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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
CAS Number	1345-04-6
3D model (JSmol)	Interactive image
ChemSpider	17621613
ECHA InfoCard	100.014.285
PubChem CID	16689752
UNII	F79059A38U
CompTox Dashboard (EPA)	DTXSID6030732
InChI InChI=1S/3O.2SbKey: IHBMMJGTJFPEQY-UHFFFAOYSA-N
SMILES S=S=S
Properties
Chemical formula	Sb2S3
Molar mass	339.70 g·mol
Appearance	Grey or black orthorhombic crystals (stibnite)
Density	4.562g cm (stibnite)
Melting point	550 °C (1,022 °F; 823 K) (stibnite)
Boiling point	1,150 °C (2,100 °F; 1,420 K)
Solubility in water	0.00017 g/(100 mL) (18 °C)
Magnetic susceptibility (χ)	−86.0·10 cm/mol
Refractive index (nD)	4.046
Thermochemistry
Heat capacity (C)	123.32 J/(mol·K)
Std enthalpy of formation (ΔfH298)	−157.8 kJ/mol
Hazards
NFPA 704 (fire diamond)	2 0 0
Lethal dose or concentration (LD, LC):
LD50 (median dose)	> 2000 mg/kg (rat, oral)
NIOSH (US health exposure limits):
PEL (Permissible)	TWA 0.5 mg/m (as Sb)
REL (Recommended)	TWA 0.5 mg/m (as Sb)
Related compounds
Other anions	Antimony trioxide Antimony triselenide Antimony telluride
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 , 100 kPa). Infobox references

Antimony trisulfide (Sb₂S₃) is found in nature as the crystalline mineral stibnite and the amorphous red mineral (actually a mineraloid) metastibnite. 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. Historically the stibnite form was used as a grey pigment in paintings produced in the 16th century. 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.

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.

Preparation and reactions

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

2 Sb + 3 S → Sb₂S₃

Sb₂S₃ is precipitated when H₂S is passed through an acidified solution of Sb(III). 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.

Sb₂S₃ is readily oxidised, reacting vigorously with oxidising agents. 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.

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):

3 Na₂S + Sb₂S₃ → 2 Na₃SbS₃

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

[SbS₃], [SbS₂], [Sb₂S₅], [Sb₄S₉], [Sb₄S₇] and [Sb₈S₁₇]

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:

Sb₂S₃ + 3 S + 2 S → 2 [SbS₄]

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. Similar ribbons occur in Bi₂S₃ and Sb₂Se₃. 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). 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.

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.

• Antimony(III) compounds
• Sesquisulfides