thenoyltrifluoroacetone-benzene solution from an aqueous solution of the radiation products, and the selectivity to a certain element is achieved by adjusting the pH (to about 6.0 for actinium). An alternative procedure is anion exchange with an appropriate resin in nitric acid, which can result in a separation factor of 1,000,000 for radium and actinium vs. thorium in a two-stage process. Actinium can then be separated from radium, with a ratio of about 100, using a low cross-linking cation exchange resin and nitric acid as eluant.
225Ac was first produced artificially at the Institute for Transuranium Elements (ITU) in Germany using a cyclotron and at St George Hospital in Sydney using a linac in 2000. This rare isotope has potential applications in radiation therapy and is most efficiently produced by bombarding a radium-226 target with 20–30 MeV deuterium ions. This reaction also yields 226Ac which however decays with a half-life of 29 hours and thus does not contaminate 225Ac.
Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor in vacuum at a temperature between . Higher temperatures resulted in evaporation of the product and lower ones lead to an incomplete transformation. Lithium was chosen among other alkali metals because its fluoride is most volatile.Hammond, C. R. The Elements in |
Actinium | Applications | Applications
Owing to its scarcity, high price and radioactivity, 227Ac currently has no significant industrial use, but 225Ac is currently being studied for use in cancer treatments such as targeted alpha therapies.
227Ac is highly radioactive and was therefore studied for use as an active element of radioisotope thermoelectric generators, for example in spacecraft. The oxide of 227Ac pressed with beryllium is also an efficient neutron source with the activity exceeding that of the standard americium-beryllium and radium-beryllium pairs.Russell, Alan M. and Lee, Kok Loong (2005) Structure-property relations in nonferrous metals. Wiley. , pp. 470–471 In all those applications, 227Ac (a beta source) is merely a progenitor which generates alpha-emitting isotopes upon its decay. Beryllium captures alpha particles and emits neutrons owing to its large cross-section for the (α,n) nuclear reaction:
^{9}_{4}Be + ^{4}_{2}He -> ^{12}_{6}C + ^{1}_{0}n + \gamma
The 227AcBe neutron sources can be applied in a neutron probe – a standard device for measuring the quantity of water present in soil, as well as moisture/density for quality control in highway construction.Majumdar, D. K. (2004) Irrigation Water Management: Principles and Practice. p. 108Chandrasekharan, H. and Gupta, Navindu (2006) Fundamentals of Nuclear Science – Application in Agriculture. pp. 202 ff Such probes are also used in well logging applications, in neutron radiography, tomography and other radiochemical investigations.
thumb|upright=0.70|Chemical structure of the DOTA carrier for 225Ac in radiation therapy
225Ac is applied in medicine to produce in a reusable generator or can be used alone as an agent for radiation therapy, in particular targeted alpha therapy (TAT). This isotope has a half-life of 10 days, making it much more suitable for radiation therapy than 213Bi (half-life 46 minutes). Additionally, 225Ac decays to nontoxic 209Bi rather than toxic lead, which is the final product in the decay chains of several other candidate isotopes, namely 227Th, 228Th, and 230U. Not only 225Ac itself, but also its daughters, emit alpha particles which kill cancer cells in the body. The major difficulty with application of 225Ac was that intravenous injection of simple actinium complexes resulted in their accumulation in the bones and liver for a period of tens of years. As a result, after the cancer cells were quickly killed by alpha particles from 225Ac, the radiation from the actinium and its daughters might induce new mutations. To solve this problem, 225Ac was bound to a chelating agent, such as citrate, ethylenediaminetetraacetic acid (EDTA) or diethylene triamine pentaacetic acid (DTPA). This reduced actinium accumulation in the bones, but the excretion from the body remained slow. Much better results were obtained with such chelating agents as HEHA () or DOTA () coupled to trastuzumab, a monoclonal antibody that interferes with the HER2/neu receptor. The latter delivery combination was tested on mice and proved to be effective against leukemia, lymphoma, breast, ovarian, neuroblastoma and prostate cancers.
The medium half-life of 227Ac (21.77 years) makes it a very convenient radioactive isotope in modeling the slow vertical mixing of oceanic waters. The associated processes cannot be studied with the required accuracy by direct measurements of current velocities (of the order 50 meters per year). However, evaluation of the concentration depth-profiles for different isotopes allows estimating the mixing rates. The physics behind this method is as follows: oceanic waters contain homogeneously dispersed 235U. Its decay product, 231Pa, gradually precipitates to the bottom, so that its concentration first increases with depth and then stays nearly constant. 231Pa decays to 227Ac; however, the concentration of the latter isotope does not follow the 231Pa depth profile, but instead increases toward the sea bottom. This occurs because of the mixing processes which raise some additional 227Ac from the sea bottom. Thus analysis of both 231Pa and 227Ac depth profiles allows researchers to model the mixing behavior.
There are theoretical predictions that AcHx hydrides (in this case with very high pressure) are a candidate for a near room-temperature superconductor as they have Tc significantly higher than H3S, possibly near 250 K. |
Actinium | Precautions | Precautions
227Ac is highly radioactive and experiments with it are carried out in a specially designed laboratory equipped with a tight glove box. When actinium trichloride is administered intravenously to rats, about 33% of actinium is deposited into the bones and 50% into the liver. Its toxicity is comparable to, but slightly lower, than that of americium and plutonium. For trace quantities, fume hoods with good aeration suffice; for gram amounts, hot cells with shielding from the intense gamma radiation emitted by 227Ac are necessary. |
Actinium | See also | See also
Actinium series |
Actinium | Notes | Notes |
Actinium | References | References |
Actinium | Bibliography | Bibliography
|
Actinium | External links | External links
Actinium at The Periodic Table of Videos (University of Nottingham)
NLM Hazardous Substances Databank – Actinium, Radioactive
Actinium in
Category:Chemical elements
Category:Chemical elements with face-centered cubic structure
Category:Actinides |
Actinium | Table of Content | Distinguish, History, Properties, Chemical compounds, Oxides, Halides, Other compounds, Isotopes, Occurrence and synthesis, Applications, Precautions, See also, Notes, References, Bibliography, External links |
Americium | good article | Americium is a synthetic chemical element; it has symbol Am and atomic number 95. It is radioactive and a transuranic member of the actinide series in the periodic table, located under the lanthanide element europium and was thus named after the Americas by analogy.
