antimony


from Wikipedia, the free encyclopedia
properties
General
Name , symbol , atomic number Antimony, Sb, 51
Element category Semi-metals
Group , period , block 15 , 5 , p
Appearance shiny silver gray
CAS number 7440-36-0
EC number 231-146-5
ECHA InfoCard 100.028.314
Mass fraction of the earth's envelope 0.65 ppm
Atomic
Atomic mass 121.760 (1) u
Atomic radius (calculated) 145 (133) pm
Covalent radius 139 pm
Van der Waals radius 206 pm
Electron configuration [ Kr ] 4 d 10 5 s 2 5 p 3
1. Ionization energy 8th.608 389 (12) eV 830.58 kJ / mol
2. Ionization energy 16.626 (25) eV1 604.2 kJ / mol
3. Ionization energy 25th.3235 eV2 443.35 kJ / mol
4. Ionization energy 43.804 (25) eV4 226.4 kJ / mol
5. Ionization energy 55.00 (10) eV5 307 kJ / mol
Physically
Physical state firmly
Crystal structure trigonal
density 6.697 g / cm 3
Mohs hardness 3.0
magnetism diamagnetic ( Χ m = −6.8 10 −5 )
Melting point 903.78 K (630.63 ° C)
boiling point 1908 K (1635 ° C)
Molar volume 18.19 · 10 −6 m 3 · mol −1
Heat of evaporation 193 kJ / mol
Heat of fusion 19.7 kJ mol −1
Electric conductivity 2.5 · 10 6 A · V −1 · m −1
Thermal conductivity 24 W m −1 K −1
Chemically
Oxidation states −3, 3 , 5
Normal potential 0.150  V (Sb 3+ + 3 e - → Sb)
Electronegativity 2.05 ( Pauling scale )
Isotopes
isotope NH t 1/2 ZA ZE (M eV ) ZP
119 Sb {syn.} 38.19 h ε 0.594 119 Sn
120 Sb {syn.} 5.76 d ε 2,681 120 Sn
121 Sb 57.36  % Stable
122 Sb {syn.} 2.7238 d β - 1,979 122 te
ε 1.620 122 Sn
123 Sb 42.64% Stable
124 Sb {syn.} 60.20 d β - 2.905 124 te
125 Sb {syn.} 2.7582 a β - 0.767 125 te
For other isotopes see list of isotopes
safety instructions
GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
07 - Warning

Caution

H and P phrases H: 351
P: 202-281-308 + 313-405
MAK

Switzerland: 0.5 mg m −3 (measured as inhalable dust )

As far as possible and customary, SI units are used.
Unless otherwise noted, the data given apply to standard conditions .

Antimon [ antiˈmoːn ] (from Latin antimonium , probably from Arabic "al-ithmîd (un)" ( ithmid  /إثمد / Iṯmid , antimony sulfide or Stibnit )) is a chemical element with the element symbol Sb (from latin S ti b ium , (Gray) antimony ') and the ordinal number 51. In the periodic table it is in the 5th period and the fifth Main group , or 15th  IUPAC group or nitrogen group . In the stable modification it is a shiny silver and brittle semimetal .

Name, story

It is also believed that the name goes back to the late Greek anthemon (dt. Flower ). This was to describe the stem-like crystals of antimony sulfide (Sb 2 S 3 ), which appeared tufted and looked like a flower. In the 11th century, the Latin term for the mineral medicinal drug antimonium for the internal therapy of diseases is found in Constantinus Africanus .

In the 17th century the name antimony was used as a name for the metal. The Coptic name for the make-up powder antimony sulfide went over from the Greek to the Latin stibium . The abbreviation Sb used by the Swedish physician and chemist Jöns Jakob Berzelius ("father of modern chemistry") is still used today as an element symbol .

A late legendary folk etymology , immortalized in his dictionary by Samuel Johnson , says that the German monk Basilius Valentinus made the observation that pigs became fat quickly from ingesting antimony. He also tried this out on his friars, whereupon they died, so that the term "antimoine" ( anti-monkish ) was coined, from which "antimony" later emerged.

