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 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 17621613

PubChem CID

* 16689752

UNII |

* F79059A38U Y

InChI

* InChI=1S/3O.2Sb

Key: IHBMMJGTJFPEQY-UHFFFAOYSA-N

SMILES

* S=[Sb]S[Sb]=S

Properties

Chemical formula

| Sb

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)

Solubility in water

| 0.00017 g/(100 mL) (18 °C)

Magnetic susceptibility (χ)

| −86.0·10−6 cm3/mol

Refractive index (nD)

| 4.046
Thermochemistry

Heat capacity (C)

| 123.32 J/(mol·K)

Std enthalpy of
formation (ΔfH⦵298)

| −157.8 kJ/mol
Hazards
NFPA 704 (fire diamond)  |

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/m3 (as Sb)[2]

REL (Recommended)

| TWA 0.5 mg/m3 (as Sb)[2]
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 [77 °F], 100 kPa).

Infobox references

Antimony trisulfide (Sb

3) 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 is also used as friction materials in break lining. It is very important critical primer material for military applications and tracer bullets.[5] It also is used in the production of ruby-colored glass and in plastics as a flame retardant.[6] Historically the stibnite form was used as a grey pigment in paintings produced in the 16th century.[7] In 1817, the dye and fabric chemist, John Mercer discovered the non-stoichiometric compound Antimony Orange (approximate formula Sb

3 * Sb

3), the first good orange pigment available for cotton fabric printing.[8]

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.[9]

## Preparation and reactions

3 can be prepared from the elements at temperature 500–900 °C:[6]

2 Sb + 3 S → Sb

3 is precipitated when H
2S is passed through an acidified solution of Sb(III).[10] This reaction has been used as a gravimetric method for determining antimony, bubbling H
2S through a solution of Sb(III) compound in hot HCl deposits an orange form of Sb

3 which turns black under the reaction conditions.[11]

3 is readily oxidised, reacting vigorously with oxidising agents.[6] It burns in air with a blue flame. It reacts with incandescence with cadmium, magnesium and zinc chlorates. Mixtures of Sb

3 and chlorates may explode.[12]

In the extraction of antimony from antimony ores the alkaline sulfide process is employed where Sb

3 reacts to form thioantimonate(III) salts (also called thioantimonite):[13]

3 Na
2S + Sb

3 → 2 Na
3SbS

A number of salts containing different thioantimonate(III) ions can be prepared from Sb

3. These include:[14]

[SbS
3]3−, [SbS
2]−
, [Sb

5]4−, [Sb

9]6−, [Sb

7]2− and [Sb

17]10−

Schlippe's salt, Na
3SbS
4 * 9H2O, a thioantimonate(V) salt is formed when Sb

3 is boiled with sulfur and sodium hydroxide. The reaction can be represented as:[10]

3 \+ 3 S2− \+ 2 S → 2 [SbS
4]3−

## Structure

The structure of the black needle-like form of Sb

3, stibnite, consists of linked ribbons in which antimony atoms are in two different coordination environments, trigonal pyramidal and square pyramidal.[10] Similar ribbons occur in Bi

3 and Sb
2Se
3.[15] 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).[16] Other paper shows that the actual coordination polyhedra of antimony are in fact SbS
7, with (3+4) coordination at the M1 site and (5+2) at the M2 site.[clarification needed] These coordinations consider the presence of secondary bonds. Some of the secondary bonds impart cohesion and are connected with packing.[17]