Americium was first produced in 1944 by the group of Glenn T. Seaborg from Berkeley, California, at the Metallurgical Laboratory of the University of Chicago, as part of the Manhattan Project. Although it is the third element in the transuranic series, it was discovered fourth, after the heavier curium. The discovery was kept secret and only released to the public in November 1945. Most americium is produced by uranium or plutonium being bombarded with neutrons in nuclear reactors – one tonne of spent nuclear fuel contains about 100 grams of americium. It is widely used in commercial ionization chamber smoke detectors, as well as in neutron sources and industrial gauges. Several unusual applications, such as nuclear batteries or fuel for space ships with nuclear propulsion, have been proposed for the isotope 242mAm, but they are as yet hindered by the scarcity and high price of this nuclear isomer.
Americium is a relatively soft radioactive metal with a silvery appearance. Its most common isotopes are 241Am and 243Am. In chemical compounds, americium usually assumes the oxidation state +3, especially in solutions. Several other oxidation states are known, ranging from +2 to +7, and can be identified by their characteristic optical absorption spectra. The crystal lattices of solid americium and its compounds contain small intrinsic radiogenic defects, due to metamictization induced by self-irradiation with alpha particles, which accumulates with time; this can cause a drift of some material properties over time, more noticeable in older samples. |
Americium | History | History
thumb|left|The 60-inch cyclotron at the Lawrence Radiation Laboratory, University of California, Berkeley, in August 1939
Although americium was likely produced in previous nuclear experiments, it was first intentionally synthesized, isolated and identified in late autumn 1944, at the University of California, Berkeley, by Glenn T. Seaborg, Leon O. Morgan, Ralph A. James, and Albert Ghiorso. They used a 60-inch cyclotron at the University of California, Berkeley.Obituary of Dr. Leon Owen (Tom) Morgan (1919–2002), Retrieved 28 November 2010 The element was chemically identified at the Metallurgical Laboratory (now Argonne National Laboratory) of the University of Chicago. Following the lighter neptunium, plutonium, and heavier curium, americium was the fourth transuranium element to be discovered. At the time, the periodic table had been restructured by Seaborg to its present layout, containing the actinide row below the lanthanide one. This led to americium being located right below its twin lanthanide element europium; it was thus by analogy named after the Americas: "The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series."Seaborg, G. T.; James, R.A. and Morgan, L. O.: "The New Element Americium (Atomic Number 95)", THIN PPR (National Nuclear Energy Series, Plutonium Project Record), Vol 14 B The Transuranium Elements: Research Papers, Paper No. 22.1, McGraw-Hill Book Co., Inc., New York, 1949. Abstract; Full text (January 1948), Retrieved 28 November 2010Greenwood, p. 1252
The new element was isolated from its oxides in a complex, multi-step process. First plutonium-239 nitrate (239PuNO3) solution was coated on a platinum foil of about 0.5 cm2 area, the solution was evaporated and the residue was converted into plutonium dioxide (PuO2) by calcining. After cyclotron irradiation, the coating was dissolved with nitric acid, and then precipitated as the hydroxide using concentrated aqueous ammonia solution. The residue was dissolved in perchloric acid. Further separation was carried out by ion exchange, yielding a certain isotope of curium. The separation of curium and americium was so painstaking that those elements were initially called by the Berkeley group as pandemonium (from Greek for all demons or hell) and delirium (from Latin for madness).
Initial experiments yielded four americium isotopes: 241Am, 242Am, 239Am and 238Am. Americium-241 was directly obtained from plutonium upon absorption of two neutrons. It decays by emission of a α-particle to 237Np; the half-life of this decay was first determined as years but then corrected to 432.2 years.
The times are half-lives
The second isotope 242Am was produced upon neutron bombardment of the already-created 241Am. Upon rapid β-decay, 242Am converts into the isotope of curium 242Cm (which had been discovered previously). The half-life of this decay was initially determined at 17 hours, which was close to the presently accepted value of 16.02 h.
The discovery of americium and curium in 1944 was closely related to the Manhattan Project; the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children Quiz Kids five days before the official presentation at an American Chemical Society meeting on 11 November 1945, when one of the listeners asked whether any new transuranium element besides plutonium and neptunium had been discovered during the war. After the discovery of americium isotopes 241Am and 242Am, their production and compounds were patented listing only Seaborg as the inventor.Seaborg, Glenn T. "Element", Filing date: 23 August 1946, Issue date: 10 November 1964 The initial americium samples weighed a few micrograms; they were barely visible and were identified by their radioactivity. The first substantial amounts of metallic americium weighing 40–200 micrograms were not prepared until 1951 by reduction of americium(III) fluoride with barium metal in high vacuum at 1100 °C. |
Americium | Occurrence | Occurrence
thumb|Americium was detected in the fallout from the Ivy Mike nuclear test.
The longest-lived and most common isotopes of americium, 241Am and 243Am, have half-lives of 432.2 and 7,370 years, respectively. Therefore, any primordial americium (americium that was present on Earth during its formation) should have decayed by now. Trace amounts of americium probably occur naturally in uranium minerals as a result of neutron capture and beta decay (238U → 239Pu → 240Pu → 241Am), though the quantities would be tiny and this has not been confirmed. Extraterrestrial long-lived 247Cm is probably also deposited on Earth and has 243Am as one of its intermediate decay products, but again this has not been confirmed.
Existing americium is concentrated in the areas used for the atmospheric nuclear weapons tests conducted between 1945 and 1980, as well as at the sites of nuclear incidents, such as the Chernobyl disaster. For example, the analysis of the debris at the testing site of the first U.S. hydrogen bomb, Ivy Mike, (1 November 1952, Enewetak Atoll), revealed high concentrations of various actinides including americium; but due to military secrecy, this result was not published until later, in 1956. Trinitite, the glassy residue left on the desert floor near Alamogordo, New Mexico, after the plutonium-based Trinity nuclear bomb test on 16 July 1945, contains traces of americium-241. Elevated levels of americium were also detected at the crash site of a US Boeing B-52 bomber aircraft, which carried four hydrogen bombs, in 1968 in Greenland.
