|silvery lustrous gray
|Name, symbol, number||antimony, Sb, 51|
|Group, period, block||15, 5, p|
|Standard atomic weight||121.760(1) g·mol−1|
|Electron configuration||[Kr] 4d10 5s2 5p3|
|Electrons per shell||2, 8, 18, 18, 5 (Image)|
|Density (near r.t.)||6.697 g·cm−3|
|Liquid density at m.p.||6.53 g·cm−3|
|Melting point||903.78 K, 630.63 °C, 1167.13 °F|
|Boiling point||1860 K, 1587 °C, 2889 °F|
|Heat of fusion||19.79 kJ·mol−1|
|Heat of vaporization||193.43 kJ·mol−1|
|Specific heat capacity||(25 °C) 25.23 J·mol−1·K−1|
|Oxidation states||5, 3, -3|
|Electronegativity||2.05 (Pauling scale)|
|1st: 834 kJ·mol−1|
|2nd: 1594.9 kJ·mol−1|
|3rd: 2440 kJ·mol−1|
|Atomic radius||140 pm|
|Covalent radius||139±5 pm|
|Van der Waals radius||206 pm|
|Electrical resistivity||(20 °C) 417 nΩ·m|
|Thermal conductivity||(300 K) 24.4 W·m−1·K−1|
|Thermal expansion||(25 °C) 11 µm·m−1·K−1|
|Speed of sound (thin rod)||(20 °C) 3420 m/s|
|Young's modulus||55 GPa|
|Shear modulus||20 GPa|
|Bulk modulus||42 GPa|
|Brinell hardness||294 MPa|
|CAS registry number||7440-36-0|
|Most stable isotopes|
|Main article: Isotopes of antimony|
Antimony ( // -ti-mo-nee;[note 2] Latin: stibium) is a chemical element with the symbol Sb and an atomic number of 51. A silvery lustrous grey metalloid, it is found in nature mainly as antimony sulfide, commonly known as stibnite. Antimony compounds are principally used as fire retardants, and its alloys are useful. An emerging application is the use of antimony in microelectronics.
Antimony is a soft metal (2 on mohs scale). A coin made of antimony issued in the Keichow Province of China in 1931 was unpopular because the metal was so soft the coins would wear out fast. After the first issue no others were produced. It is resistant to attack by acids.
Four allotropes of antimony are known: a stable metallic form, and three meta-stable forms which are explosive, black and yellow. Metallic antimony is a brittle, silver-white shiny metal. When molten antimony is slowly cooled, metallic antimony crystallizes in an hexagonal cell, isomorphic with that of the black allotrope of arsenic.
A rare explosive form of antimony can be formed from the electrolysis of antimony(III) trichloride. When scratched with a sharp implement, an exothermic reaction occurs and white fumes given off as metallic antimony is formed; alternatively, when rubbed with a pestle in a mortar, a strong detonation occurs. Black antimony is formed when gaseous metallic antimony is rapidly cooled. It oxidies in air and is sometimes spontaneously combustible. At 100 °C, it gradually transforms into the stable form.
The yellow allotrope of antimony is the most unstable. It has only been generated by oxidation of stibine (SbH3) at -90 °C. Above this temperature and in ambient light, this meta stable allotrope transforms into the stabler black allotrope.
Antimony exists as two stable isotopes, one with seventy neutrons, the other with seventy-two.
The abundance of antimony in the Earth's crust is estimated at 0.2 to 0.5 parts per million, comparable to thallium at 0.5 parts per million and silver at 0.07 ppm. Even though this element is not abundant, it is found in over 100 mineral species. Antimony is sometimes found native, but more frequently it is found in the sulfide stibnite (Sb2S3) which is the predominant ore mineral. Commercial forms of antimony are generally ingots, broken pieces, granules, and cast cake. Other forms are powder, shot, and single crystals.
In 2005, China was the top producer of antimony with about 84% world share followed at a distance by South Africa, Bolivia and Tajikistan, reports the British Geological Survey. The mine with the largest deposits in China is Xikuangshan mine in Hunan Province with a estimated deposit of 2.1 million metric tons.
Antimony has no natural role in biology.
