Antimony (pronounced /ˈæntɨmɵnɪ/ AN-ti-mo-nee)[note 1] is a chemical element with the symbol Sb (Latin: stibium) and atomic number 51. A metalloid, antimony has four allotropic forms. The stable form of antimony is a blue-white metalloid. Yellow and black antimony are unstable non-metals. Antimony is used in electronics and flame-proofing, in paints, rubber, ceramics, enamels, drugs to treat Leishmania infection and a wide variety of alloys.

Etymology

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, the female form, which is superior, heavier, and less friable, is probably native metallic antimony.[2]

The Egyptians called antimony mśdmt; in hieroglyphics, the vowels are uncertain, but there is an Arabic tradition that the word is ميسديميت mesdemet.[3][4] 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.[5]

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 2] So does the hypothetical Greek word ἀντίμόνος antimonos, "against one", explained as "not found as metal", or "not found unalloyed".[6][7] 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.[8]

The early uses of antimonium include the translations, in 1050-1100, by Constantine the African of Arabic medical treatises.[9] Several authorities believe that antimonium is a scribal corruption of some Arabic form; Meyerhof derives it from ithmid;[10] other possibilities include Athimar, the Arabic name of the metal, and a hypothetical *as-stimmi, derived from or parallel to the Greek.[11]

Properties

Antimony in its elemental form is a silvery white, brittle, fusible, crystalline solid that exhibits poor electrical and heat conductivity properties and vaporizes at low temperatures. A metalloid, antimony resembles a metal in its appearance and in many of its physical properties, but does not chemically react as a metal. It is reactive with oxidizing acids and halogens. Antimony and some of its alloys are unusual in that they expand on cooling. Antimony is geochemically categorized as a chalcophile, occurring with sulfur and the heavy metals lead, copper, and silver.

The abundance of antimony in the Earth's crust is estimated at 0.2 to 0.5 parts per million.[12]

Applications

Antimony is increasingly being used in the semiconductor industry in the production of diodes, infrared detectors, and Hall-effect devices. As an alloy, this metalloid greatly increases lead's hardness and mechanical strength. The most important use of antimony is as a hardener in lead for lead-acid batteries.[13] Uses include

* antifriction alloys, such as Babbit metal[14]
* small arms, buckshot, and tracer ammunition
* cable sheathing
* matches[15]
* medications such as antiprotozoan drugs
* HF pH electrode construction
* plumbing
* soldering - some "lead-free" solders contain 5% Sb[16]
* used in the past to treat Schistosomiasis; today Praziquantel is universally used
* used in type metal, e.g. for linotype printing machines[17]
* used in pewter[18]
* used to harden alloys with low tin content in the manufacturing of organ pipes
* as a dopant for ultra-high conductivity n-type silicon wafers[19]
* in nuclear reactors together with beryllium in startup neutron sources

Antimony compounds in the form of oxides, sulfides, sodium antimonate, and antimony trichloride are used in the making of flame-proofing compounds, ceramic enamels, glass, paints, and pottery. Antimony trioxide is the most important of the antimony compounds and is primarily used in flame-retardant formulations. These flame-retardant applications include such markets as 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. Antimony sulfide is also one of the ingredients of safety matches.

In the 1950s, tiny beads of a lead-antimony alloy were used to dope the emitters and collectors of NPN alloy junction transistors with antimony.[20]

The natural sulfide of antimony, stibnite, was known and used in Biblical times, as a medication and in Islamic/Pre-Islamic times as a cosmetic. The Sunan Abi Dawood reports, “Muhammad said: 'Among the best types of collyrium is antimony (ithmid) for it clears the vision and makes the hair sprout.'”[21]

Stibnite is still used in some developing countries as a medication. Antimony has been used for the treatment of schistosomiasis. Antimony attaches itself to sulfur atoms in certain enzymes which are used by both the parasite and human host. Small doses can kill the parasite without causing damage to the patient. Antimony and its compounds are used in several veterinary preparations like Anthiomaline or Lithium antimony thiomalate, which is used as a skin conditioner in ruminants. Antimony has a nourishing or conditioning effect on keratinized tissues, at least in animals. Tartar emetic is another antimony preparation which is used as an anti-schistosomal drug. Treatments chiefly involving antimony have been called antimonials.

Antimony-based drugs such as meglumine antimoniate, is also considered the drugs of choice for the 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.

