Hydride, lithium

There is one other important way in which borane can be stabilised. Diborane reacts with a suspension of lithium hydride in dry ether thus... 

When lithium hydride is allowed to react with aluminium chloride in ether solution, two reactions occur ... 

In the absence of excess lithium hydride, aluminium hydride slowly precipitates as a white polymer (A1H3) . With excess lithium hydride, the reaction ... 

Lithium aluminium hydride LiAlH is a useful and conveuient reagent for the selective reduction of the carbonyl group and of various other polar functional groups. It is obtained by treatment of finely powdered lithium hydride with an ethereal solution of anhydrous aluminium chloride ... 

The electrostatic potential map of hydrogen fluoride (HF) was shown in the preceding section and IS repeated here Compare it to the electrostatic po tential map of lithium hydride (LiH)... 

Uthium Mydride. Lithium hydride [7580-67-8] is very stable thermally and melts without decomposition. In the temperature range 600—800°C, the dissociation pressure for hydrogen, Pp, in units of kPa is expressed by... 

Lithium hydride reacts vigorously with siUcates above 180°C. Therefore, glass, quart2, and porcelain containers cannot be used in preparative processes. That only traces dissolve in polar solvents such as ether reflects its significant (60—75%) covalent bond character. It is completely soluble in, and forms eutectic melting compositions with, a number of fused salts. 

Normally, lithium hydride ignites in air only at high temperatures. When heated it reacts vigorously with CO2 and nitrogen. With the former, lithium formate is obtained. Reaction at high temperature with nitrogen produces lithium nitride. Therefore, dry limestone or NaCl powders are used to extinguish LiH fires. Lithium hydride reacts exothermically with moist air and violently with water. 

Preparation. Commercial manufacture of LiAlH uses the original synthetic method (44), ie, addition of a diethyl ether solution of aluminum chloride to a slurry of lithium hydride (Fig. 2). 

The stoichiometry (4 mol lithium hydride to 1 mol LiAlH ) makes this an inherently expensive process, even though high yields of pure product are obtained. For large-scale production, metathesis from NaAlH is economically preferred. 

Although there is Httle toxicity information pubHshed on hydrides, a threshold limit value (TLV) for lithium hydride in air of 25 fig/has been established (52). More extensive data are available (53) for sodium borohydride in the powder and solution forms. The acute oral LD q of NaBH is 50-100 mg/kg for NaBH and 50-1000 mg/kg for the solution. The acute dermal LD q (on dry skin) is 4-8 g/kg for NaBH and 100-500 mg/kg for the solution. The reaction or decomposition by-product sodium metaborate is slightly toxic orally (LD q is 2000-4000 mg/kg) and nontoxic dermally. 

The reaction of hydrogen and lithium readily gives lithium hydride [7580-67-8], LiH, which is stable at temperatures from the melting poiat up to 800°C. Lithium reacts with aitrogea, evea at ordiaary temperatures, to form the reddish browa nitride, Li3N. Lithium bums when heated in oxygen to... 

Uses. The largest use of lithium metal is in the production of organometaUic alkyl and aryl lithium compounds by reactions of lithium dispersions with the corresponding organohaHdes. Lithium metal is also used in organic syntheses for preparations of alkoxides and organosilanes, as weU as for reductions. Other uses for the metal include fabricated lithium battery components and manufacture of lithium alloys. It is also used for production of lithium hydride and lithium nitride. 

Lithium is used in metallurgical operations for degassing and impurity removal (see Metallurgy). In copper (qv) refining, lithium metal reacts with hydrogen to form lithium hydride which subsequendy reacts, along with further lithium metal, with cuprous oxide to form copper and lithium hydroxide and lithium oxide. The lithium salts are then removed from the surface of the molten copper. 

Lithium Amide. Lithium amide [7782-89-0], LiNH2, is produced from the reaction of anhydrous ammonia and lithium hydride. The compound can also be prepared by the removal of ammonia from solutions of lithium metal in the presence of catalysts (54). Lithium amide starts to decompose at 320°C and melts at 375°C. Decomposition of the amide above 400°C results first in lithium imide, Li2NH, and eventually in lithium nitride, Li N. Lithium amide is used in the production of antioxidants (qv) and antihistamines (see HiSTAMlNE AND HISTAMINE ANTAGONISTS). 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

The reductions of chlorosilanes by lithium aluminum hydride, lithium hydride, and other metal hydrides, MH, offers the advantages of higher yield and purity as well as dexibiUty in producing a range of siUcon hydrides comparable to the range of siUcon haUdes (59). The general reaction is as follows ... 

Lithium hydride is perhaps the most usehil of the other metal hydrides. The principal limitation is poor solubiUty, which essentially limits reaction media to such solvents as dioxane and dibutyl ether. Sodium hydride, which is too insoluble to function efficiently in solvents, is an effective reducing agent for the production of silane when dissolved in a LiCl—KCl eutectic at 348°C (63—65). Magnesium hydride has also been shown to be effective in the reduction of chloro- and fluorosilanes in solvent systems (66) and eutectic melts (67). 

Aromatic polysulfites can be produced if bisphenols, eg, bisphenol A, are heated with diphenyl sulfite in the presence of lithium hydride (112). Halosulfates and Halosulfites. A general method for the preparation of alkyl halosulfates and halosulfites is the treatment of the alcohol with sulfuryl or thionyl chloride at low temperatures while passing an inert gas through the mixture to remove hydrogen chloride (113). 

Lithium hydride. [7580-67-8] M 7.95, m 680", d 0.76-0.77. It should be a white powder otherwise replace it. It darkens rapidly on exposure to air and is decomposed by H2O to give H2 and LiOH, and reacts with lower alcohols. One gram in H2O liberates 2.8L of H2 (Could be explosive). 

ALUMINUM LITHIUM HYDRIDE see LITHIUM ALUMINUM HYDRIDE ... 

---