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Aluminium sulfide

Aluminum sulfide is a chemical compound with the formula Al<sub>2</sub>S<sub>3</sub>. This colorless species has an interesting structural chemistry, existing in several forms. The material is sensitive to moisture, hydrolyzing to hydrated aluminum oxides/hydroxides. This can begin when the sulfide is exposed to the atmosphere. The hydrolysis reaction generates gaseous hydrogen sulfide (H<sub>2</sub>S).

Crystal structure

More than six crystalline forms of aluminum 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.

The β and γ phases are obtained by annealing the most stable α-Al<sub>2</sub>S<sub>3</sub> phase at several hundred degrees Celsius. Compressing aluminum sulfide to 2–65 bar results in the δ phase where vacancies are arranged in a superlattice of tetragonal symmetry.

Unlike Al<sub>2</sub>O<sub>3</sub>, in which the Al(III) centers occupy octahedral holes, the more expanded framework of Al<sub>2</sub>S<sub>3</sub> 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-Al<sub>2</sub>S<sub>3</sub> forms, with a structure akin to γ-Al<sub>2</sub>O<sub>3</sub>.

Molecular derivatives of Al<sub>2</sub>S<sub>3</sub> are not known. Mixed Al-S-Cl compounds are however known. Al<sub>2</sub>Se<sub>3</sub> and Al<sub>2</sub>Te<sub>3</sub> are also known.

Preparation

Aluminum sulfide is readily prepared by ignition of the elements

2 Al + 3 S → Al<sub>2</sub>S<sub>3</sub>

This reaction is extremely exothermic and it is not necessary or desirable to heat the whole mass of the sulfur-aluminum 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&nbsp;°C and may melt its way through steel. The cooled product is very hard.

References