In other regions, the average radioactivity of surface soil due to residual americium is only about 0.01 picocuries per gram (0.37 mBq/g). Atmospheric americium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 1,900 times higher concentration of americium inside sandy soil particles than in the water present in the soil pores; an even higher ratio was measured in loam soils.Human Health Fact Sheet on Americium , Los Alamos National Laboratory, Retrieved 28 November 2010
Americium is produced mostly artificially in small quantities, for research purposes. A tonne of spent nuclear fuel contains about 100 grams of various americium isotopes, mostly 241Am and 243Am.Hoffmann, Klaus Kann man Gold machen? Gauner, Gaukler und Gelehrte. Aus der Geschichte der chemischen Elemente (Can you make gold? Crooks, clowns, and scholars. From the history of the chemical elements), Urania-Verlag, Leipzig, Jena, Berlin 1979, no ISBN, p. 233 Their prolonged radioactivity is undesirable for the disposal, and therefore americium, together with other long-lived actinides, must be neutralized. The associated procedure may involve several steps, where americium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure is well known as nuclear transmutation, but it is still being developed for americium.Baetslé, L. Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management , Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001, Retrieved 28 November 2010Fioni, Gabriele; Cribier, Michel and Marie, Frédéric Can the minor actinide, americium-241, be transmuted by thermal neutrons? , Department of Astrophysics, CEA/Saclay, Retrieved 28 November 2010 The transuranic elements from americium to fermium occurred naturally in the natural nuclear fission reactor at Oklo, but no longer do so.
Americium is also one of the elements that have theoretically been detected in Przybylski's Star. |
Americium | Synthesis and extraction | Synthesis and extraction |
Americium | Isotope nucleosynthesis | Isotope nucleosynthesis
thumb|Chromatographic elution curves revealing the similarity between the lanthanides Tb, Gd, and Eu and the corresponding actinides Bk, Cm, and Am
Americium has been produced in small quantities in nuclear reactors for decades, and kilograms of its 241Am and 243Am isotopes have been accumulated by now.Greenwood, p. 1262 Nevertheless, since it was first offered for sale in 1962, its price, about of 241Am, remains almost unchanged owing to the very complex separation procedure.Smoke detectors and americium , World Nuclear Association, January 2009, Retrieved 28 November 2010 The heavier isotope 243Am is produced in much smaller amounts; it is thus more difficult to separate, resulting in a higher cost of the order .Hammond C. R. "The elements" in
Americium is not synthesized directly from uranium – the most common reactor material – but from the plutonium isotope 239Pu. The latter needs to be produced first, according to the following nuclear process:
^{238}_{92}U ->[\ce{(n,\gamma)}] ^{239}_{92}U ->[\beta^-][23.5 \ \ce{min}] ^{239}_{93}Np ->[\beta^-][2.3565 \ \ce{d}] ^{239}_{94}Pu
The capture of two neutrons by 239Pu (a so-called (n,γ) reaction), followed by a β-decay, results in 241Am:
^{239}_{94}Pu ->[\ce{2(n,\gamma)}] ^{241}_{94}Pu ->[\beta^-][14.35 \ \ce{yr}] ^{241}_{95}Am
The plutonium present in spent nuclear fuel contains about 12% of 241Pu. Because it beta-decays to 241Am, 241Pu can be extracted and may be used to generate further 241Am. However, this process is rather slow: half of the original amount of 241Pu decays to 241Am after about 15 years, and the 241Am amount reaches a maximum after 70 years.BREDL Southern Anti-Plutonium Campaign, Blue Ridge Environmental Defense League, Retrieved 28 November 2010
The obtained 241Am can be used for generating heavier americium isotopes by further neutron capture inside a nuclear reactor. In a light water reactor (LWR), 79% of 241Am converts to 242Am and 10% to its nuclear isomer 242mAm:The "metastable" state is marked by the letter m. article/200410/000020041004A0333355.php Abstract
Americium-242 has a half-life of only 16 hours, which makes its further conversion to 243Am extremely inefficient. The latter isotope is produced instead in a process where 239Pu captures four neutrons under high neutron flux:
^{239}_{94}Pu ->[\ce{4(n,\gamma)}] \ ^{243}_{94}Pu ->[\beta^-][4.956 \ \ce{h}] ^{243}_{95}Am |
Americium | Metal generation | Metal generation
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 techniquesPenneman, pp. 34–48 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.Penneman, p. 25
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.Gmelin Handbook of Inorganic Chemistry, System No. 71, transuranics, Part B 1, pp. 57–67.Penneman, p. 3
An alternative is the reduction of americium dioxide by metallic lanthanum or thorium:
|
Americium | Physical properties | Physical properties
thumb|Double-hexagonal close packing with the layer sequence ABAC in the crystal structure of α-americium (A: green, B: blue, C: red)
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/cm3, americium is less dense than both curium (13.52 g/cm3) and plutonium (19.8 g/cm3); but has a higher density than europium (5.264 g/cm3)—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).
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 Fmm 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.
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.
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 along the shorter a axis and for the longer c hexagonal axis. The enthalpy of dissolution of americium metal in hydrochloric acid at standard conditions is , from which the standard enthalpy change of formation (ΔfH°) of aqueous Am3+ ion is . The standard potential Am3+/Am0 is . |
Americium | Chemical properties | Chemical properties
Americium metal readily reacts with oxygen and dissolves in aqueous acids. The most stable oxidation state for americium is +3.Penneman, p. 4 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: Am3+ (yellow-reddish), Am4+ (yellow-reddish), ; (yellow), (brown) and (dark green).Americium , Das Periodensystem der Elemente für den Schulgebrauch (The periodic table of elements for schools) chemie-master.de (in German), Retrieved 28 November 2010Greenwood, p. 1265 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.Penneman, pp. 10–14
Americium compounds with oxidation state +4 and higher are strong oxidizing agents, comparable in strength to the permanganate ion () in acidic solutions.Wiberg, p. 1956 Whereas the Am4+ ions are unstable in solutions and readily convert to Am3+, compounds such as americium dioxide (AmO2) and americium(IV) fluoride (AmF4) are stable in the solid state.
The pentavalent oxidation state of americium was first observed in 1951. In acidic aqueous solution the ion is unstable with respect to disproportionation.Greenwood, p. 1275 The reaction
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 and are comparable to uranates and the ion is comparable to the uranyl ion, . 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. |
Americium | Chemical compounds | Chemical compounds |
Americium | Oxygen compounds | Oxygen 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.Wiberg, p. 1972 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.Greenwood, p. 1267
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.Penneman, p. 5 |
Americium | Halides | Halides
Halides of americium are known for the oxidation states +2, +3 and +4,Wiberg, p. 1969 where the +3 is most stable, especially in solutions.
