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Monday, February 6, 2017

What is Lithium aluminium hydride

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula LiAlH4. It was discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic synthesis, especially for the reduction of esters, carboxylic acids, and amides. The solid is dangerously reactive toward water, releasing gaseous hydrogen (H2). Some related derivatives have been discussed for hydrogen storage.
LAH is a colorless solid, but commercial samples are usually gray due to contamination.This material can be purified by recrystallization from diethyl ether. Large-scale purifications employ a Soxhlet extractor. Commonly, the impure gray material is used in synthesis, since the impurities are innocuous and can be easily separated from the organic products. The pure powdered material is pyrophoric, but not its large crystals. Some commercial materials contain mineral oil to inhibit reactions with atmospheric moisture, but more commonly it is packed in moisture-proof plastic sacks.

LAH violently reacts with water, including atmospheric moisture. The reaction proceeds according to the following idealized equation:
LiAlH4 + 4 H2O → LiOH + Al(OH)3 + 4 H2

This reaction provides a useful method to generate hydrogen in the laboratory. Aged, air-exposed samples often appear white because they have absorbed enough moisture to generate a mixture of the white compounds lithium hydroxide and aluminium hydroxide.
LAH crystallizes in the monoclinic space group P21/c. The unit cell has the dimensions: a = 4.82, b = 7.81, and c = 7.92 Å, α = γ=90° and β=112°. In the structure, Li+ centers are surrounded by five AlH−4 tetrahedra. The Li+ centers are bonded to one hydrogen atom from each of the surrounding tetrahedra creating a bipyramid arrangement. At high pressures (>2.2 GPa) a phase transition may occur to give β-LAH.
X-ray powder diffraction pattern of as-received LiAlH4. The asterisk designates an impurity, possibly LiCl.
LiAH was first prepared from the reaction between lithium hydride (LiH) and aluminium chloride:

4 LiH + AlCl3 → LiAlH4 + 3 LiCl

In addition to this method, the industrial synthesis entails the initial preparation of sodium aluminium hydride from the elements under high pressure and temperature:

Na + Al + 2 H2 → NaAlH4

LiAlH4 is then prepared by a salt metathesis reaction according to:

NaAlH4 + LiCl → LiAlH4 + NaCl

which proceeds in a high yield of LAH. LiCl is removed by filtration from an ethereal solution of LiAH, with subsequent precipitation of LiAH to yield a product containing around 1% w/w LiCl.