Antimony trisulfide

Antimony trisulfide (Sb2S3) is found in nature as the crystalline mineral stibnite and the amorphous red mineral (actually a mineraloid)[3] metastibnite.[4] It is manufactured for use in safety matches, military ammunition, explosives and fireworks. It also is used in the production of ruby-colored glass and in plastics as a flame retardant.[5] Historically the stibnite form was used as a grey pigment in paintings produced in the 16th century.[6] In 1817, the dye and fabric chemist, John Mercer discovered the non-stoichiometric compound Antimony Orange (approximate formula Sb2S3·Sb2O3), the first good orange pigment available for cotton fabric printing.[7]

Antimony trisulfide
Names
IUPAC names
Antimony(III) sulfide
Diantimony trisulfide
Other names
  • Antimonous sulfide
  • Antimony sesquisulfide
  • Antimony sulfide
  • Antimony vermilion
  • Black antimony
  • Sulphuret of antimony
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.014.285
UNII
  • InChI=1S/3O.2Sb
    Key: IHBMMJGTJFPEQY-UHFFFAOYSA-N
  • S=[Sb]S[Sb]=S
Properties
Sb2S3
Molar mass 339.70 g·mol−1
Appearance Grey or black orthorhombic crystals (stibnite)
Density 4.562g cm−3 (stibnite)[1]
Melting point 550 °C (1,022 °F; 823 K) (stibnite)[1]
Boiling point 1,150 °C (2,100 °F; 1,420 K)
0.00017 g/(100 mL) (18 °C)
−86.0·10−6 cm3/mol
4.046
Thermochemistry
123.32 J/(mol·K)
−157.8 kJ/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
2
0
0
Lethal dose or concentration (LD, LC):
> 2000 mg/kg (rat, oral)
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 0.5 mg/m3 (as Sb)[2]
REL (Recommended)
 TWA 0.5 mg/m3 (as Sb)[2]
Related compounds
Other anions
Other cations
 Arsenic trisulfide
Bismuth(III) sulfide
Related compounds
 Antimony pentasulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Antimony trisulfide was also used as the image sensitive photoconductor in vidicon camera tubes. It is a semiconductor with a direct band gap of 1.8–2.5 eV. With suitable doping, p and n type materials can be produced.[8]

Preparation and reactions

Sb2S3 can be prepared from the elements at temperature 500–900 °C:[5]

2 Sb + 3 S → Sb2S3

Sb2S3 is precipitated when H2S is passed through an acidified solution of Sb(III).[9] This reaction has been used as a gravimetric method for determining antimony, bubbling H2S through a solution of Sb(III) compound in hot HCl deposits an orange form of Sb2S3 which turns black under the reaction conditions.[10]

Sb2S3 is readily oxidised, reacting vigorously with oxidising agents.[5] It burns in air with a blue flame. It reacts with incandescence with cadmium, magnesium and zinc chlorates. Mixtures of Sb2S3 and chlorates may explode.[11]

In the extraction of antimony from antimony ores the alkaline sulfide process is employed where Sb2S3 reacts to form thioantimonate(III) salts (also called thioantimonite):[12]

3 Na2S + Sb2S3 → 2 Na3SbS3

A number of salts containing different thioantimonate(III) ions can be prepared from Sb2S3. These include:[13]

[SbS3]3−, [SbS2]−, [Sb2S5]4−, [Sb4S9]6−, [Sb4S7]2− and [Sb8S17]10−

Schlippe's salt, Na3SbS4·9H2O, a thioantimonate(V) salt is formed when Sb2S3 is boiled with sulfur and sodium hydroxide. The reaction can be represented as:[9]

Sb2S3 + 3 S2− + 2 S → 2 [SbS4]3−

Structure

The structure of the black needle-like form of Sb2S3, stibnite, consists of linked ribbons in which antimony atoms are in two different coordination environments, trigonal pyramidal and square pyramidal.[9] Similar ribbons occur in Bi2S3 and Sb2Se3.[14] The red form, metastibnite, is amorphous. Recent work suggests that there are a number of closely related temperature dependent structures of stibnite which have been termed stibnite (I) the high temperature form, identified previously, stibnite (II) and stibnite (III).[15] Other paper shows that the actual coordination polyhedra of antimony are in fact SbS7, with (3+4) coordination at the M1 site and (5+2) at the M2 site. These coordinations consider the presence of secondary bonds. Some of the secondary bonds impart cohesion and are connected with packing.[16]

References
  1. Haynes, W. M., ed. (2014). CRC Handbook of Chemistry and Physics (95th ed.). Boca Raton, FL: CRC Press. pp. 4–48. ISBN 978-1-4822-0867-2.
  2. NIOSH Pocket Guide to Chemical Hazards. "#0036". National Institute for Occupational Safety and Health (NIOSH).
  3. "Metastibnite".
  4. SUPERGENE METASTIBNITE FROM MINA ALACRAN, PAMPA LARGA, COPIAPO, CHILE, Alan H Clark, THE AMERICAN MINERALOGIST. VOL. 55., 1970
  5. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 581–582. ISBN 978-0-08-037941-8.
  6. Eastaugh, Nicholas (2004). Pigment Compendium: A Dictionary of Historical Pigments. Butterworth-Heinemann. p. 359. ISBN 978-0-7506-5749-5.
  7. Parnell, Edward A (1886). The life and labours of John Mercer. London: Longmans, Green & Co. p. 23.
  8. Electrochemistry of Metal Chalcogenides, Mirtat Bouroushian, Springer, 2010
  9. Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, p. 765-766, ISBN 0-12-352651-5
  10. A.I. Vogel, (1951), Quantitative Inorganic analysis, (2d edition), Longmans Green and Co
  11. Hazardous Laboratory Chemicals Disposal Guide, Third Edition, CRC Press, 2003, Margaret-Ann Armour, ISBN 9781566705677
  12. Anderson, Corby G. (2012). "The metallurgy of antimony". Chemie der Erde - Geochemistry. 72: 3–8. Bibcode:2012ChEG...72....3A. doi:10.1016/j.chemer.2012.04.001. ISSN 0009-2819.
  13. Inorganic Reactions and Methods, The Formation of Bonds to Group VIB (O, S, Se, Te, Po) Elements (Part 1) (Volume 5) Ed. A.P, Hagen,1991, Wiley-VCH, ISBN 0-471-18658-9
  14. Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
  15. Kuze S., Du Boulay D., Ishizawa N., Saiki A, Pring A.; (2004), X ray diffraction evidence for a monoclinic form of stibnite, Sb2S3, below 290K; American Mineralogist, 9(89), 1022-1025.
  16. Kyono, A.; Kimata, M.; Matsuhisa, M.; Miyashita, Y.; Okamoto, K. (2002). "Low-temperature crystal structures of stibnite implying orbital overlap of Sb 5s 2 inert pair electrons". Physics and Chemistry of Minerals. 29 (4): 254–260. Bibcode:2002PCM....29..254K. doi:10.1007/s00269-001-0227-1. S2CID 95067785.
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