Antimony trisulfide

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Antimony trisulfide
Kristallstruktur Stibnit.png
Sulfid antimonity.JPG
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 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/3O.2Sb
    Key: IHBMMJGTJFPEQY-UHFFFAOYSA-N
  • S=[Sb]S[Sb]=S
Properties
Sb2S3
Molar mass 339.70 g·mol−1
AppearanceGrey 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.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
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).

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]

Contents

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.[ citation needed ] 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.[ clarification needed ] These coordinations consider the presence of secondary bonds. Some of the secondary bonds impart cohesion and are connected with packing. [16]

Related Research Articles

<span class="mw-page-title-main">Antimony</span> Chemical element, symbol Sb and atomic number 51

Antimony is a chemical element with the symbol Sb (from Latin stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient times and were powdered for use as medicine and cosmetics, often known by the Arabic name kohl. The earliest known description of the metalloid in the West was written in 1540 by Vannoccio Biringuccio.

<span class="mw-page-title-main">Pnictogen</span> Group (V) elements of the periodic table with valency 5

A pnictogen is any of the chemical elements in group 15 of the periodic table. Group (V) is also known as the nitrogen group or nitrogen family. Group (V) consists of the elements nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and moscovium (Mc).

<span class="mw-page-title-main">Stibnite</span> Sulfide mineral

Stibnite, sometimes called antimonite, is a sulfide mineral with the formula Sb2S3. This soft grey material crystallizes in an orthorhombic space group. It is the most important source for the metalloid antimony. The name is derived from the Greek στίβι stibi through the Latin stibium as the former name for the mineral and the element antimony.

In chemistry, antimonite refers to a salt of antimony(III), such as NaSb(OH)4 and NaSbO2 (meta-antimonite), which can be prepared by reacting alkali with antimony trioxide, Sb2O3. These are formally salts of antimonous acid, Sb(OH)3, whose existence in solution is dubious. Attempts to isolate it generally form Sb2O3·xH2O, antimony(III) oxide hydrate, which slowly transforms into Sb2O3.

<span class="mw-page-title-main">Cadmium sulfide</span> Chemical compound

Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow solid. It occurs in nature with two different crystal structures as the rare minerals greenockite and hawleyite, but is more prevalent as an impurity substituent in the similarly structured zinc ores sphalerite and wurtzite, which are the major economic sources of cadmium. As a compound that is easy to isolate and purify, it is the principal source of cadmium for all commercial applications. Its vivid yellow color led to its adoption as a pigment for the yellow paint "cadmium yellow" in the 18th century.

<span class="mw-page-title-main">Arsenic trisulfide</span> Chemical compound

Arsenic trisulfide is the inorganic compound with the formula As2S3. It is a dark yellow solid that is insoluble in water. It also occurs as the mineral orpiment, which has been used as a pigment called King's yellow. It is produced in the analysis of arsenic compounds. It is a group V/VI, intrinsic p-type semiconductor and exhibits photo-induced phase-change properties.

<span class="mw-page-title-main">Stibine</span> Chemical compound

Stibine (IUPAC name: stibane) is a chemical compound with the formula SbH3. A pnictogen hydride, this colourless, highly toxic gas is the principal covalent hydride of antimony, and a heavy analogue of ammonia. The molecule is pyramidal with H–Sb–H angles of 91.7° and Sb–H distances of 170.7 pm (1.707 Å). This gas has an offensive smell like hydrogen sulfide (rotten eggs).

<span class="mw-page-title-main">Antimony trioxide</span> Chemical compound

Antimony(III) oxide is the inorganic compound with the formula Sb2O3. It is the most important commercial compound of antimony. It is found in nature as the minerals valentinite and senarmontite. Like most polymeric oxides, Sb2O3 dissolves in aqueous solutions with hydrolysis. A mixed arsenic-antimony oxide occurs in nature as the very rare mineral stibioclaudetite.

<span class="mw-page-title-main">Chromium(III) oxide</span> Chemical compound

Chromium(III) oxide is an inorganic compound with the formula Cr
2O
3. It is one of the principal oxides of chromium and is used as a pigment. In nature, it occurs as the rare mineral eskolaite.