The extraction of antimony from ores depends on the quality of the ore, which is usually a sulfide. The suflide is converted to an oxide and advantage is often taken of the volatility of antimony(III) oxide, which is recovered from roasting. This material is often used directly for the main applications, impurities being arsenic and sulfide. Antimony can be isolated from its ore by a reduction with scrap iron:
- Sb2S3 + 3Fe → 2Sb + 3FeS
Isolating antimony from its oxide, is performed by a carbothermal reduction:
- 2Sb2O3 + 3 C → 4 Sb + 3 CO2
|Country||Tonnes||% of total|
|People's Republic of China||126,000||84.0|
Antimony compounds are often classified into those of Sb(III) and Sb(V). Relative to its neighboring elements As, the 5+ oxidaton state is more oxidizing.
Oxides and hydroxides
Antimony trioxide (Sb4O6) is formed when antimony is burnt in an excess of air. In the gas phase, this compound exists as Sb4O6, but polymerises as a solid. Antimony pentoxide, (Sb4O10) can only be formed by oxidation by concentrated nitric acid. Antimony also forms a mixed-valence oxide, antimony tetroxide (Sb2O4), which features both Sb(III) and Sb(V). Unlike phosphorus and arsenic, these various oxides are amphoteric and do not form well-defined oxoacids and react with acids to form antimony salts.
Antimonous acid Sb(OH)3 is unstable with respect to olation to the oxide. Its conjugate base sodium antimonite ([Na3SbO3]4) forms upon fusing sodium oxide and Sb4O6.:763 Transition metal antimonites are best described as mixed metal oxides.:122 Antimonic acid exists only as the hydrate HSb(OH)6, forming salts containing the antimonate anion Sb(OH)−6. Dehydrating metal salts containing this anion yields mixed oxides.:143
Many antimony ores are sulfides, including stibnite (Sb2S3), pyrargyrite (Ag3SbS3), zinkenite, jamesonite, and boulangerite.:757 Antimony pentasulfide is known, but is non-stoichiometric and contains only antimony in the +3 oxidation state. Several thioantimonides are known such as [Sb6S10]2− and [Sb8S13]2−.
Antimony forms two series of halides: SbX3 and SbX5, where X is one of the halogens. The trihalides SbF3, SbCl3, SbBr3, and SbI3 are all molecular compounds having trigonal pyramidal molecular geometry. The trifluoride SbF3 is prepared by the reaction of Sb2O3 with HF::761-762
- Sb2O3 + HF → 2 SbF3 + 3 H2O
It is Lewis acidic and readily accepts fluoride ions to form the complex anions SbF−4 and SbF2−5. Molten SbF3 is a weak electrical conductor. The trichloride SbCl3 is prepared by dissolving Sb2S3 in hydrochloric acid:
- Sb2S3 + HCl → 2 SbCl3 + 3 H2S
The pentahalides SbF5 and SbCl5 have trigonal bipyramidal molecular geometry in the gas phase, but in the liquid phase, SbF5 is polymeric, whereas SbCl5 is monomeric.:761 SbF5 is a powerful Lewis acid used to make the superacid fluoroantimonic acid ("HSbF6").
Oxyhalides are common for antimony than arsenic and phosphorus. Antimony trioxide dissolves in concentrated acid to form antimony oxo- (antimonyl) compounds such as SbOCl and (SbO)2SO4.:764
Hydride and organic derivatives
Organoantimony compounds are typically prepared by alkylation of antimony halides with Grignard reagents. 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 Sb(C6H5)3 (triphenylstibine), Sb2(C6H5)4 (with an Sb-Sb bond), and cyclic [Sb(C6H5)]n. Pentacoordinated organoantimony compounds are common, an examples being Sb(C6H5)5 and several related halides.
- Sb3− + 3 H+ → SbH3
Stibine can also be produced by treating Sb3+ salts with hydride reagents. Antimony does not react with hydrogen directly to form stibine.
An artifact made of antimony dating to about 3000 BC was found at Tello, 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. One contemporary commented, "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' must represent the lost art of rendering antimony malleable."Moorey, P. R. S. (1994). Paracelsus von Hohenheim (of whom Thölde was one), came to associate the practice of alchemy with the preparation of chemical medicines.
