LiH is diamagnetic and an ionic conductor with an electric conductivity gradually increasing from 2×10−5Ω−1cm−1 at 443°C to 0.18Ω−1cm−1 at 754°C; there is no discontinuity in this increase through the melting point.[3]:36 The dielectric constant of LiH decreases from 13.0 (static, low frequencies) to 3.6 (visible-light frequencies).[3]:35 LiH is a soft material with a Mohs hardness of 3.5.[3]:42 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.[3]:39
The thermal conductivity of LiH decreases with temperature and depends on morphology: the corresponding values are 0.125W/(cm·K) for crystals and 0.0695W/(cm·K) for compacts at 50°C, and 0.036W/(cm·K) for crystals and 0.0432W/(cm·K) for compacts at 500°C.[3]:60 The linear thermal expansion coefficient is 4.2×10−5/°C at room temperature.[3]:49
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.[3]:147 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.[3]:5
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.[3]:160 ff. Large single crystals (about 80mm long and 16mm 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.[3]:154 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).[3]:155
Cracking in cast LiH after machining with a fly cutter. Scale is in inches.
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.[3]:171
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.[7]
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.[3]:6
LiH is highly reactive towards water and other protic reagents:[3]:7
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.[3]:22
LiH pellets slowly expand in moist air, forming LiOH; however, the expansion rate is below 10% within 24 hours in a pressure of 2Torr of water vapor.[3]:7 If moist air contains carbon dioxide, then the product is lithium carbonate.[3]:8 LiH reacts with ammonia, slowly at room temperature, but the reaction accelerates significantly above 300°C.[3]:10 LiH reacts slowly with higher alcohols and phenols, but vigorously with lower alcohols.[3]:14
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.[3]:8 Many reactions of LiH with oxygen-containing species yield LiOH, which in turn irreversibly reacts with LiH at temperatures above 300°C:[3]:10
Lithium hydride is rather unreactive at moderate temperatures with O2 or Cl2. It is, therefore, used in the synthesis of other useful hydrides,[8] e.g.,
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.[9][10]
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:
Lithium hydride (LiH) is sometimes a desirable material for the shielding of nuclear reactors, with the isotope lithium-6 (Li-6), and it can be fabricated by casting.[12][13]
Moderator
Lithium deuteride, in the form of lithium-7deuteride (7Li2H or 7LiD), is a good moderator for nuclear reactors, because deuterium (2H or D) has a lower neutron absorption cross-section than ordinary hydrogen or protium (1H) does, and the cross-section for 7Li is also low, decreasing the absorption of neutrons in a reactor. 7Li is preferred for a moderator because it has a lower neutron capture cross-section, and it also forms less tritium (3H or T) under bombardment with neutrons.[14]
Thermonuclear weapons
Lithium deuteride (LiD), specifically with the rare isotope 6 3Li, but also with the more common isotope of 7 3Li, is the primary fusion fuel in thermonuclear weapons of both the Teller–Ulam design and "Sloika" types. In both designs, a nuclear fission trigger explodes to heat and compress the lithium deuteride, and to bombard it with neutrons to produce tritium in an exothermic reaction:
The high-energy neutron produced by the deuterium-tritium reaction can then go on to react with more LiD, or go on to induce nuclear fission in fissionable materials (which can include uranium-238 in this context, because the fusion neutron is of sufficiently high energy), which can produce more neutrons, to continue the process.[15] The maximum explosive yield of lithium deuteride fusion is around 50 kilotons per kilogram of material reacted, making it about 3 times more energy dense than nuclear fission.[16]
Using lithium deuteride as a thermonuclear fuel source simplifies thermonuclear weapons design over attempts to use pure deuterium (which must be kept cryogenically cold to stay in a liquid form, as was done as part of the Ivy Mike experiment in 1952), or to produce large amounts of gaseous tritium, which is prohibitively expensive. Lithium deuteride allows the tritium to be formed in situ as part of the reaction. The ignition and burn rate of LiD is much higher than pure deuterium, and the burn time is shorter than a pure deuterium-tritium reaction, and it requires a strong source of neutrons to sustain the tritium production cycle. It is also necessarily heavier than pure deuterium. But the practical advantages outweigh these deficits.[16]
Before the Castle Bravonuclear weapons test in 1954, it was thought that only the less common isotope 6 3Li would breed tritium when struck with fast neutrons. The Castle Bravo test showed (accidentally) that the more plentiful 7 3Li also does so in significant quantities under the extreme conditions of an exploding thermonuclear weapon, and the test yield was 2.5 times larger than predicted as a result of this additional tritium production.
Safety
LiH reacts violently with water to give hydrogen gas and LiOH, which is caustic. Consequently, LiH dust can explode in humid air, or even in dry air due to static electricity. At concentrations of 5–55 mg/m3 in air the dust is extremely irritating to the mucous membranes and skin and may cause an allergic reaction. Because of the irritation, LiH is normally rejected rather than accumulated by the body.[3]:157,182
Some lithium salts, which can be produced in LiH reactions, are toxic. LiH fire should not be extinguished using carbon dioxide, carbon tetrachloride, or aqueous fire extinguishers; it should be smothered by covering with a metal object or graphite or dolomite powder. Sand is less suitable, as it can explode when mixed with burning LiH, especially if not dry. LiH is normally transported in oil, using containers made of ceramic, certain plastics or steel, and is handled in an atmosphere of dry argon or helium.[3]:156 Whilst nitrogen can be used, it will react with lithium at elevated temperatures.[3]:157 LiH normally contains some metallic lithium, which corrodes steel or silica containers at elevated temperatures.[3]:173–174,179
References
123Lide, D. R., ed. (2005). CRC Handbook of Chemistry and Physics (86thed.). Boca Raton, Florida: CRC Press. p.4.70. ISBN0-8493-0486-5.
↑Solvent-and catalyst-free mechanochemical synthesis of alkali metal monohydrides IZ Hlova, A Castle, JF Goldston, S Gupta, T Prost… - Journal of Materials Chemistry A, 2016
↑Welch, Frank H. (February 1974). "Lithium hydride: A space age shielding material". Nuclear Engineering and Design. 26 (3): 440–460. doi:10.1016/0029-5493(74)90082-X.
↑York, Herbert F. (1976). The Advisors: Oppenheimer, Teller, and the Superbomb. Stanford University Press. p.28. In the 1960s and 1970s, the U.S. Department of Energy declassified the following statements about lithium hydrides as thermonuclear fuels: "The fact that lithium, deuterium (Li6D, LiD) are used in unspecified thermonuclear weapons." "The mere fact that normal lithium deuteride (LinD) is used in unspecified TN weapons." "The fact that compounds of Li6 containing tritium are used in the design of weapons as TN fuel." U.S. Department of Energy, Office of Declassification (January 1, 2001). "RESTRICTED DATA DECLASSIFICATION DECISIONS 1946 TO THE PRESENT (RDD-7)". Federation of American Scientists.
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