Oxidation state F Cl Br I +4 Americium(IV) fluoride AmF4 pale pink +3 Americium(III) fluoride AmF3 pink Americium(III) chloride AmCl3 pink Americium(III) bromide AmBr3 light yellow Americium(III) iodide AmI3 light yellow +2 Americium(II) chloride AmCl2 black Americium(II) bromide AmBr2 black Americium(II) iodide AmI2 black
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:
Orthorhombic AmCl2: a = , b = and c =
Tetragonal AmBr2: a = and c = . They can also be prepared by reacting metallic americium with an appropriate mercury halide HgX2, where X = Cl, Br or I:Greenwood, p. 1272
{Am} + \underset{mercury\ halide}{HgX2} ->[{} \atop 400 - 500 ^\circ \ce C] {AmX2} + {Hg}
Americium(III) fluoride (AmF3) is poorly soluble and precipitates upon reaction of Am3+ and fluoride ions in weak acidic solutions:
Am^3+ + 3F^- -> AmF3(v)
The tetravalent americium(IV) fluoride (AmF4) is obtained by reacting solid americium(III) fluoride with molecular fluorine:Greenwood, p. 1271
2AmF3 + F2 -> 2AmF4
Another known form of solid tetravalent americium fluoride is KAmF5.Penneman, p. 6 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.
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 R). The bromide is an exception with the orthorhombic PuBr3-type structure and space group Cmcm. Crystals of americium(III) chloride 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.
Oxyhalides of americium in the form AmVIO2X2, AmVO2X, AmIVOX2 and AmIIIOX can be obtained by reacting the corresponding americium halide with oxygen or Sb2O3, and AmOCl can also be produced by vapor phase hydrolysis:
AmCl3 + H2O -> AmOCl + 2HCl |
Americium | Chalcogenides and pnictides | Chalcogenides and pnictides
The known chalcogenides of americium include the sulfide AmS2, selenides AmSe2 and Am3Se4, and tellurides Am2Te3 and AmTe2. The pnictides of americium (243Am) of the AmX type are known for the elements phosphorus, arsenic, antimony and bismuth. They crystallize in the rock-salt lattice. |
Americium | Silicides and borides | Silicides and borides
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.Lupinetti, A. J. et al. "Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions", Filed 4 Apr 2002, Issued 14 December 2004 |
Americium | Organoamericium compounds | Organoamericium compounds
thumb|upright=0.55|Predicted structure of amerocene [(η8-C8H8)2Am]
Analogous to uranocene, americium is predicted to form the organometallic compound amerocene with two cyclooctatetraene ligands, with the chemical formula (η8-C8H8)2Am. A cyclopentadienyl complex is also known that is likely to be stoichiometrically AmCp3.
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 Am3+ 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. |
Americium | Biological aspects | Biological aspects
Americium is an artificial element of recent origin, and thus does not have a biological requirement.Toeniskoetter, Steve; Dommer, Jennifer and Dodge, Tony The Biochemical Periodic Tables – Americium, University of Minnesota, Retrieved 28 November 2010 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. In the laboratory, both americium and curium were found to support the growth of methylotrophs. |
Americium | Fission | Fission
The isotope 242mAm (half-life 141 years) has the largest cross sections for absorption of thermal neutrons (5,700 barns),Pfennig, G.; Klewe-Nebenius, H and Seelmann Eggebert, W. (Eds.): Karlsruhe nuclide, 7 Edition 2006. that results in a small critical mass for a sustained nuclear chain reaction. The critical mass for a bare 242mAm 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. Abstract Such small critical mass is favorable for portable nuclear weapons, but those based on 242mAm are not known yet, probably because of its scarcity and high price. The critical masses of the two readily available isotopes, 241Am and 243Am, are relatively high – 57.6 to 75.6 kg for 241Am and 209 kg for 243Am.Institut de Radioprotection et de Sûreté Nucléaire, "Evaluation of nuclear criticality safety data and limits for actinides in transport", p. 16. Scarcity and high price yet hinder application of americium as a nuclear fuel in nuclear reactors.
There are proposals of very compact 10-kW high-flux reactors using as little as 20 grams of 242mAm. Such low-power reactors would be relatively safe to use as neutron sources for radiation therapy in hospitals. |
Americium | Isotopes | Isotopes
About 18 isotopes and 11 nuclear isomers are known for americium, having mass numbers 229, 230, and 232 through 247. There are two long-lived alpha-emitters; 243Am has a half-life of 7,370 years and is the most stable isotope, and 241Am has a half-life of 432.2 years. The most stable nuclear isomer is 242m1Am; it has a long half-life of 141 years. The half-lives of other isotopes and isomers range from 0.64 microseconds for 245m1Am to 50.8 hours for 240Am. 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.
Americium-241 decays to 237Np 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.
Americium-242 is a short-lived isotope with a half-life of 16.02 h. It mostly (82.7%) converts by β-decay to 242Cm, but also by electron capture to 242Pu (17.3%). Both 242Cm and 242Pu transform via nearly the same decay chain through 238Pu down to 234U.
Nearly all (99.541%) of 242m1Am decays by internal conversion to 242Am and the remaining 0.459% by α-decay to 238Np. The latter subsequently decays to 238Pu and then to 234U.
Americium-243 transforms by α-emission into 239Np, which converts by β-decay to 239Pu, and the 239Pu changes into 235U by emitting an α-particle. |
Americium | Applications | Applications |
Americium | Ionization-type smoke detector | Ionization-type smoke detector
Americium is used in the most common type of household smoke detector, which uses 241Am in the form of americium dioxide as its source of ionizing radiation. This isotope is preferred over 226Ra because it emits 5 times more alpha particles and relatively little harmful gamma radiation.
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.Residential Smoke Alarm Performance, Thomas Cleary. Building and Fire Research Laboratory, National Institute of Standards and Technology; UL Smoke and Fire Dynamics Seminar. November 2007Bukowski, R. W. et al. (2007) Performance of Home Smoke Alarms Analysis of the Response of Several Available Technologies in Residential Fire Settings , NIST Technical Note 1455-1 |
Americium | Radionuclide | Radionuclide
As 241Am has a roughly similar half-life to 238Pu (432.2 years vs. 87 years), it has been proposed as an active element of radioisotope thermoelectric generators, for example in spacecraft.Basic elements of static RTGs , G.L. Kulcinski, NEEP 602 Course Notes (Spring 2000), Nuclear Power in Space, University of Wisconsin Fusion Technology Institute (see last page) Although americium produces less heat and electricity – the power yield is 114.7 mW/g for 241Am and 6.31 mW/g for 243Am (cf. 390 mW/g for 238Pu) – and its radiation poses more threat to humans owing to neutron emission, the European Space Agency is considering using americium for its space probes.Space agencies tackle waning plutonium stockpiles, Spaceflight now, 9 July 2010
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 242mAm, 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 242mAm 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.
One more proposal which utilizes the high nuclear fission rate of 242mAm 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 242mAm charge of such battery could provide about 140 kW of power over a period of 80 days.Genuth, Iddo Americium Power Source , The Future of Things, 3 October 2006, Retrieved 28 November 2010 Even with all the potential benefits, the current applications of 242mAm are as yet hindered by the scarcity and high price of this particular nuclear isomer.
