Antimony (III) sulfide

Crystal structure
__ Sb 3+      __ S 2−
General
Surname	Antimony (III) sulfide
other names	Antimony trisulfide Antimony shine Antimony orange Stibnite Diantimony trisulfide Gray shine Sulfur antimony Antimony black
Ratio formula	Sb 2 S 3
Brief description	dark gray to black (crystalline form) orange-red (amorphous) odorless solid
External identifiers / databases
CAS number 1345-04-6 EC number 215-713-4 ECHA InfoCard 100.014.285 PubChem 16689752 Wikidata Q409041
properties
Molar mass	339.68 g mol −1
Physical state	firmly
density	4.12-4.64 g · cm −3
Melting point	550 ° C
boiling point	1150 ° C
solubility	practically insoluble in water
safety instructions
GHS labeling of hazardous substances Caution H and P phrases H: 302-332-411 P: 273
Toxicological data	> 2000 mg kg −1 ( LD 50 ,  rat ,  oral )
Thermodynamic properties
ΔH f 0	−127.6 kJ mol −1
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Antimony (III) sulfide is a chemical compound of the elements antimony and sulfur . It belongs to the group of sulfides .

Occurrence

Antimony (III) sulfide occurs naturally in the form of the mineral stibnite (gray shine). To obtain pure antimony (III) sulphide, gray skewer ores with larger proportions of mineral by-products (gangue) are initially heated to such an extent that the relatively low-melting compound flows off on an inclined surface ( Seigerarbeit ). The segregated product with a content of 92% to 98% antimony (III) sulfide is known as antimonium crudum .

Extraction and presentation

Pure antimony (III) sulfide can be produced by reacting antimony (III) chloride with thioacetamide in ethanol or in glacial acetic acid .

Antimony (III) sulfide can also be produced by melting the elements together

${\displaystyle {\ce {2Sb + 3S -> Sb2S3}}}$

or by introducing hydrogen sulfide into acidified solutions of trivalent or pentavalent antimony compounds.

${\displaystyle {\ce {2SbO+ + 3H2S -> Sb2S3 + 2H2O + 2H+}}}$

properties

Antimony (III) sulfide is a dark gray to black (crystalline form) or orange-red (amorphous form) odorless solid that is practically insoluble in water. The orange-red form obtained during precipitation reactions changes into the more stable gray version when heated in the absence of air (under nitrogen from 270 ° C). In air, it decomposes to form antimony (III) oxide at temperatures above 300 ° C. In boiling water or on contact with water vapor, it slowly decomposes with the formation of hydrogen sulfide.

${\displaystyle {\ce {Sb2S3 + H2O -> Sb2O3 + 3H2S ^}}}$

Antimony (III) sulphide is sparingly soluble in hot ammonia water, soluble in strong acids and lyes and forms antimony (III) chloride with boiling hydrochloric acid .

${\displaystyle {\ce {Sb2S3 + 6HCl -> 2SbCl3 + 3H2S ^}}}$

With dilute nitric acid it forms antimony (III) oxide , with concentrated antimonic acid .

${\displaystyle {\ce {Sb2S3 + 2HNO3 + 2H2O -> 2Sb2O3 + 3S + 2NO ^ + 3H2O}}}$

Antimony (III) sulfide crystallizes in the orthorhombic crystal system in the space group Pnma (space group no. 62) with the lattice parameters a = 1131.07  pm , b = 383.63 pm and c = 1122.85 pm. In the unit cell contains four formula units .

use

Antimony (III) sulfide was previously used as a pigment under the name of antimony black . The mineral is since the ancient times known and as a black make-up powder for coloring of eyelids and eyebrows used (but also for the treatment of hemorrhoids ). Today the compound is still used in pyrotechnics , ruby ​​red glass , as a dye for plastics and as a flame retardant .

It reacts with potassium chlorate and was part of the first real match with friction ignition by John Walker around 1826 :

${\displaystyle {\ce {3KClO3 + Sb2S3 -> 3KCl + Sb2O3 + 3SO2 ^}}}$

Nowadays it is no longer used in matchmaking in ignition heads, but only rarely in friction surfaces for safety matches.

Antimony (III) sulfide is a semiconductor with high photosensitivity that has been used in television cameras and various optoelectronic devices.

It can also be used to produce antimony by reacting with iron

${\displaystyle {\ce {Sb2S3 + 3Fe -> 2Sb + 3FeS}}}$

or oxygen and carbon can be used.