History
An unshaded circle surmounted by a cross.
One of the alchemical symbols for antimony
An irregular piece of silvery stone with spots of variation in lustre and shade.
Native massive antimony with oxidation products

Antimony's sulfide compound, antimony(III) sulfide, Sb2S3 was recognized in antiquity, at least as early as 3000 BC. Pastes of Sb2S3 powder in fat[23] or in other materials have been used since that date as eye cosmetics in the Middle East and farther afield; in this use, Sb2S3 is called kohl. It was used to darken the brows and lashes, or to draw a line around the perimeter of the eye.

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.[7] There is some uncertainty as to the description of the artifact from Tello. Although it is sometimes reported to be a vase, a recent detailed discussion reports it to be rather a fragment of indeterminate purpose.[24] The first European description of a procedure for isolating antimony is in the book De la pirotechnia of 1540 by Vannoccio Biringuccio, written in Italian. This book precedes the more famous 1556 book in Latin by Agricola, De re metallica, even though Agricola has been often incorrectly credited with the discovery of metallic antimony. A text describing the preparation of metallic antimony that was published in Germany in 1604 purported to date from the early fifteenth century, and if authentic it would predate Biringuccio. The book, written in Latin, was called "Currus Triumphalis Antimonii" (The Triumphal Chariot of Antimony), and its putative author was a certain Benedictine monk, writing under the name Basilius Valentinus. 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 Thölde (ca. 1565-ca. 1624). There is now agreement among professional historians that the Currus Triumphalis... was written after the middle of the sixteenth century and that Thölde was likely its author.[23][25] An English translation of the "Currus Triumphalis" appeared in English in 1660, under the title The Triumphant Chariot of Antimony. The work remains of great interest, chiefly because it documents how followers of the renegade German physician, Philippus Theophrastus Paracelsus von Hohenheim (of whom Thölde was one), came to associate the practice of alchemy with the preparation of chemical medicines.

According to the traditional history of Middle Eastern alchemy, 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?][26] 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 first natural occurrence of pure antimony ('native 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 Silvermine in the Bergslagen mining district of Sala, Västmanland, Sweden.[27]

Production
See also: Category:Antimonide minerals and Category:Antimonate minerals
Antimony output in 2005
World production trend of antimony

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 deposites in China is Xikuangshan mine in Hunan Province with a estimated deposit of 2.1 million metric tons.[28]
Country Tonnes % of total
People's Republic of China 126,000 84.0
South Africa 6,000 4.0
Bolivia 5,225 3.5
Tajikistan 4,073 2.7
Russia 3,000 2.0
Top 5 144,298 96.2
Total world 150,000 100.0

Chiffres de 2003, métal contenue dans les minerais et concentrés, source: L'état du monde 2005 (French)

Precautions
See also: Arsenic poisoning

Antimony and many of its compounds are toxic. Clinically, antimony poisoning is very similar to arsenic poisoning. In small doses, antimony causes headache, dizziness, and depression. Larger doses cause violent and frequent vomiting, and will lead to death in a few days.

Antimony leaches from polyethylene terephthalate (PET) bottles into liquids. While levels observed for bottled water are below drinking water guidelines,[29][30] 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.[31][32] The guidelines are:

* World Health Organization: 20 µg/L
* Japan: 15 µg/L[33]
* United States Environmental Protection Agency, Health Canada and the Ontario Ministry of Environment: 6 µg/L
* German Federal Ministry of Environment: 5 µg/L[29]

Chemistry
See also: Category:Antimony compounds

Chalcogen compounds

Many antimony ores are sulfides, including stibnite (Sb2S3), pyrargyrite (Ag3SbS3), zinkenite, jamesonite, and boulangerite.[34]:757 Antimony pentasulfide is known, but is non-stoichiometric and contains only antimony in the +3 oxidation state.[35] Several complex anions of antimony and sulfur are known, such as [Sb6S10]2− and [Sb8S13]2−.[36]

Antimony trioxide is produced by burning elemental antimony in excess air:[37]

4 Sb + 3 O₂ → Sb₄O₆

It exists as Sb4O6 molecules in the gas phase. These molecules are also present in the cubic form of the solid phase, but the rhombic form is polymeric: [Sb2O3]x.[34]

The pentoxide Sb4O10 is not formed directly from burning antimony; it requires oxidation by concentrated nitric acid:[38]

4 Sb + 20 HNO₃ → Sb₄O₁₀ + 20 NO₂ + 10 H₂O

Antimony also forms a mixed-valence oxide, Sb₂SO₄, where antimony is present in both the +3 and +5 oxidation states.[38]