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. |
Americium | Neutron source | Neutron source
The oxide of 241Am 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:
^{241}_{95}Am -> ^{237}_{93}Np + ^{4}_{2}He + \gamma
^{9}_{4}Be + ^{4}_{2}He -> ^{12}_{6}C + ^{1}_{0}n + \gamma
The most widespread use of 241AmBe 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. 241Am neutron sources are also used in well logging applications, as well as in neutron radiography, tomography and other radiochemical investigations. |
Americium | Production of other elements | Production of other elements
Americium is a starting material for the production of other transuranic elements and transactinides – for example, 82.7% of 242Am decays to 242Cm and 17.3% to 242Pu. In the nuclear reactor, 242Am is also up-converted by neutron capture to 243Am and 244Am, which transforms by β-decay to 244Cm:
^{243}_{95}Am ->[\ce{(n,\gamma)}] ^{244}_{95}Am ->[\beta^-][10.1 \ \ce{h}] ^{244}_{96}Cm
Irradiation of 241Am by 12C or 22Ne ions yields the isotopes 247Es (einsteinium) or 260Db (dubnium), respectively. Furthermore, the element berkelium (243Bk isotope) had been first intentionally produced and identified by bombarding 241Am 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 243Am with 15N ions. Besides, one of the synthesis reactions for lawrencium, discovered by scientists at Berkeley and Dubna, included bombardment of 243Am with 18O. |
Americium | Spectrometer | Spectrometer
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 241Am 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).Nuclear Data Viewer 2.4 , NNDC Americium-241 gamma rays were also used to provide passive diagnosis of thyroid function. This medical application is however obsolete. |
Americium | Health concerns | Health concerns
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.Public Health Statement for Americium Section 1.5., Agency for Toxic Substances and Disease Registry, April 2004, Retrieved 28 November 2010
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 241Am 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.Frisch, Franz Crystal Clear, 100 x energy, Bibliographisches Institut AG, Mannheim 1977, , p. 184
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.Ken Silverstein, The Radioactive Boy Scout: When a teenager attempts to build a breeder reactor. Harper's Magazine, November 1998 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. |
Americium | See also | See also
Actinides in the environment
:Category:Americium compounds |
Americium | Notes | Notes |
Americium | References | References |
Americium | Bibliography | Bibliography
Penneman, R. A. and Keenan T. K. The radiochemistry of americium and curium, University of California, Los Alamos, California, 1960
|
Americium | Further reading | Further reading
Nuclides and Isotopes – 14th Edition, GE Nuclear Energy, 1989.
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Americium | External links | External links
Americium at The Periodic Table of Videos (University of Nottingham)
ATSDR – Public Health Statement: Americium
World Nuclear Association – Smoke Detectors and Americium
Category:Chemical elements
Category:Chemical elements with double hexagonal close-packed structure
Category:Actinides
Category:Carcinogens
Category:Synthetic elements |
Americium | Table of Content | good article, History, Occurrence, Synthesis and extraction, Isotope nucleosynthesis, Metal generation, Physical properties, Chemical properties, Chemical compounds, Oxygen compounds, Halides, Chalcogenides and pnictides, Silicides and borides, Organoamericium compounds, Biological aspects, Fission, Isotopes, Applications, Ionization-type smoke detector, Radionuclide, Neutron source, Production of other elements, Spectrometer, Health concerns, See also, Notes, References, Bibliography, Further reading, External links |
Astatine | Featured article | 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.
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.
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 () '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. |
Astatine | Characteristics | 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 (205–211At) are in any case synthetic and do not occur in nature.
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. |
Astatine | Physical | Physical
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).
Astatine sublimes less readily than 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.
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/cm3.
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 , dissociation energy <, 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. |
Astatine | Chemical | Chemical
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 10−10 mol·L−1. 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.
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−1, 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−1, which continues the trend of decreasing first ionization energies down the halogen group (fluorine, 1681; chlorine, 1251; bromine, 1140; iodine, 1008). |
Astatine | Compounds | 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.
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.
thumb|left|upright=0.6|Hydrogen astatide space-filling model
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 At0 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 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.
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 has since been determined to be , a hydrolysis product of AtO+ (another such hydrolysis product being AtOOH). The well characterized 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 , such as by xenon difluoride (in a hot alkaline solution) or periodate (in a neutral or alkaline solution), yields the perastatate ion ; 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 may form bonds to the other chalcogens; these include S7At+ and with sulfur, a coordination selenourea compound with selenium, and an astatine–tellurium colloid with tellurium.
thumb|upright=0.9|Structure of astatine monoiodide, one of the astatine interhalogens and the heaviest known diatomic interhalogen
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 and ions, or in a chloride solution, they may produce species like or 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, or 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. |
Astatine | History | 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 '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.
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.
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.
thumb|upright|alt=A greyscale photo of the upper body of a man|Emilio Segrè, one of the discoverers of the main-group element astatine
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 , 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.
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 () meaning , 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.
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 | Isotopes | Isotopes
+ Alpha decay characteristics for sample astatine isotopes Massnumber Half-life Probabilityof alphadecay Alpha-decayhalf-life 207 % 208 % 209 % 210 % 211 % 212 ≈100% 213 % 214 % 219 % 220 % 221 experimentallyalpha-stable ∞
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'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 215At is in fact beta-stable, as it has the lowest mass of all isobars with A = 215. Astatine-210 and most of the lighter isotopes exhibit beta plus decay (positron emission), astatine-217 and heavier isotopes except astatine-218 exhibit beta minus decay, while astatine-211 undergoes electron capture.
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.
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-213m1; its half-life of 110 nanoseconds is shorter than 125 nanoseconds for astatine-213, the shortest-lived ground state. |
Astatine | Natural occurrence | Natural occurrence
thumb|upright=0.7|alt=a sequence of differently colored balls, each containing a two-letter symbol and some numbers|Neptunium series, showing the decay products, including astatine-217, formed from neptunium-237
Astatine is the rarest naturally occurring element. The total amount of astatine in the Earth's crust (quoted mass 2.36 × 1025 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).
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 × 10−10 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.
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 | Synthesis | Synthesis |
Astatine | Formation | Formation
+ Possible reactions after bombarding bismuth-209 with alpha particles Reaction Energy of alpha particle Threshold energy Maximum production + → + 2 n 20.7 MeV 30–31 MeV + → + 3 n 28.4–28.6 MeV 37 MeV + → + 4 n 35.9 MeV
thumb|left|The bismuth target after irradiation contains minuscule quantities of astatine-211.