The silver mine in the Swedish municipality of Sala in Västmanland is considered the type locality for solid antimony . However, metallic antimony was already known to the Chinese and Babylonians . Some of its compounds were already used in the Bronze Age as an additive to copper in order to produce bronze (finds from Velem-St. Vid in Hungary).

Occurrence

Solid antimony with well-developed, shiny crystal surfaces and cracks

Antimony is a rare element. Since it is also in the nature solid (ie in elemental form) can be found, it is by the International Mineralogical Association (IMA) under the system no. 1.CA.05 recognized as a mineral .

So far (as of 2011), solid antimony has been found at around 300 sites worldwide. For example in several regions of Australia ; in the Bolivian departments of La Paz and Potosí ; Minas Gerais in Brazil; Black Forest , Fichtel Mountains , Upper Palatinate Forest , Odenwald and in the Harz Mountains in Germany; Seinäjoki in Finland; several regions of France ; Lombardy , Piedmont , Sardinia and Trentino-South Tyrol in Italy; some regions of Canada ; some regions of Austria ; East and West Siberia and the Urals in Russia; in addition to Västmanland, Dalarna , Gästrikland , Närke , Södermanland , Värmland and Västerbotten in Sweden; in some regions of Slovakia ; Bohemia and Moravia in the Czech Republic and in many regions of the USA . One of the world's most important deposits for native antimony and antimony ores is the Murchison greenstone belt in the Murchison Range of South Africa.

So far, 264 antimony minerals are known (as of 2010). The sulphide mineral Stibnit Sb 2 S 3 (gray spike gloss) with a maximum content of 71.7% Sb is mainly used industrially . The mineral with the highest Sb content in a chemical compound is the natural antimony-arsenic alloy Paradocrasite (max . 92%). However, with only three localities, in contrast to stibnite (around 2500 localities), it occurs much less often. Further sources of antimony are the minerals Valentinite Sb 2 O 3 (white spit gloss), Breithauptit NiSb (antimony nickel, nickel antimonide), Kermesite Sb 2 S 2 O (red spit gloss) and Sb 2 S 5 (gold sulfur).

Extraction and presentation

Development over time of worldwide antimony production

Technically, antimony is extracted from the antimony luster . One process is based on roasting and reduction with carbon ( roasting reduction process ):

Another possibility is to carry out the reduction with iron ( precipitation method ):

At the beginning of the 21st century, between 110,000 and 160,000 tons of antimony were mined worldwide. Since 1900, the output has increased more than tenfold.

87% of antimony production takes place in China (as of 2015).

properties

Crystallographic Data
Idealized crystal form of a ditrigonal scalenohedron

Idealized crystal form of a ditrigonal scalenohedron.

Crystal system trigonal - ditrigonal-scalenohedral
Space group R 3 m (No. 166)Template: room group / 166
Lattice parameter
(unit cell )
a  = 431  pm ; c  = 1127 pm
Number (Z) of the formula units Z = 6

Modifications

Antimony can appear in three different modifications , with metallic or gray antimony being the most permanent modification.

Under normal conditions, antimony crystallizes trigonal in a rhombohedral arrangement in the space group R 3 m (No. 166) described according to the Hermann-Mauguin symbology with the lattice parameters a  = 431  pm and c  = 1127 pm as well as six formula units per unit cell .  Template: room group / 166

By quenching antimony vapor on cold surfaces, amorphous , black and very reactive antimony is produced, which is converted back into metallic antimony by heating. By electrolytic manufacture gives rise to explosive antimony, which merges in scratching explosively aufglühend and sparks to metallic antimony. However, this form always contains some chlorine and cannot be considered a modification. Yellow antimony is also not an independent modification, but a highly polymeric chemical compound with hydrogen .

Physical Properties

Metallic antimony is silver-white, very shiny, leafy, coarsely crystalline. It can be easily crushed due to its brittleness. Electrical and thermal conductivity are low.