<span class="mw-page-title-main">Sodium thioantimoniate</span> Chemical compound

Sodium thioantimoniate or sodium tetrathioantimonate(V) is an inorganic compound with the formula Na3SbS4. The nonahydrate of this chemical, Na3SbS4·9H2O, is known as Schlippe's salt, named after Johann Karl Friedrich von Schlippe (1799–1867). These compounds are examples of sulfosalts. They were once of interest as species generated in qualitative inorganic analysis.

Antimony pentafluoride is the inorganic compound with the formula SbF5. This colourless, viscous liquid is a strong Lewis acid and a component of the superacid fluoroantimonic acid, formed upon mixing liquid HF with liquid SbF5 in 1:1 ratio. It is notable for its strong Lewis acidity and the ability to react with almost all known compounds.

<span class="mw-page-title-main">Antimony trichloride</span> Chemical compound

Antimony trichloride is the chemical compound with the formula SbCl3. It is a soft colorless solid with a pungent odor and was known to alchemists as butter of antimony.

<span class="mw-page-title-main">Antimony triiodide</span> Chemical compound

Antimony triiodide is the chemical compound with the formula SbI3. This ruby-red solid is the only characterized "binary" iodide of antimony, i.e. the sole compound isolated with the formula SbxIy. It contains antimony in its +3 oxidation state. Like many iodides of the heavier main group elements, its structure depends on the phase. Gaseous SbI3 is a molecular, pyramidal species as anticipated by VSEPR theory. In the solid state, however, the Sb center is surrounded by an octahedron of six iodide ligands, three of which are closer and three more distant. For the related compound BiI3, all six Bi—I distances are equal.

<span class="mw-page-title-main">Antimony triselenide</span> Chemical compound

Antimony triselenide is the chemical compound with the formula Sb2Se3. The material exists as the sulfosalt mineral antimonselite, which crystallizes in an orthorhombic space group. In this compound, antimony has a formal oxidation state +3 and selenium −2. The bonding in this compound has covalent character as evidenced by the black color and semiconducting properties of this and related materials. The low-frequency dielectric constant (ε0) has been measured to be 133 along the c axis of the crystal at room temperature, which is unusually large. Its band gap is 1.18 eV at room temperature.

A polysulfane is a chemical compound of formula H2Sn, where n > 1. Compounds containing 2 – 8 sulfur atoms have been isolated, longer chain compounds have been detected, but only in solution. H2S2 is colourless, higher members are yellow with the colour increasing with the sulfur content.In the chemical literature the term polysulfanes is sometimes used for compounds containing −(S)n−, e.g. organic polysulfanes R1−(S)n−R2.

Antimony pentasulfide is an inorganic compound of antimony and sulfur, also known as antimony red. It is a nonstoichiometric compound with a variable composition. Its structure is unknown. Commercial samples are contaminated with sulfur, which may be removed by washing with carbon disulfide in a Soxhlet extractor.

<span class="mw-page-title-main">Antimony tetroxide</span> Chemical compound

Antimony tetroxide is an inorganic compound with the formula Sb2O4. This material, which exists as the mineral cervantite, is white but reversibly yellows upon heating. The material, with empirical formula SbO2, is called antimony tetroxide to signify the presence of two kinds of Sb centers.

<span class="mw-page-title-main">Bismuth(III) sulfide</span> Chemical compound

Bismuth(III) sulfide is a chemical compound of bismuth and sulfur. It occurs in nature as the mineral bismuthinite.

<span class="mw-page-title-main">Copper(I) sulfide</span> Chemical compound

Copper(I) sulfide is a copper sulfide, a chemical compound of copper and sulfur. It has the chemical compound Cu2S. It is found in nature as the mineral chalcocite. It has a narrow range of stoichiometry ranging from Cu1.997S to Cu2.000S. Samples are typically black.

<span class="mw-page-title-main">Antimony(III) sulfate</span> Chemical compound

Antimony sulfate, Sb2(SO4)3, is a hygroscopic salt formed by reacting antimony or its compounds with hot sulfuric acid. It is used in doping of semiconductors and in the production of explosives and fireworks.

References

  1. 1 2 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. 1 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. 1 2 3 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. 1 2 3 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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