Unlike phosphorus and arsenic, the various antimony oxides do not form well-defined oxoacids. The hypothetical antimonous acid Sb(OH)3 only exists as its salts,[34]:763 such as sodium antimonite ([Na₃SbO₃]₄), formed by fusing sodium oxide and Sb₄O₆. Transition metal antimonites are best described as mixed metal oxides.[39]: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.[39]:143

On the other hand, the antimony oxides are amphoteric, and react with acid to form antimony salts. Antimony trioxide dissolves in concentrated acid to form antimony oxo- (antimonyl) compounds such as SbOCl and (SbO)₂SO₄.[34]:764

Halogen compounds

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:[34]:761-762

Sb₂O₃ + HF → 2 SbF₃ + 3 H₂O

It is a strong Lewis acid that 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.[34]:761 SbF₅ is a powerful Lewis acid used to make the superacid fluoroantimonic acid (HSbF₆), and is an important solvent used in the study of noble gas compounds.

Antimonides

Antimony forms antimonides with metals, such as indium antimonide (InSb), and silver antimonide (Ag₃Sb).[34]:760 Treating antimonides with acid produces the unstable toxic gas stibine, SbH₃:[40]

Sb³⁻ + 3 H⁺ → SbH₃

Stibine may also be produced by reacting Sb3+ salts with sources of the hydride ion H−. Antimony does not react with hydrogen directly to form stibine.[41]

See also

* Antimonial
* Antimony pill
* Phase change memory
* Naturalis Historia
* Pliny the Elder

Notes

1. ^ In the UK, the variable vowel /ɵ/ is usually pronounced as a schwa [ə]; in the US, it is generally a full [oʊ].
2. ^ The use of a symbol resembling an upside down "female" symbol for antimony could also hint at a satirical pun in this origin