Chemical properties

With nascent hydrogen, antimony reacts to form the unstable antimony hydride SbH 3 . Antimony is not attacked by air and water at room temperature. Above the melting point, it burns in air with a bluish-white flame to form antimony (III) oxide . It dissolves in hot concentrated mineral acids . It reacts violently with the halogens at room temperature to form the corresponding halides.

In compounds, antimony is predominantly in the +3 and +5 oxidation states. In metal antimonides such as potassium antimonide K 3 Sb it forms Sb 3− ions.

Isotopes

There are two stable isotopes of antimony : 121 Sb and 123 Sb.

use

Alloys

Most of the antimony produced is processed into alloys and shows the following properties:

  • It is used to harden lead and tin alloys .
  • In contrast to most other metals, it expands when the melt cools (as a result of conversion into another modification): The antimony content can be adjusted so that such alloys do not shrink or even expand somewhat when cooling; In the case of parts manufactured in casting molds, the metal presses itself into all nooks and crannies as it solidifies, so that even complex shapes and strongly patterned surfaces can be produced without voids .

Important alloys:

medicine

Antimony (or a preparation obtained from antimony ore) became an ( iatrochemical ) “lead drug” in the 16th and 17th centuries , but was - like other Paracelsian drugs - controversial and banned in France between 1615 and 1688.

Emetic tartar was long used as a nauseating agent ( antimony pill ), today it is still sometimes used to examine the stomach contents of birds.

Both schistosomiasis and trypanosomes were combated with tartar emetic ( potassium antimonyl tartrate ) from the beginning of the 19th century . Emetic tartar was made by storing wine in an antimony beaker for a day and then drinking it. In the meantime, more effective and better tolerated drugs are being used.

Antimony preparations are mostly used as less toxic pentavalent forms for the drug therapy of leishmaniasis and schistosomiasis , but no longer as the first choice in developed countries. Here, antimony inhibits the enzyme phosphofructokinase , which is the rate-limiting step in glycolysis .

additional

Flaming match

toxicity

Antimony can be fatal with ingestion of 200 to 1200 mg. In toxicology, three forms of antimony are known, of which the gaseous antimony hydride ( Stiban , SbH 3 ) is the most dangerous form, which induces massive hemolysis . After toxicity, emetic tartar follows with trivalent ("trivalent") antimony, while pentavalent antimony is the least toxic.

95% of the trivalent antimony is absorbed into red blood cells within the first two hours after ingestion and is therefore mainly concentrated in organs with a strong blood supply. The excretion occurs mainly by binding to glutathione via the bile with a correspondingly high enterohepatic circulation , and only a small part is on the kidney excreted. 90% of potassium antimonyl tartrate is excreted within the first day after intake, the remaining 10% over 16 days due to slower elimination kinetics .

It is believed that antimony similar to arsenic , the function of the pyruvate dehydrogenase complex inhibits and thus of a lack intra cellular energy source adenosine triphosphate leads (ATP). This leads to the formation of chelate complexes between the antimony and thiol groups of the corresponding enzymes. In the body, it has a toxic effect in numerous organs, such as the digestive tract , liver , kidneys , heart and central nervous system . Antimony reaches its highest concentration in the liver, where it can lead to hepatitis or even liver failure . At the heart there are changes in the ECG with inversion and reduction of the T wave and a prolonged QT interval . Acute kidney failure can lead to temporary or permanent hemodialysis .

In addition to supportive measures such as infusion therapy (both to compensate for the loss of fluid due to vomiting and to protect the kidneys) and close monitoring of the vital functions and the ECG, active charcoal , N-acetylcysteine as a precursor of glutathione, are therapeutically used in antimony poisoning increased secretion and a chelating agent, e.g. B. Dimercaprol .

Results from research indicate that antimony compounds irritate the skin and mucous membranes. These compounds are likely to break away from plastic and textiles.

Safety instructions and limit values

Of the antimony compounds, the EU has classified antimony fluoride as toxic (T) and the chlorides as corrosive (C), and also as dangerous for the environment (N); all other antimony compounds as harmful (Xn) and dangerous for the environment (N). Antimony itself is not listed there; according to the safety data sheet, it is labeled as irritant .