Pure antimony was well known to Jābir ibn Hayyān, sometimes called "the Father of Chemistry", in the 8th century. Here there is still an open controversy: Marcellin Berthelot, who translated a number of Jābir's books, stated that antimony is never mentioned in them, but other authors[who?] claim that Berthelot translated only some of the less important books, while the more interesting ones (some of which might describe antimony) are not yet translated, and their content is completely unknown.
The ancient words for antimony mostly have, as their chief meaning, kohl, the sulfide of antimony. Pliny the Elder, however, distinguishes between male and female forms of antimony; his male form is probably the sulfide, while the female form, which is superior, heavier, and less friable, is probably native metallic antimony.
The Egyptians called antimony mśdmt; in hieroglyphics, the vowels are uncertain, but there is an Arabic tradition that the word is ميسديميت mesdemet. The Greek word, στίμμι stimmi, is probably a loan word from Arabic or Egyptian sdm
, and is used by the Attic tragic poets of the 5th century BC; later Greeks also used στἰβι stibi, as did Celsus and Pliny, writing in Latin, in the first century AD. Pliny also gives the names stimi [sic], larbaris, alabaster, and the "very common" platyophthalmos, "wide-eye" (from the effect of the cosmetic). Later Latin authors adapted the word to Latin as stibium. The Arabic word for the substance, as opposed to the cosmetic, can appear as تحميض، ثمود، وثمود، وثمود ithmid, athmoud, othmod, or uthmod. Littré suggests the first form, which is the earliest, derives from stimmida, (one) accusative for stimmi.
The use of Sb as the standard chemical symbol for antimony is due to the 18th century chemical pioneer, Jöns Jakob Berzelius, who used this abbreviation of the name stibium. The medieval Latin form, from which the modern languages and late Byzantine Greek, take their names, is antimonium. The origin of this is uncertain; all suggestions have some difficulty either of form or interpretation. The popular etymology, from ἀντίμοναχός anti-monachos or French antimoine, still has adherents; this would mean "monk-killer", and is explained by many early alchemists being monks, and antimony being poisonous.[note 3] So does the hypothetical Greek word ἀντίμόνος antimonos, "against one", explained as "not found as metal", or "not found unalloyed". Lippmann conjectured a Greek word, ανθήμόνιον anthemonion, which would mean "floret", and he cites several examples of related Greek words (but not that one) which describe chemical or biological efflorescence.
The early uses of antimonium include the translations, in 1050-1100, by Constantine the African of Arabic medical treatises. Several authorities believe that antimonium is a scribal corruption of some Arabic form; Meyerhof derives it from ithmid; other possibilities include Athimar, the Arabic name of the metal, and a hypothetical *as-stimmi, derived from or parallel to the Greek.
The main use of antimony is in the form of antimony trioxide is used in the making of flame-proofing compounds. Markets for these flame-retardant applications include children's clothing, toys, aircraft and automobile seat covers. It is also used in the fiberglass composites industry as an additive to polyester resins for such items as light aircraft engine covers. The resin will burn while a flame is held to it but will extinguish itself as soon as the flame is removed.Fireproofing consumes about half of the annual production.
Antimony forms a highly useful alloy with lead, increasing its hardness and mechanical strength. The Sb-Pb alloy is use in lead-acid batteries. It is used in antifriction alloys, such as Babbit metal.. It is used as an alloy in small arms ammunition, buckshot, tracer ammunition, cable sheathing, type metal (e.g. 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.
In tiny amounts, antimony is increasingly being used in the semiconductor industry as a dopant for ultra-high conductivity n-type silicon wafers in the production of diodes, infrared detectors, and Hall-effect devices.
Few biological or medical applications exist for antimony. Treatments principally containing are known as antimonials and are used as emetics.
Antimony has a nourishing or conditioning effect on keratinized tissues, at least in animals. Antimony-based drugs, such as meglumine antimoniate, are also considered the drugs of choice for treatment of leishmaniasis in domestic animals. Unfortunately, as well as having low therapeutic indices, the drugs are poor at penetrating the bone marrow, where some of the Leishmania amastigotes reside, and so cure of the disease – especially the visceral form – is very difficult.
Elemental antimony as an antimony pill was once used as a medicine. It could be reused by others after ingestion.
Antimony and many of its compounds are toxic, and the effects of antimony poisoning are similar to arsenic poisoning. 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; otherwise it can damage the kidneys and the liver, causing violent and frequent vomiting, and will lead to death in a few days.