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 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.
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. Although higher energies can produce more astatine-211, it will produce unwanted astatine-210 that decays to toxic polonium-210 as well. Instead, the maximum energy of the particle accelerator is set to be below or slightly above the threshold of astatine-210 production, in order to maximize the production of astatine-211 while keeping the amount of astatine-210 at an acceptable level. |
Astatine | Separation methods | Separation methods
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 | Dry | Dry
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 | Wet | Wet
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 | Uses and precautions | Uses and precautions
+ Several 211At-containing molecules and their experimental uses Agent Applications [211At]astatine-tellurium colloids Compartmental tumors 6-[211At]astato-2-methyl-1,4-naphtaquinol diphosphate Adenocarcinomas 211At-labeled methylene blue Melanomas Meta-[211At]astatobenzyl guanidine Neuroendocrine tumors 5-[211At]astato-2'-deoxyuridine Various 211At-labeled biotin conjugates Various pretargeting 211At-labeled octreotide Somatostatin receptor 211At-labeled monoclonal antibodies and fragments Various 211At-labeled bisphosphonates Bone metastases
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.
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.
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 sp3 carbon sites (less so from sp2 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.
Animal studies show that astatine, similarly to iodine—although to a lesser extent, perhaps because of its slightly more metallic natureStwertka, Albert. A Guide to the Elements, Oxford University Press, 1996, p. 193. —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. |
Astatine | See also | See also
Radiation protection |
Astatine | Notes | Notes |
Astatine | References | References |
Astatine | Bibliography | Bibliography
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Astatine | External links | External links
Astatine at The Periodic Table of Videos (University of Nottingham)
Astatine: Halogen or Metal?
Category:Chemical elements
Category:Chemical elements with face-centered cubic structure
Category:Halogens
Category:Synthetic elements |
Astatine | Table of Content | Featured article, Characteristics, Physical, Chemical, Compounds, History, Isotopes, Natural occurrence, Synthesis, Formation, Separation methods, Dry, Wet, Uses and precautions, See also, Notes, References, Bibliography, External links |
Atom | Short description | Atoms are the basic particles 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.
Atoms are extremely small, typically around 100 picometers across. A human hair is about a million carbon atoms wide. Atoms are smaller than the shortest wavelength of visible light, which means humans cannot see atoms with conventional microscopes. They are so small that accurately predicting their behavior using classical physics is not possible due to quantum effects.
More than 99.9994% 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).
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.
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 | History of atomic theory | History of atomic theory |
Atom | In philosophy | In philosophy
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". But this ancient idea was based in philosophical reasoning rather than scientific reasoning. Modern atomic theory is not based on these old concepts.Melsen (1952). From Atomos to Atom, pp. 18–19 In the early 19th century, the scientist John Dalton found evidence that matter really is composed of discrete units, and so applied the word atom to those units.Pullman (1998). The Atom in the History of Human Thought, p. 201 |
Atom | Dalton's law of multiple proportions | Dalton's law of multiple proportions
thumb|right|Various atoms and molecules from A New System of Chemical Philosophy (John Dalton 1808).
In the early 1800s, 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 any group of chemical compounds which all contain two particular chemical elements, the amount of Element A per measure of Element B will differ across these compounds by ratios of small whole numbers. This pattern suggested that each element combines with other elements in multiples of a basic unit of weight, with each element having a unit of unique weight. Dalton decided to call these units "atoms".Pullman (1998). The Atom in the History of Human Thought, p. 199: "The constant ratios, expressible in terms of integers, of the weights of the constituents in composite bodies could be construed as evidence on a macroscopic scale of interactions at the microscopic level between basic units with fixed weights. For Dalton, this agreement strongly suggested a corpuscular structure of matter, even though it did not constitute definite proof."
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 the grey oxide there is one atom of oxygen for every atom of tin, and in the white oxide there are two atoms of oxygen for every atom of tin (SnO and SnO2).Dalton (1817). A New System of Chemical Philosophy vol. 2, p. 36Melsen (1952). From Atomos to Atom, p. 137
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. These substances are known today as iron(II) oxide and iron(III) oxide, and their formulas are FeO and Fe2O3 respectively. Iron(II) oxide's formula is normally written as FeO, but since it is a crystalline substance we could alternately write it as Fe2O2, and when we contrast that with Fe2O3, the 2:3 ratio for the oxygen is plain to see.Dalton (1817). A New System of Chemical Philosophy vol. 2, p. 28Millington (1906). John Dalton, p. 113
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.Dalton (1808). A New System of Chemical Philosophy vol. 1, pp. 316–319Holbrow et al. (2010). Modern Introductory Physics, pp. 65–66 |
Atom | Discovery of the electron | Discovery of the electron
In 1897, J. J. Thomson discovered that cathode rays can be deflected by electric and magnetic fields, which meant that cathode rays are not a form of light but made of electrically charged particles, and their charge was negative given the direction the particles were deflected in. He measured these particles to be 1,700 times lighter than hydrogen (the lightest atom).In his book The Corpuscular Theory of Matter (1907), Thomson estimates electrons to be 1/1700 the mass of hydrogen. He called these new particles corpuscles but they were later renamed electrons since these are the particles that carry electricity."The Mechanism Of Conduction In Metals" , Think Quest. Thomson also showed that electrons were identical to particles given off by photoelectric and radioactive materials. Thomson explained that an electric current is the passing of electrons from one atom to the next, and when there was no current the electrons embedded themselves in the atoms. This in turn meant that atoms were not indivisible as scientists thought. The atom was composed of electrons whose negative charge was balanced out by some source of positive charge to create an electrically neutral atom. Ions, Thomson explained, must be atoms which have an excess or shortage of electrons.J. J. Thomson (1907). On the Corpuscular Theory of Matter, p. 26: "The simplest interpretation of these results is that the positive ions are the atoms or groups of atoms of various elements from which one or more corpuscles have been removed [...] while the negative electrified body is one with more corpuscles than the unelectrified one." |
Atom | Discovery of the nucleus | Discovery of the nucleus
thumb|right|The Rutherford scattering experiments: The extreme scattering of some alpha particles suggested the existence of a nucleus of concentrated charge.