The International Agency for Research on Cancer (IARC) has classified antimony (III) oxide as a potentially carcinogenic substance .

In the EU, a limit value of 5 µg / l applies to drinking water. Investigations of fruit juices filled in PET bottles (for which no guidelines exist) revealed antimony concentrations of up to 44.7 µg / l in undiluted juice concentrates.

In 2016, antimony was included in the EU's ongoing action plan ( CoRAP ) in accordance with Regulation (EC) No. 1907/2006 (REACH) as part of substance evaluation . The effects of the substance on human health and the environment are re-evaluated and, if necessary, follow-up measures are initiated. Antimony uptake was caused by concerns about worker exposure , high (aggregated) tonnage, high risk characterization ratio (RCR) and widespread use, as well as the possible risk of carcinogenic properties. The reassessment has been running since 2018 and is being carried out by Germany .

proof

Flame color of antimony

Preliminary samples:

Flame color : pale blue flame, little characteristic phosphor salt pearl: colorless (disrupted by all elements that produce a colored pearl)

Detection reaction :

Reduction by base metals, for example iron, zinc or tin.

In solutions that are not too acidic, base metals reduce antimony cations Sb (III), Sb (V) and Sb (III) / (V) to metallic antimony:

2 Sb 3+ + 3 Fe → 2 Sb + 3 Fe 2+

The substance to be tested for antimony is placed in a hydrochloric acid solution and iron powder is added. A black, flaky precipitate of metallic antimony forms in the solution or directly on the iron. Evidence on an iron nail is also possible. A black deposit on the nail is evidence of antimony, which has precipitated elementarily here.

The Marsh sample allows an unambiguous detection of antimony. If the pyrolytically deposited substance (dark, shiny mirror) does not dissolve in ammoniacal hydrogen peroxide , arsenic and germanium are excluded as possible alternatives.

The highly sensitive determination of tiny traces of antimony is carried out using the hydride technique of atomic spectrometry . In principle, the Marsh probe is coupled with atomic absorption spectrometry. The matrix effects of the sample solution can thereby be suppressed very effectively.

Another method is to add rhodamine B solution to an aqueous solution that contains antimony ions. A colored complex is formed which can be extracted with isopropyl ether. However, this proof is quite unspecific, since gold , cadmium , gallium , thallium , uranium and tungsten ions also form colored complexes.

links

  • Antimony hydrogen , also called monostibane SbH 3 .
    Poisonous gas that is formed from antimony and active acids.
  • Distibane (Sb 2 H 4 )

Halogen compounds

Oxygen compounds

  • There are salts that are derived from the hypothetical water-rich form of the antimony acid HSb (OH) 4 . The antimony acid itself, the antimony trihydroxide (H 3 SbO 3 / Sb (OH) 3 ), cannot be isolated. It acts as a weak acid due to the reaction (p K S = 11). It is amphoteric and can also act as a very weak base ( )
  • Antimonic acid (HSb (OH) 6 )

Sulfur compounds

  • Antimony trisulfide , also called antimony luster (Sb 2 S 3 )
    Gray-black stems with a metallic sheen. Starting material for the production of metallic antimony. Soluble in strong acids. Use for matches, ruby ​​glasses and camouflage paints (reflection of IR light).
  • Antimony pentasulfide , formerly known as gold sulfur (Sb 2 S 5 )

Other connections

literature

Web links

Wiktionary: Antimony  - explanations of meanings, word origins, synonyms, translations
Commons : Antimony  album with pictures, videos and audio files
Wikibooks: Internship Inorganic Chemistry / Antimony  - Learning and teaching materials