## References

1. ↑ 1.0 1.1 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. ↑ 2.0 2.1 NIOSH Pocket Guide to Chemical Hazards. "#0036". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0036.html.
3. ↑ "Metastibnite". https://www.mindat.org/min-2686.html.
4. ↑ SUPERGENE METASTIBNITE FROM MINA ALACRAN, PAMPA LARGA, COPIAPO, CHILE, Alan H Clark, THE AMERICAN MINERALOGIST. VOL. 55., 1970
5. ↑ www.antimonytrisulfide.com
6. ↑ 6.0 6.1 6.2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 581–582. ISBN 978-0-08-037941-8.
7. ↑ Eastaugh, Nicholas (2004). Pigment Compendium: A Dictionary of Historical Pigments. Butterworth-Heinemann. p. 359. ISBN 978-0-7506-5749-5.
8. ↑ Parnell, Edward A (1886). The life and labours of John Mercer. London: Longmans, Green & Co.. pp. 23.
9. ↑ Electrochemistry of Metal Chalcogenides, Mirtat Bouroushian, Springer, 2010
10. ↑ 10.0 10.1 10.2 Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils, ed., Inorganic Chemistry, San Diego/Berlin: Academic Press/De Gruyter, p. 765-766, ISBN 0-12-352651-5
11. ↑ A.I. Vogel, (1951), Quantitative Inorganic analysis, (2d edition), Longmans Green and Co
12. ↑ Hazardous Laboratory Chemicals Disposal Guide, Third Edition, CRC Press, 2003, Margaret-Ann Armour, ISBN 9781566705677
13. ↑ Anderson, Corby G. (2012). "The metallurgy of antimony". Chemie der Erde - Geochemistry 72: 3–8. doi:10.1016/j.chemer.2012.04.001. ISSN 0009-2819. Bibcode: 2012ChEG...72....3A.
14. ↑ 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
15. ↑ Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
16. ↑ 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.
17. ↑ 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. doi:10.1007/s00269-001-0227-1. Bibcode: 2002PCM....29..254K.

* v
* t
* e

Antimony compounds

* SbBr3
* Sb(C2H3O2)3
* SbCl3
* SbCl5
* SbF3
* SbF5
* SbH3
* SbI3
* Sb2O3
* Sb2O4
* Sb2O5
* Sb2S3
* Sb2S5
* Sb2(SO4)3
* Sb2Se3
* Sb2Te3

* v
* t
* e

Sulfides

| H2S
H2S2 |  |  |  |  |  |  |  |  |  |  |  |  |  |  |  |  | He

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Li2S | BeS |  |  |  |  |  |  |  |  |  |  | B2S3 | CS2
COS | (NH4)SH | O | F | Ne
Na2S
Na2Sx | MgS |  |  |  |  |  |  |  |  |  |  | Al2S3 | SiS
SiS2 | PxSy | S | Cl | Ar
K2S | CaS | Sc2S3 | TiS2 | V | CrS
Cr2S3 | MnS
MnS2 | FeS
Fe3S4 | CoS | NiS | Cu2S
CuS | ZnS | GaS
Ga2S3 | GeS
GeS2 | As2S3
As4S3 | SeS2 | Br | Kr
Rb2S | SrS | Y2S3 | ZrS2 | NbS2 | MoS2 | Tc | Ru | Rh2S3 | PdS | Ag2S | CdS | In2S3 | SnS
SnS2 | Sb2S3
Sb2S5 | TeS2 | I | Xe
Cs2S | BaS | *  | HfS2 | TaS2 | WS2
WS3 | ReS2
Re2S7 | Os | Ir2S3
IrS2 | PtS
PtS2 | Au2S
Au2S3 | HgS | Tl2S | PbS
PbS2 | Bi2S3 | Po | At | Rn
Fr | Ra | **  | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og |  |  |  |  |  |  |  |
|  | ↓ |  |  |  |  |  |  |  |  |  |  |  |  |  |  |
| * | La2S3 | CeS
Ce2S3 | Pr2S3 | Nd2S3 | Pm2S3 | SmS
Sm2S3 | Eu2S3 | Gd2S3 | Tb2S3 | Dy2S3 | Ho2S3 | Er2S3 | Tm2S3 | Yb2S3 | Lu2S3 |
| ** | Ac | ThS2 | Pa | US2 | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr |

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