Lithium hydride (LiH) is an inorganic compound composed of lithium and hydrogen. This alkali metal hydride is a colorless solid, although commercial samples are grey. Characteristic of a salt-like (ionic) hydride, it has a high melting point, and it is not soluble but reactive with all protic organic solvents. It is soluble and nonreactive with certain molten salts such as lithium fluoride, lithium borohydride, and sodium hydride. With a molar mass of 7.95 g/mol, it is the lightest ionic compound.
Physical properties LiH is diamagnetic and an ionic conductor with an electric conductivity gradually increasing from 2×10−5 Ω−1cm−1 at 443 °C to 0.18 Ω−1cm−1 at 754 °C; there is no discontinuity in this increase through the melting point. The dielectric constant of LiH decreases from 13.0 (static, low frequencies) to 3.6 (visible-light frequencies). LiH is a soft material with a Mohs hardness of 3.5. Its compressive creep (per 100 hours) rapidly increases from < 1% at 350 °C to > 100% at 475 °C, meaning that LiH cannot provide mechanical support when heated. The thermal conductivity of LiH decreases with temperature and depends on morphology: the corresponding values are 0.125 W/(cm·K) for crystals and 0.0695 W/(cm·K) for compacts at 50 °C, and 0.036 W/(cm·K) for crystals and 0.0432 W/(cm·K) for compacts at 500 °C. The linear thermal expansion coefficient is 4.2×10−5/°C at room temperature.
Synthesis and processing LiH is produced by treating lithium metal with hydrogen gas:
2 Li + H2 → 2 LiH This reaction is especially rapid at temperatures above 600 °C. Addition of 0.001–0.003% carbon, and/or increasing temperature/pressure, increases the yield up to 98% at 2-hour residence time. However, the reaction proceeds at temperatures as low as 29 °C. The yield is 60% at 99 °C and 85% at 125 °C, and the rate depends significantly on the surface condition of LiH. Less common ways of LiH synthesis include thermal decomposition of lithium aluminium hydride (200 °C), lithium borohydride (300 °C), n-butyllithium (150 °C), or ethyllithium (120 °C), as well as several reactions involving lithium compounds of low stability and available hydrogen content. Chemical reactions yield LiH in the form of lumped powder, which can be compressed into pellets without a binder. More complex shapes can be produced by casting from the melt. Large single crystals (about 80 mm long and 16 mm in diameter) can be then grown from molten LiH powder in hydrogen atmosphere by the Bridgman–Stockbarger technique. They often have bluish color owing to the presence of colloidal Li. This color can be removed by post-growth annealing at lower temperatures (~550 °C) and lower thermal gradients. Major impurities in these crystals are Na (20–200 ppm), O (10–100 ppm), Mg (0.5–6 ppm), Fe (0.5-2 ppm) and Cu (0.5-2 ppm).
Bulk cold-pressed LiH parts can be easily machined using standard techniques and tools to micrometer precision. However, cast LiH is brittle and easily cracks during processing. A more energy efficient route to form lithium hydride powder is by ball milling lithium metal under high hydrogen pressure. To prevent cold welding of lithium metal (due to its high ductility), small amounts of lithium hydride powder are added during this process.
Reactions LiH powder reacts rapidly with air of low humidity, forming LiOH, Li2O and Li2CO3. In moist air the powder ignites spontaneously, forming a mixture of products including some nitrogenous compounds. The lump material reacts with humid air, forming a superficial coating, which is a viscous fluid. This inhibits further reaction, although the appearance of a film of "tarnish" is quite evident. Little or no nitride is formed on exposure to humid air. The lump material, contained in a metal dish, may be heated in air to slightly below 200 °C without igniting, although it ignites readily when touched by an open flame. The surface condition of LiH, presence of oxides on the metal dish, etc., have a considerable effect on the ignition temperature. Dry oxygen does not react with crystalline LiH unless heated strongly, when an almost explosive combustion occurs. LiH is highly reactive towards water and other protic reagents:
LiH + H2O → Li+ + H2 + OH− LiH is less reactive with water than Li and thus is a much less powerful reducing agent for water, alcohols, and other media containing reducible solutes. This is true for all the binary saline hydrides. LiH pellets slowly expand in moist air, forming LiOH; however, the expansion rate is below 10% within 24 hours in a pressure of 2 Torr of water vapor. If moist air contains carbon dioxide, then the product is lithium carbonate. LiH reacts with ammonia, slowly at room temperature, but the reaction accelerates significantly above 300 °C. LiH reacts slowly with higher alcohols and phenols, but vigorously with lower alcohols. LiH reacts with sulfur dioxide to give the dithionite:
2 LiH + 2 SO2 → Li2S2O4 + H2 though above 50 °C the product is lithium sulfide instead. LiH reacts with acetylene to form lithium carbide and hydrogen. With anhydrous organic acids, phenols and acid anhydrides, LiH reacts slowly, producing hydrogen gas and the lithium salt of the acid. With water-containing acids, LiH reacts faster than with water. Many reactions of LiH with oxygen-containing species yield LiOH, which in turn irreversibly reacts with LiH at temperatures above 300 °C:
LiH + LiOH → Li2O + H2 Lithium hydride is rather unreactive at moderate temperatures with O2 or Cl2. It is, therefore, used in the synthesis of other useful hydrides, e.g.,
8 LiH + Al2Cl6 → 2 Li[AlH4] + 6 LiCl 2 LiH + B2H6 → 2 Li[BH4]
Applications
Hydrogen storage and fuel With a hydrogen content in proportion to its mass three times that of NaH, LiH has the highest hydrogen content of any hydride. LiH is periodically of interest for hydrogen storage, but applications have been thwarted by its stability to decomposition. Thus removal of H2 requires temperatures above the 700 °C used for its synthesis, such temperatures are expensive to create and maintain. The compound was once tested as a fuel component in a model rocket.
Precursor to complex metal hydrides LiH is not usually a hydride-reducing agent, except in the synthesis of hydrides of certain metalloids. For example, silane is produced in the reaction of lithium hydride and silicon tetrachloride by the Sundermeyer process:
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