Aluminium sulfide explained

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 aluminium 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 SymmetrySpace
group
a (A)c (A)ρ (g/cm3)
αHexagonalP61 6.423 17.832.32
β HexagonalP63mc3.579 5.829 2.495
γTrigonal6.4717.26 2.36
δ TetragonalI41/amd 7.02629.8192.71

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 1,100 °C and may melt its way through steel. The cooled product is very hard.

Notes and References

  1. Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. .
  2. Book: Hans Landolt. D. Bimberg, Richard Börnstein. Richard Börnstein. Halbleiter. 23 September 2011. 1982. Springer. 978-3-540-13507-4. 12–.
  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) . fr . 7 . 632–696.
  4. 10.1002/zaac.19936190604. Synthese und Kristallstruktur einer Neuen hexagonalen Modifikation von Al2S3 mit fünffach koordiniertem Aluminum. 1993. Krebs. Bernt. Schiemann. Anke. läGe. Mechtild. Zeitschrift für anorganische und allgemeine Chemie. 619. 6. 983.
  5. 10.1016/0022-4596(70)90024-1. High-pressure spinel type Al2S3 and MnAl2S4. 1970. Donohue. P. Journal of Solid State Chemistry. 2. 1. 6–8 . 1970JSSCh...2....6D .
  6. Book: McPherson, William . A course in general chemistry . Henderson . William E. . Ginn and Company . 1913 . Boston . 445.