Individual evidence

  1. ^ Harry H. Binder: Lexicon of the chemical elements. S. Hirzel Verlag, Stuttgart 1999, ISBN 3-7776-0736-3 .
  2. The values ​​for the properties (info box) are taken from www.webelements.com (antimony) , unless otherwise stated .
  3. CIAAW, Standard Atomic Weights Revised 2013 .
  4. ^ IUPAC, Standard Atomic Weights Revised 2013 .
  5. Manjeera Mantina, Adam C. Chamberlin, Rosendo Valero, Christopher J. Cramer, Donald G. Truhlar: Consistent van der Waals Radii for the Whole Main Group. In: J. Phys. Chem. A. 113, 2009, pp. 5806-5812, doi: 10.1021 / jp8111556 .
  6. a b c d e entry on antimony in Kramida, A., Ralchenko, Yu., Reader, J. and NIST ASD Team (2019): NIST Atomic Spectra Database (ver. 5.7.1) . Ed .: NIST , Gaithersburg, MD. doi : 10.18434 / T4W30F ( https://physics.nist.gov/asd ). Retrieved June 11, 2020.
  7. a b c d e entry on antimony at WebElements, https://www.webelements.com , accessed on June 11, 2020.
  8. David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Properties of the Elements and Inorganic Compounds, pp. 4-142-4-147. The values ​​there are based on g / mol and are given in cgs units. The value specified here is the SI value calculated from it, without a unit of measure.
  9. a b Yiming Zhang, Julian RG Evans, Shoufeng Yang: Corrected Values ​​for Boiling Points and Enthalpies of Vaporization of Elements in Handbooks. In: Journal of Chemical & Engineering Data . 56, 2011, pp. 328-337, doi: 10.1021 / je1011086 .
  10. a b Entry on antimony in the GESTIS substance database of the IFA , accessed on April 26, 2017(JavaScript required) .
  11. Entry on Antimony in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on August 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .
  12. Swiss Accident Insurance Fund (Suva): Limit values ​​- current MAK and BAT values (search for 7440-36-0 or antimony ), accessed on November 2, 2015.
  13. Willem F. Daems: To Helmut Gebelein: Alchemie. Munich: Eugen Diederichs 1991. In: Würzburger medical history reports. Volume 11, 1993, pp. 405-407, here: p. 406.
  14. ^ Doris Schwarzmann-Schafhauser: Antimonstreit. In: Werner E. Gerabek u. a. (Ed.): Encyclopedia of medical history. De Gruyter, Berlin / New York 2005, ISBN 3-11-015714-4 , p. 72.
  15. ^ Mindat - Sala Silver Mine, Sala, Västmanland, Sweden .
  16. IMA / CNMNC List of Mineral names - Antimony (English, PDF 1.8 MB, p. 14).
  17. Mindat - Localities for Antimony (English).
  18. ^ Mineral profile of Limpopo region . at www.geoscience.org.za (English).
  19. Webmineral - Mineral Species sorted by the element Sb (Antimony) .
  20. Mindat - Paradocrasite .
  21. Mindat - Stibnite .
  22. ddc.arte.tv  ( page no longer available , search in web archivesInfo: The link was automatically marked as defective. Please check the link according to the instructions and then remove this notice.@1@ 2Template: Toter Link / ddc.arte.tv  
  23. ^ Hugo Strunz , Ernest H. Nickel: Strunz Mineralogical Tables . 9th edition. E. Schweizerbart'sche Verlagbuchhandlung (Nägele and Obermiller), Stuttgart 2001, ISBN 3-510-65188-X , p. 50 .
  24. ^ William M. Haynes: CRC Handbook of Chemistry and Physics . 96th edition. CRC Press, 2015, ISBN 978-1-4822-6097-7 , pp. 4–4 ( google.de [accessed on March 22, 2016]).
  25. Lautenschläger among other things: Taschenbuch der Chemie. 15.5 Antimony and Antimony Compounds. ( Memento of March 4, 2016 in the Internet Archive ) Verlag Harri Deutsch, Frankfurt am Main 2001.