Antimony is incompatible with strong oxidizing agents, strong acids, halogen acids, chlorine, or fluorine. Keep away from heat.
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/L
- United States Environmental Protection Agency, Health Canada and the Ontario Ministry of Environment: 6 µg/L
- German Federal Ministry of Environment: 5 µg/L
- ^ In the UK, the variable vowel /ɵ/ is usually pronounced as a schwa [ə]; in the US, it is generally a full [oʊ].
- ^ In the UK, the variable vowel /ɵ/ is usually pronounced as a schwa [ə]; in the US, it is generally a full [oʊ].
- ^ The use of a symbol resembling an upside down "female" symbol for antimony could also hint at a satirical pun in this origin
- ^ Magnetic susceptibility of the elements and inorganic compounds, in Handbook of Chemistry and Physics 81st edition, CRC press.
- ^ "Metals Used in Coins and Medals". ukcoinpics.co.uk. http://www.ukcoinpics.co.uk/metal.html.
- ^ Wang, Chung Wu (1919). "The Chemistry of Antimony". Antimony: Its History, Chemistry, Minerology, Geology, Metallurgy, Uses, Preparation, Analysis, Production and Valuation with Complete Bibliographies. London, United Kingdom: Charles Geiffin and Co. Ltd. pp. 6–33. http://library.sciencemadness.org/library/books/antimony.pdf.
- ^ "Antimony Statistics and Information". United States Geological Survey. http://minerals.usgs.gov/minerals/pubs/commodity/antimony/.
- ^ Peng, J (2003). "Samarium–neodymium isotope systematics of hydrothermal calcites from the Xikuangshan antimony deposit (Hunan, China): the potential of calcite as a geochronometer". Chemical Geology 200: 129. doi:10.1016/S0009-2541(03)00187-6.
- ^ a b c Sabina C. Grund, Kunibert Hanusch, Hans J. Breunig, Hans Uwe Wolf “Antimony and Antimony Compounds” in Ullmann's Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi: 10.1002/14356007.a03_055.pub2
- ^ a b Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.
- ^ Daniel L. Reger; Scott R. Goode; David W. Ball (2009). Chemistry: Principles and Practice (3rd ed.). Cengage Learning. p. 883.
- ^ a b c d e f g Wiberg, Egon; Wiberg, Nils and Holleman, Arnold Frederick (2001). Inorganic chemistry. Academic Press.
- ^ a b James E. House (2008). Inorganic chemistry. Academic Press. p. 502.
- ^ a b S. M. Godfrey; C. A. McAuliffe; A. G. Mackie; R. G. Pritchard (1998). Nicholas C. Norman. ed. Chemistry of arsenic, antimony, and bismuth. Springer. ISBN 075140389X.
- ^ Long, G (1969). "The oxidation number of antimony in antimony pentasulfide". Inorganic and Nuclear Chemistry Letters 5: 21. doi:10.1016/0020-1650(69)80231-X.
- ^ Lees, R; Powell, A; Chippindale, A (2007). "The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes". Journal of Physics and Chemistry of Solids 68: 1215. doi:10.1016/j.jpcs.2006.12.010.
- ^ Louis Kahlenberg (2008). Outlines of Chemistry – A Textbook for College Students. READ BOOKS. pp. 324–325. ISBN 140976995X.
- ^ a b Kirk-Othmer Encyclopedia of Chemical Technology, 5th ed. 2004. Entry for antimony.
- ^ Already in 1710 Wilhelm Gottlob Freiherr von Leibniz, after careful inquiry, concluded that the work was spurious, that there was no monk named Basilius Valentinus, and the book's author was its ostensible editor, Johann
- ^ s.v. "Basilius Valentinus." Harold Jantz was perhaps the only modern scholar to deny Thölde's authorship, but he too agrees that the work dates from after 1550: see his catalogue of German Baroque literature.
- ^ Dampier, William Cecil (1961). A history of science and its relations with philosophy & religion.. London: Cambridge U.P.. p. 73. ISBN 9780521093668. http://books.google.com/?id=6kM4AAAAIAAJ&pg=PA73.
- ^ "Native antimony". Mindat.org. http://www.mindat.org/min-262.html.
