Aluminium sulfide

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Aluminium sulfide
Names
Other names
Aluminium sulfide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.736 Edit this at Wikidata
EC Number
  • 215-109-0
UNII
  • InChI=1S/2Al.3S/q2*+3;3*-2 checkY
    Key: COOGPNLGKIHLSK-UHFFFAOYSA-N checkY
  • InChI=1/2Al.3S/q2*+3;3*-2
    Key: COOGPNLGKIHLSK-UHFFFAOYAY
  • [Al+3].[Al+3].[S-2].[S-2].[S-2]
Properties
Al2S3
Molar mass 150.158 g/mol
Appearance gray solid
Density 2.02 g/cm3
Melting point 1,100 °C (2,010 °F; 1,370 K)
Boiling point 1,500 °C (2,730 °F; 1,770 K) sublimes
decomposes
Solubility insoluble in acetone
Structure
trigonal
Thermochemistry
105.1 J/mol K
116.9 J/mol K
-724 kJ/mol
Hazards
GHS labelling:
GHS02: FlammableGHS07: Exclamation mark
Danger
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
4
0
2
Safety data sheet (SDS) [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Aluminium sulfide is a chemical compound with the formula Al2S3. This colorless species has an interesting structural chemistry, existing in several forms. The material is sensitive to moisture, hydrolyzing to hydrated aluminum oxides/hydroxides.[1] This can begin when the sulfide is exposed to the atmosphere. The hydrolysis reaction generates gaseous hydrogen sulfide (H2S).

Crystal structure

More than six crystalline forms of aluminium sulfide are known and only some are listed below. Most of them have rather similar, wurtzite-like structures, and differ by the arrangement of lattice vacancies, which form ordered or disordered sublattices.[2][3]

Form Symmetry Space
group
a (A) c (A) ρ (g/cm3)
α Hexagonal P61 6.423 17.83 2.32
β Hexagonal P63mc 3.579 5.829 2.495
γ Trigonal 6.47 17.26 2.36
δ Tetragonal I41/amd 7.026 29.819 2.71

The β and γ phases are obtained by annealing the most stable α-Al2S3 phase at several hundred degrees Celsius.[4] Compressing aluminium sulfide to 2–65 bar results in the δ phase where vacancies are arranged in a superlattice of tetragonal symmetry.[5]

Unlike Al2O3, in which the Al(III) centers occupy octahedral holes, the more expanded framework of Al2S3 stabilizes the Al(III) centers into one third of the tetrahedral holes of a hexagonally close-packed arrangement of the sulfide anions. At higher temperature, the Al(III) centers become randomized to give a "defect wurtzite" structure. And at still higher temperatures stabilize the γ-Al2S3 forms, with a structure akin to γ-Al2O3.

Molecular derivatives of Al2S3 are not known. Mixed Al-S-Cl compounds are however known. Al2Se3 and Al2Te3 are also known.

Preparation

Aluminium sulfide is readily prepared by ignition of the elements[6]

2 Al + 3 S → Al2S3

This reaction is extremely exothermic and it is not necessary or desirable to heat the whole mass of the sulfur-aluminium mixture; (except possibly for very small amounts of reactants). The product will be created in a fused form; it reaches a temperature greater than 1100 °C and may melt its way through steel. The cooled product is very hard.

References

  1. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  2. ^ Hans Landolt; D. Bimberg, Richard Börnstein; Richard Börnstein (1982). Halbleiter. Springer. pp. 12–. ISBN 978-3-540-13507-4. Retrieved 23 September 2011.
  3. ^ Flahaut, J. (1952). "Contribution à l'étude du sulfure d'aluminium et des thioaluminates" [Contribution to the study of aluminum sulfide and thioaluminates]. Annales de Chimie (Paris) (in French). 7: 632–696.
  4. ^ Krebs, Bernt; Schiemann, Anke; läGe, Mechtild (1993). "Synthese und Kristallstruktur einer Neuen hexagonalen Modifikation von Al2S3 mit fünffach koordiniertem Aluminum". Zeitschrift für anorganische und allgemeine Chemie. 619 (6): 983. doi:10.1002/zaac.19936190604.
  5. ^ Donohue, P (1970). "High-pressure spinel type Al2S3 and MnAl2S4". Journal of Solid State Chemistry. 2 (1): 6–8. Bibcode:1970JSSCh...2....6D. doi:10.1016/0022-4596(70)90024-1.
  6. ^ McPherson, William; Henderson, William E. (1913). A course in general chemistry. Boston: Ginn and Company. p. 445.