Antimony trisulfide

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Antimony trisulfide
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Template:Longitem Template:Chem2
Molar mass Template:Chem molar mass
Appearance Grey or black orthorhombic crystals (stibnite)
Density 4.562g cm−3 (stibnite)[1]
Melting point Template:Chembox CalcTemperatures
Boiling point Template:Chembox CalcTemperatures
Template:Longitem −86.0·10−6 cm3/mol
Template:Longitem 4.046
Template:Longitem 123.32 J/(mol·K)
Template:Longitem −157.8 kJ/mol
Template:Longitem Template:Ubl
Template:Longitem Arsenic trisulfide
Bismuth(III) sulfide
Template:Longitem Antimony pentasulfide

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Antimony trisulfide (Template:Chem2) is found in nature as the crystalline mineral stibnite and the amorphous red mineral (actually a mineraloid)[2] metastibnite.[3] It is manufactured for use in safety matches, military ammunition, explosives and fireworks. It is also used as a friction material in brake linings. It is a critical primer material for military applications and tracer bullets.[4] 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 Template:Chem2), the first good orange pigment available for cotton fabric printing.[7]

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.Script error: No such module "Unsubst". With suitable doping, p and n type materials can be produced.[8]

Preparation and reactions

Template:Chem2 can be prepared from the elements at temperature 500–900 °C:[5]

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Template:Chem2 is precipitated when [[hydrogen sulfide|Template:Chem2]] is passed through an acidified solution of Sb(III).[9] This reaction has been used as a gravimetric method for determining antimony, bubbling Template:Chem2 through a solution of Sb(III) compound in hot HCl deposits an orange form of Template:Chem2 which turns black under the reaction conditions.[10]

Template:Chem2 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 Template:Chem2 and chlorates may explode.[11]

In the extraction of antimony from antimony ores the alkaline sulfide process is employed where Template:Chem2 reacts to form thioantimonate(III) salts (also called thioantimonite):[12]

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A number of salts containing different thioantimonate(III) ions can be prepared from Template:Chem2. These include:[13]

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Schlippe's salt, Template:Chem2, a thioantimonate(V) salt is formed when Template:Chem2 is boiled with sulfur and sodium hydroxide. The reaction can be represented as:[9]

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Structure

The structure of the black needle-like form of Template:Chem2, 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 Template:Chem2 and Template:Chem2.[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 Template:Chem2, with (3+4) coordination at the M1 site and (5+2) at the M2 site.Template:Cln These coordinations consider the presence of secondary bonds. Some of the secondary bonds impart cohesion and are connected with packing.[16]

References

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  3. SUPERGENE METASTIBNITE FROM MINA ALACRAN, PAMPA LARGA, COPIAPO, CHILE, Alan H Clark, THE AMERICAN MINERALOGIST. VOL. 55., 1970
  4. www.antimonytrisulfide.com
  5. a b c Script error: No such module "citation/CS1".
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  8. Electrochemistry of Metal Chalcogenides, Mirtat Bouroushian, Springer, 2010
  9. a b c Template:Holleman&Wiberg
  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, Template:ISBN
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  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, Template:ISBN
  14. Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications Template:ISBN
  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.
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Template:Antimony compounds Template:Sulfides