- ^ Pliny, Natural history, 33.33; W.H.S. Jones, the Loeb Classical Library translator, supplies a note suggesting the identifications.
- ^ Albright, W. F. (1918). "Notes on Egypto-Semitic Etymology. II". The American Journal of Semitic Languages and Literatures 34 (4): 230. http://links.jstor.org/sici?sici=1062-0516%28191807%2934%3A4%3C215%3ANOEEI%3E2.0.CO%3B2-J.
- ^ Sarton, George (1935). "Review of Al-morchid fi'l-kohhl, ou Le guide d'oculistique, translated by Max Meyerhof" (in French). Isis 22 (2): 541. http://links.jstor.org/sici?sici=0021-1753%28193502%2922%3A2%3C539%3A%28FOLGD%3E2.0.CO%3B2-L. quotes Meyerhof, the translator of the book he is reviewing.
- ^ LSJ, s.v., vocalisation, spelling, and declension vary; Endlich, p.28; Celsus, 6.6.6 ff; Pliny Natural History 33.33; Lewis and Short: Latin Dictionary. OED, s. "antimony".
- ^ Fernando, Diana (1998). Alchemy : an illustrated A to Z. Blandford. Fernando even derives it from the story of how "Basil Valentine" and his fellow monastic alchemists poisoned themselves by working with antimony; antimonium is found two centuries before his time. "Popular etymology" from OED; as for antimonos, the pure negative would be more naturally expressed by a- "not".
- ^ Lippman, p.643-5
- ^ Lippman, p.642, writing in 1919, says "zuerst".
- ^ Meyerhof as quoted in Sarton, asserts that ithmid or athmoud became corrupted in the medieval "traductions barbaro-latines".; the OED asserts that some Arabic form is the origin, and if ithmid is the root, posits athimodium, atimodium, atimonium, as intermediate forms.
- ^ Endlich, p.28; one of the advantages of as-stimmi would be that it has a whole syllable in common with antimonium.
- ^ Kiehne, Heinz Albert (2003). "Types of Alloys". Battery technology handbook. CRC Press. pp. 60–61. ISBN 9780824742492. http://books.google.com/?id=1HSsx9fPAKkC&pg=PA60.
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- ^ Hull, Charles (1992). Pewter. Osprey Publishing. pp. 1–5. ISBN 9780747801528. http://books.google.com/?id=3_zyycVRw18C.
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- ^ National Research Council (1970). Trends in usage of antimony: report. National Academies. p. 50. http://books.google.com/?id=TyQrAAAAYAAJ&pg=PA50.
- ^ MSDS, Baker
- ^ "Antimony leaching from polyethylene terephthalate (PET) plastic used for bottled drinking water:". National Center for Biotechnology Information, U.S. National Library of Medicine. http://www.ncbi.nlm.nih.gov/pubmed/17707454.
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- ^ "London Free Press:". Lfpress.com. http://www.lfpress.com/cgi-bin/publish.cgi?p=120232&x.
- ^ Hansen, Claus; Tsirigotaki, Alexandra; Bak, Søren Alex; Pergantis, Spiros A.; Stürup, Stefan; Gammelgaard, Bente; Hansen, Helle Rüsz (17 February 2010). "Elevated antimony concentrations in commercial juices". Journal of Environmental Monitoring 12 (4): 822. doi:10.1039/b926551a. PMID 20383361. http://www.rsc.org/Publishing/Journals/EM/article.asp?doi=b926551a.
- ^ Borland, Sophie (1. March 2010). "Fruit juice cancer warning as scientists find harmful chemical in 16 drinks". Daily Mail. http://www.dailymail.co.uk/news/article-1254534/Fruit-juice-cancer-warning-scientists-harmful-chemical-16-drinks.html.
- ^ Wakayama, Hiroshi, "Revision of Drinking Water Standards in Japan", Ministry of Health, Labor and Welfare (Japan), 2003; Table 2, p. 84
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- Edmund Oscar von Lippmann (1919) Entstehung und Ausbreitung der Alchemie, teil 1. Berlin: Julius Springer. In German.
- Public Health Statement for Antimony
- National Pollutant Inventory – Antimony and compounds
- WebElements.com – Antimony
- Chemistry in its element podcast (MP3) from the Royal Society of Chemistry's Chemistry World: Antimony