The electrons in the atom logically had to be balanced out by a commensurate amount of positive charge, but Thomson had no idea where this positive charge came from, so he tentatively proposed that it was everywhere in the atom, the atom being in the shape of a sphere. This was the mathematically simplest hypothesis to fit the available evidence, or lack thereof. Following from this, Thomson imagined that the balance of electrostatic forces would distribute the electrons throughout the sphere in a more or less even manner.J. J. Thomson (1907). The Corpuscular Theory of Matter, p. 103: "In default of exact knowledge of the nature of the way in which positive electricity occurs in the atom, we shall consider a case in which the positive electricity is distributed in the way most amenable to mathematical calculation, i.e., when it occurs as a sphere of uniform density, throughout which the corpuscles are distributed." Thomson's model is popularly known as the plum pudding model, though neither Thomson nor his colleagues used this analogy. Thomson's model was incomplete, it was unable to predict any other properties of the elements such as emission spectra and valencies. It was soon rendered obsolete by the discovery of the atomic nucleus.
Between 1908 and 1913, Ernest Rutherford and his colleagues Hans Geiger and Ernest Marsden performed a series of experiments in which they bombarded thin foils of metal with a beam of alpha particles. They did this to measure the scattering patterns of the alpha particles. They spotted a small number of alpha particles being deflected by angles greater than 90°. This shouldn't have been possible according to the Thomson model of the atom, whose charges were too diffuse to produce a sufficiently strong electric field. The deflections should have all been negligible. Rutherford proposed that the positive charge of the atom is concentrated in a tiny volume at the center of the atom and that the electrons surround this nucleus in a diffuse cloud. This nucleus carried almost all of the atom's mass. Only such an intense concentration of charge, anchored by its high mass, could produce an electric field that could deflect the alpha particles so strongly.Heilbron (2003). Ernest Rutherford and the Explosion of Atoms, pp. 64–68 |
Atom | Bohr model | Bohr model
right|thumb|The Bohr model of the atom, with an electron making instantaneous "quantum leaps" from one orbit to another with gain or loss of energy. This model of electrons in orbits is obsolete.
A problem in classical mechanics is that an accelerating charged particle radiates electromagnetic radiation, causing the particle to lose kinetic energy. Circular motion counts as acceleration, which means that an electron orbiting a central charge should spiral down into that nucleus as it loses speed. In 1913, the physicist Niels Bohr proposed a new model in which the electrons of an atom were assumed to orbit the nucleus but could only do so in a finite set of orbits, and could jump between these orbits only in discrete changes of energy corresponding to absorption or radiation of a photon. This quantization was used to explain why the electrons' orbits are stable and why elements absorb and emit electromagnetic radiation in discrete spectra. Bohr's model could only predict the emission spectra of hydrogen, not atoms with more than one electron. |
Atom | Discovery of protons and neutrons | Discovery of protons and neutrons
Back in 1815, William Prout observed that the atomic weights of many elements were multiples of hydrogen's atomic weight, which is in fact true for all of them if one takes isotopes into account. In 1898, J. J. Thomson found that the positive charge of a hydrogen ion is equal to the negative charge of an electron, and these were then the smallest known charged particles. Thomson later found that the positive charge in an atom is a positive multiple of an electron's negative charge.J. J. Thomson (1907). The Corpuscular Theory of Matter. p. 26–27: "In an unelectrified atom there are as many units of positive electricity as there are of negative; an atom with a unit of positive charge is a neutral atom which has lost one corpuscle, while an atom with a unit of negative charge is a neutral atom to which an additional corpuscle has been attached." In 1913, Henry Moseley discovered that the frequencies of X-ray emissions from an excited atom were a mathematical function of its atomic number and hydrogen's nuclear charge. In 1919, Rutherford bombarded nitrogen gas with alpha particles and detected hydrogen ions being emitted from the gas, and concluded that they were produced by alpha particles hitting and splitting the nuclei of the nitrogen atoms.
These observations led Rutherford to conclude that the hydrogen nucleus is a singular particle with a positive charge equal to the electron's negative charge.The Development of the Theory of Atomic Structure (Rutherford 1936). Reprinted in Background to Modern Science: Ten Lectures at Cambridge arranged by the History of Science Committee 1936:"In 1919 I showed that when light atoms were bombarded by α-particles they could be broken up with the emission of a proton, or hydrogen nucleus. We therefore presumed that a proton must be one of the units of which the nuclei of other atoms were composed..." He named this particle "proton" in 1920.Footnote by Ernest Rutherford: 'At the time of writing this paper in Australia, Professor Orme Masson was not aware that the name "proton" had already been suggested as a suitable name for the unit of mass nearly 1, in terms of oxygen 16, that appears to enter into the nuclear structure of atoms. The question of a suitable name for this unit was discussed at an informal meeting of a number of members of Section A of the British Association at Cardiff this year. The name "baron" suggested by Professor Masson was mentioned, but was considered unsuitable on account of the existing variety of meanings. Finally the name "proton" met with general approval, particularly as it suggests the original term "protyle " given by Prout in his well-known hypothesis that all atoms are built up of hydrogen. The need of a special name for the nuclear unit of mass 1 was drawn attention to by Sir Oliver Lodge at the Sectional meeting, and the writer then suggested the name "proton."' The number of protons in an atom (which Rutherford called the "atomic number"Eric Scerri (2020). The Periodic Table: Its Story and Its Significance, p. 185Helge Kragh (2012). Niels Bohr and the Quantum Atom, p. 33) was found to be equal to the element's ordinal number on the periodic table and therefore provided a simple and clear-cut way of distinguishing the elements from each other. The atomic weight of each element is higher than its proton number, so Rutherford hypothesized that the surplus weight was carried by unknown particles with no electric charge and a mass equal to that of the proton.
In 1928, Walter Bothe observed that beryllium emitted a highly penetrating, electrically neutral radiation when bombarded with alpha particles. It was later discovered that this radiation could knock hydrogen atoms out of paraffin wax. Initially it was thought to be high-energy gamma radiation, since gamma radiation had a similar effect on electrons in metals, but James Chadwick found that the ionization effect was too strong for it to be due to electromagnetic radiation, so long as energy and momentum were conserved in the interaction. In 1932, Chadwick exposed various elements, such as hydrogen and nitrogen, to the mysterious "beryllium radiation", and by measuring the energies of the recoiling charged particles, he deduced that the radiation was actually composed of electrically neutral particles which could not be massless like the gamma ray, but instead were required to have a mass similar to that of a proton. Chadwick now claimed these particles as Rutherford's neutrons. |
Atom | The current consensus model | The current consensus model
thumb|right|The modern model of atomic orbitals draws zones where an electron is most likely to be found at any moment.
