Lithium trihydrated

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. 

Lithium Borates. Two lithium borates are of minor commercial importance, the tetraborate trihydrate and metaborate hydrates. 

Lithium nitrate [7790-69-4] M 68.9, m 253", d 2.38. Crystd from water or EtOH. Dried at 180° for several days by repeated melting under vacuum. If it is crystallised from water keeping the temperature above 70°, formation of trihydrate is avoided. The anhydrous salt is dried at 120° and stored in a vac desiccator over CaS04. After 99% salt was recrystd 3 times it contained metal (ppm) Ca (1.6), K (1.1), Mo (0.4), Na (2.2). 

Lithium perchlorate [7791-03-9] M 106.4, pK -2.4 to -3.1 (for HCIO4). Crystd from water or 50% aq MeOH. Rendered anhydrous by heating the trihydrate at 170-180° in an air oven. It can then be recrystd twice from acetonitrile and again dried under vacuum [Mohammad and Kosower J Am Chem Soc 93 2713 19711... 

Lithium. salts show a great propensity to crystallize as hydrates, the trihydrates being particularly common, e.g. LiX.3HiO, X = Cl, Br, I, CIOi, CIOj, MnO.1, NO3, BF4, etc. In most of these Li is coordinated by 6H2O to form chains of face-sharing octahedra ... 

Catalyst A mixture of 5.26 g of rhodium chloride trihydrate, 0.34 g of palladium chloride, 18 g of carbon (Darco G-60), and 200 ml of water is rapidly stirred and heated to 80°. A solution of lithium hydroxide hydrate (2.7 g) in 10 ml of water is added in one portion and the heating discontinued. Stirring is continued overnight, after which the mixture is filtered and washed with 100 ml of 0.5 % aqueous acetic acid. The product is dried in a vacuum oven at 65°. About 20 g of the catalyst is thus obtained. 

To a solution of 2 g. of rhodium(III) chloride trihydrate in 70 ml. of ethanol is added 12 g. of triphenylphosphine in 250 ml. of hot ethanol. After refluxing until the red solution begins to lighten in color (about 5 minutes), 8 g. of lithium bromide dissolved in 50 ml. of hot ethanol is added and the mixture refluxed for an hour. The orange prisms of the complex are collected by filtration, washed with 50 ml. of anhydrous ether, and dried in vacuum yield 5.1 g. (64% based on rhodium). 

LAURIC ACID, VINYL ESTER, 30, 106 Laurone, 31, 68 Lauroyl chloride, 31,68 Laurylmethylamine, 36, 48 Lead acetate trihydrate, 31, 19 Lead sulfide, 31, 19 Lead tetraacetate, 35, 18 Lithium aluminum hydride, 32, 46 33, 33, 82 36, 49... 

Campos, Sampedro and Rodriguez studied theoretically in 1998 the competition of the concerted and stepwise mechanism of hydrogen migration and lithium iodide a-eUmination in the trihydrate 1-iodo-l-lithioethene 28. Since the lithiated derivative of 1-iodoethane readily decomposes to ethylene, experimental techniques are found to be of less use. Their ab initio theoretical calculations indicate that the preferred mechanism is the concerted rather than stepwise pathway as illustrated in Eigure 33. Their studies also suggest that 1-iodo-l-thioethene prefers to be a monomer in THE and the activation barriers for the cis and trans hydrogen migration are nearly the same. 

At a glance, the result of the X-ray structure analysis of 5 contradicts theoretical calculations that predict the bridged structure 6 to be the most stable alternative of Cl2CHLi. However, calculations of the trihydrate of Cl2CHLi result in the stmcmre 7 wherein the lithium is solvated by three water molecules . The similarity between the calculated trihydrate 7 and the tris(pyridine) coordinated structure 5 is obvious. 

The trihydrate salt is obtained by neutrahzation of lithium hydroxide or lithium carbonate solution with pure hydriodic acid followed by concentration of the solution for crystallization ... 

Based on the early racemic synthesis of 4 (cis series), it had already been demonstrated that 2-azetidinone ring closure could be achieved via nucleophilic attack of a lithium amine anion on a (3-ester. Cyclization could be accomplished with other strong bases, but sodium bistrimethylsilylamide was found to effect efficient cyclization without significant racemization at C3. During the search for experimentally convenient bases, it was noted that Noyori (Nakamura et al., 1983) reported that tetrabutylammonium fluoride (TBAF) as well as LiF, KF, and CsF could serve as the base in Aldol reactions. Treatment of 17a or 17b with TBAF trihydrate in THF did not affect cyclization. After much experimentation it was found that addition of A,0-bistrimethylacetamide (BSA) to 19 followed by TBAF addition, effected 2-azetidinone ring closure. Further optimization found that use of catalytic TBAF (< 1%) in methylene chloride afforded near quantitative cyclization. 

M.F, Muiphy, Two Explosives Generating Condensible Products", NOLTR 63-12(1963) [Mixts studied were Lithium Perchlorate Trihydrate (3 moles) Aluminum (8 moles) and amorphous Al powd with aq hydrogen peroxide (90%)]... 

According to A. Potilitzin, the melting point of trihydrated lithium perchlorate is 95° and, between 98° and 100°, the salt loses approximately two-thirds of its combined water and all the water is lost between 130° and 150° the anhydrous salt melts at 236°, and loses no oxygen at 300° this gas is evolved at about 368°, at 380° the speed of decomposition is rapid—lithium chlorate and chloride are first... 

C. F. Rammelsberg found that if a soln. of lithium carbonate be nearly neutralized with periodic acid, a crystalline mass is obtained when evaporated in a warm place.5 The crystals have the composition trihydrated lithium dimesoperiodate, Li4l209.3H20, which can also be regarded as secondary sodium paraperiodate, Li2H3I06. They lose no water at 100°, but 9 28 per cent, is lost at 200°, and at 275° oxygen comes off as well. 

The properties of the alkali sulphates.—Lithium sulphate can be prepared as the anhydrous and hydrated as monohydrated lithium sulphate, Li2S04.H20 and sodium sulphate as the anhydrous salt, as heptahydrated sodium sulphate, NaS04-7H20 and decahydrated sodium sulphate, Na2S04-10H20. Mono- and trihydrated sodium salts have been reported—the former by J. Thomsen,22 the latter by H. Rose—but L. G. de Goppet has questioned the two last-named hydrates. 

Materials. Distilled water was used 2-propanol and trihydrous lithium perchlorate, of guaranteed reagent quality from Wako Pure Chemicals Co., were used without further purification. The purity of the 2-propanol was checked by gas chromatography, with Porapak-Q as the column packing, and found to be more than 99.9 mol %. The physical properties of pure solvents were compared with the literature values in a previous paper (2), and the agreement was satisfactory. 

Equilibrium vapor condensate was analyzed by means of density measurement at 25.00° 0.02°C. An Ostwald pycnometer (capacity ca. 5 cm3) was used. Liquid phase composition was calculated by taking a material balance. In this case, the three moles of water present in trihydrous lithium perchlorate were considered water component. The accuracies of both compositions were 0.001 mole fraction. 

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