  26. Ulrich Arndt: The "Magnet of the Wise" - Alchemical transmutation of antimony. In: Paracelsus. November 2005, pp. 12-17. ( Online version ).
  27. Wolf-Dieter Müller-Jahncke , Christoph Friedrich : History of drug therapy. Deutscher Apothekerverlag, Stuttgart 1996, ISBN 3-7692-2038-2 , pp. 65-66.
  28. ^ Doris Schwarzmann-Schafhauser: Antimonstreit. In: Werner E. Gerabek u. a. (Ed.): Encyclopedia of medical history. De Gruyter, Berlin / New York 2005, ISBN 3-11-015714-4 , p. 72.
  29. ^ Antony W. Diamond, VC Fayad, Peter S. McKinley: Commentary: Ipecac: An Improved Emetic for Wild Birds . In: Journal of Field Ornithology . tape 78 , no. 4 , 2007, p. 436-439 , doi : 10.1111 / j.1557-9263.2007.00136.x .
  30. George C. Low: The history of the use of intravenous injections of tartar emetic (Antimonium tartaratum) in tropical medicine . In: Transactions of the Royal Society of Tropical Medicine and Hygiene . tape 10 , no. 2 , 1916, p. 37 , doi : 10.1016 / S0035-9203 (16) 90068-3 .
  31. Paul Hagan: Schistosomiasis - a rich vein of research . In: Parasitology . tape 136 , no. 12 , 2009, p. 1611-1619 , doi : 10.1017 / S003118200999093X , PMID 19691867 .
  32. Vishnu Ji Ram, Mahendra Nath: Progress in Chemotherapy of Leishmaniasis . In: Current Medicinal Chemistry . Publishers, Bentham Science, Oct 1996, chapter The Antimonials , pp. 304-305 ( Google Books ).
  33. Rüdiger Dörris: Medical Microbiology . Georg Thieme Verlag, ISBN 3-13-125313-4 , p. 527 .
  34. Katja Bauer: Toxins on the shooting ranges of elite police? In: badische-zeitung.de , June 4, 2016.
  35. Alexander P. Hardt: Pyrotechnics , Pyrotechnica Publications, Post Falls Idaho USA 2001, ISBN 0-929388-06-2 , pp. 74 ff.
  36. Wendy Macías Konstantopoulos, Michele Burns Ewald, Daniel S. Pratt: Case 22-2012: A 34-Year-Old Man with Intractable Vomiting after Ingestion of an Unknown Substance. In: New England Journal of Medicine . 367, 2012, pp. 259-268.
  37. Entry on antimony compounds in the GESTIS substance database of the IFA , accessed on September 14, 2012 (JavaScript required)
  38. Federal Office of Public Health Switzerland (FOPH): Risk analysis: Antimony in food and ready meals that are prepared directly in PET trays. (PDF) August 23, 2007.
  39. Claus Hansen, Alexandra Tsirigotaki, Søren Alex Bak, Spiros A. Pergantis, Stefan Stürup, Bente Gammelgaard, Helle Rüsz Hansen: Elevated antimony concentrations in commercial juices . In: Journal of Environmental Monitoring . tape 12 , no. 4 , 2010, p. 822-824 , doi : 10.1039 / B926551A .
  40. Sophie Borland: Fruit juice cancer warning as scientists find harmful chemical in 16 drinks. Daily Mail , March 1, 2010, accessed March 1, 2010 .
  41. Community rolling action plan ( CoRAP ) of the European Chemicals Agency (ECHA): Antimony , accessed on May 20, 2019.Template: CoRAP status / 2018
  42. Entry on Rhodamine. In: Römpp Online . Georg Thieme Verlag, accessed on August 8, 2016.
  43. ^ AF Holleman , N. Wiberg : Inorganische Chemie . 103rd edition. Volume 1: Basics and main group elements. Walter de Gruyter, Berlin / Boston 2016, ISBN 978-3-11-049585-0 , p. 970 (reading sample: Part A - Basics of the chemistry of hydrogen. Google book search ).
  44. a b A. F. Holleman , N. Wiberg : Inorganische Chemie . 103rd edition. Volume 1: Basics and main group elements. Walter de Gruyter, Berlin / Boston 2016, ISBN 978-3-11-049585-0 , p. 971 (reading sample: Part A - Basics of the chemistry of hydrogen. Google book search ).