References

1. ^ Magnetic susceptibility of the elements and inorganic compounds, in Handbook of Chemistry and Physics 81st edition, CRC press.
2. ^ Pliny, Natural history, 33.33; W.H.S. Jones, the Loeb Classical Library translator, supplies a note suggesting the identifications.
3. ^ 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.
4. ^ 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.
5. ^ 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".
6. ^ Diana Fernando, Alchemy : an illustrated A to Z (1998). 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".
7. ^ a b Kirk-Othmer Encyclopedia of Chemical Technology, 5th ed. 2004. Entry for antimony.
8. ^ Lippman, p.643-5
9. ^ Lippman, p.642, writing in 1919, says "zuerst".
10. ^ 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.
11. ^ Endlich, p.28; one of the advantages of as-stimmi would be that it has a whole syllable in common with antimonium.
12. ^ "Antimony Statistics and Information". United States Geological Survey. 2009-01-31. http://minerals.usgs.gov/minerals/pubs/commodity/antimony/. Retrieved 2009-04-15.
13. ^ Kiehne, Heinz Albert (2003). "Types of Alloys". Battery technology handbook. CRC Press. pp. 60–61. ISBN 9780824742492. http://books.google.com/books?id=1HSsx9fPAKkC&pg=PA60.
14. ^ Williams, Robert S. (2007). Principles of Metallography. Read books. pp. 46–47. ISBN 9781406746716. http://books.google.com/books?id=KR82QRlAgUwC&pg=PA46.
15. ^ National Research Council (1970). Trends in usage of antimony: report. National Academies. p. 50. http://books.google.com/books?id=TyQrAAAAYAAJ&pg=PA50.
16. ^ Ipser, H.; Flandorfer, H.; Luef, Ch.; Schmetterer, C.; Saeed, U. (2007). "Thermodynamics and phase diagrams of lead-free solder materials". Journal of Materials Science: Materials in Electronics 18: 3–17. doi:10.1007/s10854-006-9009-3.
17. ^ Holmyard, E. J. (2008). Inorganic Chemistry - A Textbooks for Colleges and Schools. pp. 399–400. ISBN 9781443722537. http://books.google.de/books?id=IYZezyEvZ78C&pg=PA399.
18. ^ Hull, Charles (1992). Pewter. Osprey Publishing. pp. 1–5. ISBN 9780747801528. http://books.google.com/books?id=3_zyycVRw18C.
19. ^ O'Mara, William C.; Herring, Robert B.; Hunt, Lee Philip (1990). Handbook of semiconductor silicon technology. William Andrew. p. 473. ISBN 0815512376. http://books.google.com/books?id=COcVgAtqeKkC&pg=PA473.
20. ^ Maiti,, C. K. (2008). Selected Works of Professor Herbert Kroemer. World Scientific, 2008. p. 101. ISBN 9812709010. http://books.google.com/books?id=_7fOlKRDcCkC&pg=PA101.
21. ^ Sunan Abu-Dawud (Ahmad Hasan translation). Book 32, Number 4050. http://www.muslimaccess.com/sunnah/hadeeth/abudawud/032.html.
22. ^ "Metals Used in Coins and Medals". ukcoinpics.co.uk. http://www.ukcoinpics.co.uk/metal.html. Retrieved 2009-10-16.
23. ^ a b Priesner, Claus and Figala, Karin, ed (1998) (in German). Alchemie. Lexikon einer hermetischen Wissenschaft. München: C.H. Beck.
24. ^ The fragment was presented in a lecture in 1892. 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). Ancient Mesopotamian Materials and Industries: the Archaeological Evidence. New York: Clarendon Press. p. 241. http://books.google.de/books?id=P_Ixuott4doC&pg=PA241.
25. ^ 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.
26. ^ the late William Cecil Dampier. (1961). A history of science and its relations with philosophy & religion.. London: Cambridge U.P.. p. 73. ISBN 9780521093668. http://books.google.de/books?id=6kM4AAAAIAAJ&pg=PA73.
27. ^ "Native antimony". Mindat.org. http://www.mindat.org/min-262.html. Retrieved 2010-01-25.
28. ^ 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.
29. ^ a b Shotyk, W.; Krachler, M.; Chen, B. (2006). "Contamination of Canadian and European bottled waters with antimony from PET containers.". Journal of environmental monitoring : JEM 8 (2): 288–92. doi:10.1039/b517844b. ISSN 1464-0325. PMID 16470261.
30. ^ "London Free Press:". Lfpress.com. http://www.lfpress.com/cgi-bin/publish.cgi?p=120232&x. Retrieved 2008-09-12.
31. ^ Hansen, Claus (17. February 2010). "Elevated antimony concentrations in commercial juices". Journal of Environmental Monitoring. http://www.rsc.org/Publishing/Journals/EM/article.asp?doi=b926551a. Retrieved 2010-03-01.
32. ^ 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. Retrieved 2010-03-01.
33. ^ Wakayama, Hiroshi, "Revision of Drinking Water Standards in Japan", Ministry of Health, Labor and Welfare (Japan), 2003; Table 2, p. 84
34. ^ a b c d e f g Egon Wiberg; Nils Wiberg; Arnold Frederick Holleman (2001). Inorganic chemistry. Academic Press. ISBN 0123526515.
35. ^ G. G. Long; J. G. Stevens; L. H. Bowen; S. L. Ruby (1969). "The oxidation number of antimony in antimony pentasulfide". Inorganic and Nuclear Chemistry Letters 5 (1): 21-25. doi:10.1016/0020-1650(69)80231-X. edit
36. ^ Rachel J.E. Lees; Anthony V. Powell; Ann M. Chippindale (2007). "The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes". Journal of Physics and Chemistry of Solids 68 (5): 1215-1219. doi:10.1016/j.jpcs.2006.12.010. edit
37. ^ Daniel L. Reger; Scott R. Goode; David W. Ball (2009). Chemistry: Principles and Practice (3rd ed.). Cengage Learning. p. 883. ISBN 0534420125.
38. ^ a b James E. House (2008). Inorganic chemistry. Academic Press. p. 502. ISBN 0123567866.
39. ^ 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.
40. ^ Louis Kahlenberg (2008). Outlines of Chemistry - A Textbook for College Students. READ BOOKS. pp. 324-325. ISBN 140976995X.
41. ^ Amit Arora (2005). Text Book Of Inorganic Chemistry. Discovery Publishing House. p. 530. ISBN 818356013X.

Bibliography

* Endlich, F.M. (1888). "On Some Interesting Derivations of Mineral Names". The American Naturalist 22 (253): 28. http://links.jstor.org/sici?sici=0003-0147%28188801%2922%3A253%3C21%3AOSIDOM%3E2.0.CO%3B2-W.
* Edmund Oscar von Lippmann (1919) Entstehung und Ausbreitung der Alchemie, teil 1. Berlin: Julius Springer. In German.
* Public Health Statement for Antimony

External links

* 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