In 1925, Werner Heisenberg published the first consistent mathematical formulation of quantum mechanics (matrix mechanics). One year earlier, Louis de Broglie had proposed that all particles behave like waves to some extent, and in 1926 Erwin Schrödinger used this idea to develop the Schrödinger equation, which describes electrons as three-dimensional waveforms rather than points in space. A consequence of using waveforms to describe particles is that it is mathematically impossible to obtain precise values for both the position and momentum of a particle at a given point in time. This became known as the uncertainty principle, formulated by Werner Heisenberg in 1927. In this concept, for a given accuracy in measuring a position one could only obtain a range of probable values for momentum, and vice versa. Thus, the planetary model of the atom was discarded in favor of one that described atomic orbital zones around the nucleus where a given electron is most likely to be found. This model was able to explain observations of atomic behavior that previous models could not, such as certain structural and spectral patterns of atoms larger than hydrogen. |
Atom | Structure | Structure |
Atom | Subatomic particles | Subatomic particles
Though the word atom originally denoted a particle that cannot be cut into smaller particles, in modern scientific usage the atom is composed of various subatomic particles. The constituent particles of an atom are the electron, the proton, and the neutron.
The electron is the least massive of these particles by four orders of magnitude at , with a negative electrical charge and a size that is too small to be measured using available techniques. It was the lightest particle with a positive rest mass measured, until the discovery of neutrino mass. Under ordinary conditions, electrons are bound to the positively charged nucleus by the attraction created from opposite electric charges. If an atom has more or fewer electrons than its atomic number, then it becomes respectively negatively or positively charged as a whole; a charged atom is called an ion. Electrons have been known since the late 19th century, mostly thanks to J.J. Thomson; see history of subatomic physics for details.
Protons have a positive charge and a mass of . The number of protons in an atom is called its atomic number. Ernest Rutherford (1919) observed that nitrogen under alpha-particle bombardment ejects what appeared to be hydrogen nuclei. By 1920 he had accepted that the hydrogen nucleus is a distinct particle within the atom and named it proton.
Neutrons have no electrical charge and have a mass of .Mohr, P.J.; Taylor, B.N. and Newell, D.B. (2014), "The 2014 CODATA Recommended Values of the Fundamental Physical Constants" (Web Version 7.0). The database was developed by J. Baker, M. Douma, and S. Kotochigova. (2014). National Institute of Standards and Technology, Gaithersburg, Maryland 20899. Neutrons are the heaviest of the three constituent particles, but their mass can be reduced by the nuclear binding energy. Neutrons and protons (collectively known as nucleons) have comparable dimensions—on the order of —although the 'surface' of these particles is not sharply defined. The neutron was discovered in 1932 by the English physicist James Chadwick.
In the Standard Model of physics, electrons are truly elementary particles with no internal structure, whereas protons and neutrons are composite particles composed of elementary particles called quarks. There are two types of quarks in atoms, each having a fractional electric charge. Protons are composed of two up quarks (each with charge +) and one down quark (with a charge of −). Neutrons consist of one up quark and two down quarks. This distinction accounts for the difference in mass and charge between the two particles.
The quarks are held together by the strong interaction (or strong force), which is mediated by gluons. The protons and neutrons, in turn, are held to each other in the nucleus by the nuclear force, which is a residuum of the strong force that has somewhat different range-properties (see the article on the nuclear force for more). The gluon is a member of the family of gauge bosons, which are elementary particles that mediate physical forces. |
Atom | Nucleus | Nucleus
thumb|The binding energy needed for a nucleon to escape the nucleus, for various isotopes
All the bound protons and neutrons in an atom make up a tiny atomic nucleus, and are collectively called nucleons. The radius of a nucleus is approximately equal to femtometres, where is the total number of nucleons. This is much smaller than the radius of the atom, which is on the order of 105 fm. The nucleons are bound together by a short-ranged attractive potential called the residual strong force. At distances smaller than 2.5 fm this force is much more powerful than the electrostatic force that causes positively charged protons to repel each other.
Atoms of the same element have the same number of protons, called the atomic number. Within a single element, the number of neutrons may vary, determining the isotope of that element. The total number of protons and neutrons determine the nuclide. The number of neutrons relative to the protons determines the stability of the nucleus, with certain isotopes undergoing radioactive decay.
The proton, the electron, and the neutron are classified as fermions. Fermions obey the Pauli exclusion principle which prohibits identical fermions, such as multiple protons, from occupying the same quantum state at the same time. Thus, every proton in the nucleus must occupy a quantum state different from all other protons, and the same applies to all neutrons of the nucleus and to all electrons of the electron cloud.
A nucleus that has a different number of protons than neutrons can potentially drop to a lower energy state through a radioactive decay that causes the number of protons and neutrons to more closely match. As a result, atoms with matching numbers of protons and neutrons are more stable against decay, but with increasing atomic number, the mutual repulsion of the protons requires an increasing proportion of neutrons to maintain the stability of the nucleus.
right|thumb|upright|Illustration of a nuclear fusion process that forms a deuterium nucleus, consisting of a proton and a neutron, from two protons. A positron (e+)—an antimatter electron—is emitted along with an electron neutrino.
The number of protons and neutrons in the atomic nucleus can be modified, although this can require very high energies because of the strong force. Nuclear fusion occurs when multiple atomic particles join to form a heavier nucleus, such as through the energetic collision of two nuclei. For example, at the core of the Sun protons require energies of 3 to 10 keV to overcome their mutual repulsion—the coulomb barrier—and fuse together into a single nucleus. Nuclear fission is the opposite process, causing a nucleus to split into two smaller nuclei—usually through radioactive decay. The nucleus can also be modified through bombardment by high energy subatomic particles or photons. If this modifies the number of protons in a nucleus, the atom changes to a different chemical element.
If the mass of the nucleus following a fusion reaction is less than the sum of the masses of the separate particles, then the difference between these two values can be emitted as a type of usable energy (such as a gamma ray, or the kinetic energy of a beta particle), as described by Albert Einstein's mass–energy equivalence formula, E = mc2, where m is the mass loss and c is the speed of light. This deficit is part of the binding energy of the new nucleus, and it is the non-recoverable loss of the energy that causes the fused particles to remain together in a state that requires this energy to separate.
The fusion of two nuclei that create larger nuclei with lower atomic numbers than iron and nickel—a total nucleon number of about 60—is usually an exothermic process that releases more energy than is required to bring them together. It is this energy-releasing process that makes nuclear fusion in stars a self-sustaining reaction. For heavier nuclei, the binding energy per nucleon begins to decrease. That means that a fusion process producing a nucleus that has an atomic number higher than about 26, and a mass number higher than about 60, is an endothermic process. Thus, more massive nuclei cannot undergo an energy-producing fusion reaction that can sustain the hydrostatic equilibrium of a star. |
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