${\displaystyle {\ce {Sb2S3 + 5O2 -> Sb2O4 + 3SO2 ^}}}$

${\displaystyle {\ce {Sb2O4 + 4C -> 2Sb + 4CO ^}}}$

Since antimony (III) sulfide reflects infrared light similar to green plants, it is contained in many camouflage colors .

safety instructions

Meaningful tests of acute oral toxicity are not available for antimony (III) sulfide. However, no acute local or systemic effects of the compound have been reported from occupational exposure. In a field study on workers who inhaled antimony (III) sulfide dust over a long period of time (resulting from grinding processes), those affected showed no adverse health effects. In a second study, in which workers in the abrasive production were exposed to antimony (III) sulfide dust for a long time, an increased mortality rate due to heart disease was found. From animal experiments with sulphidic antimony ores there are indications that a carcinogenic effect cannot be excluded. However, the available database does not allow a risk assessment for humans.

Antimony (III) sulfide was included in the EU's ongoing action plan ( CoRAP ) in 2016 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 (III) sulfide ingestion was driven by concerns about worker exposure , high risk characterization ratio (RCR), other exposure / risk-based concerns and widespread use, and the potential risk of carcinogenic properties. The reassessment has been running since 2018 and is being carried out by Germany .

Individual evidence

1. ↑ ^{a b c d e f g h} Entry for CAS no. 1345-04-6 in the GESTIS substance database of the IFA , accessed on November 10, 2012(JavaScript required) .
2. ↑ ^{a b c} data sheet antimony (III) sulfide from Sigma-Aldrich , accessed on November 10, 2012 ( PDF ).
3. ↑ M. Binnewies, E. Milke: Thermochemical Data of Elements and Compunds . 2nd Edition. Wiley-VCH, Weinheim 2002, ISBN 3-527-30524-6 , pp. 828 .
4. ^ ^{A b c d} A. F. Holleman , E. Wiberg , N. Wiberg : Textbook of Inorganic Chemistry . 101st edition. Walter de Gruyter, Berlin 1995, ISBN 3-11-012641-9 , p. 817.
5. ↑ ^{a b} B. Cheng, ET Samulski: "One-step, ambient-temperature synthesis of antimony sulfide (Sb ₂ S ₃ ) micron-size polycrystals with a spherical morphology", in: Materials Research Bulletin , 2003 , 38 , p. 297-301; Full text ( Memento from September 7, 2006 in the Internet Archive ) (PDF; 196 kB)
6. ↑ RS Mane, BR Sankapal, CD Lokhande: "Non-aqueous chemical bath deposition of Sb ₂ S ₃ thin films", in: Thin Solid Films , 1999 , 353  (1), pp. 29-32; doi : 10.1016 / S0040-6090 (99) 00362-4 .
7. ↑ ^{a b c d e} A. F. Holleman , E. Wiberg , N. Wiberg : Textbook of Inorganic Chemistry . 102nd edition. Walter de Gruyter, Berlin 2007, ISBN 978-3-11-017770-1 .
8. ^ Aero Propulsion and Power Lab: Thermal Analysis Study of Antimony Sulfides , Charles K. Kelley, July 1989
9. ^ Ronald Rich: Inorganic Reactions in Water . Springer, 2007, ISBN 3-540-73962-9 , pp. 398 ( limited preview in Google Book search).
10. ↑ P. Bayliss, W. Nowacki: "Refinement of the crystal structure of stibnite, Sb ₂ S ₃ ", in: Zeitschrift für Kristallographie , 1972 , 135 , pp. 308-315; Full text (PDF; 312 kB).
11. ↑ Konrad Goehl : Observations and additions to the 'Circa instans'. In: Medical historical messages. Journal for the history of science and specialist prose research. Volume 34, 2015 (2016), pp. 69-77, here: p. 71.
12. ^ Peter Paetzold: Chemistry: An introduction . Walter de Gruyter, 2009, ISBN 3-11-020268-9 , p. 770 ( limited preview in Google Book search).
13. ↑ ^{a b} Alexander P. Hardt: Pyrotechnics , Pyrotechnica Publications, Post Falls Idaho USA 2001, ISBN 0-929388-06-2 , pp. 74 ff.
14. ↑ Entry on antimony sulfides. In: Römpp Online . Georg Thieme Verlag, accessed on May 15, 2014.
15. ↑ Community rolling action plan ( CoRAP ) of the European Chemicals Agency (ECHA): Antimony sulphide , accessed on March 26, 2019.