Chloride, lithium

Data reported for the protolysis constant of water in lithium chloride media are listed in Table 5.22. The data are solely for a temperature of 25 C, with the data being reported by Maeda et al. (1987) as given in the earlier work of Harned and Owen (1958). 

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One procedure makes use of a box on whose silk screen bottom powdered desiccant has been placed, usually lithium chloride. The box is positioned 1-2 mm above the surface, and the rate of gain in weight is measured for the film-free and the film-covered surface. The rate of water uptake is reported as u = m/fA, or in g/sec cm. This is taken to be proportional to - Cd)/R, where Ch, and Cd are the concentrations of water vapor in equilibrium with water and with the desiccant, respectively, and R is the diffusional resistance across the gap between the surface and the screen. Qualitatively, R can be regarded as actually being the sum of a series of resistances corresponding to the various diffusion gradients present ... 

Breslow supported this suggestion by demonstrating that the cycloaddition can be further accelerated by adding anti cliaotropic salts such as lithium chloride, whereas chaotropic salts such as guanidium chloride led to a retardation " "" ". On the basis of these experiments Breslow excluded all other possible explanations for the special effect of water on the Diels-Alder reaction " . 

Exp. 4) in 10 min with cooling at -30°C. After an additional 15 min 0.30 mol of a-chlororaethyl ethyl ether (note 2) was introduced in 10 min, while keeping the temperature between -20 and -30°C. A white precipitate of lithium chloride was formed. The cooling bath was then removed and the temperature was allowed to rise to +10°C. The mixture was hydrolyzed by shaking it with 200 ml of a solution of 30 g of ammonium chloride, to which 5 ml of aqueous ammonia had been added. 

Note 3. Commercial lithium chloride can be dried by heating at about 200°C/15 mmHg for 30 min. 

To a mixture of O.BB mol of anhydrous lithium chloride and 100 ml of OMSO was added a solution of 0.40 mol of the acetylenic tosylate (for a general procedure concerning the preparation of acetylenic tosylates, see Chapter VllI-3, Exp. 3) in IBO ml of DMSO. The flask was equipped for vacuum distillation (see Fig. 5). Between the receiver, which was cooled at -75°C, and the water-pump was placed a tube filled with KOH pellets. The apparatus was evacuated (10-20 mmHg) and the flask gradually heated until DMSO began to reflux in the column. The contents of... 

Some industrial processes produce predorninately latent air conditioning loads. Others dictate very low humidities and when the dew point falls below 0°C, free2ing becomes a major concern. Dehydration equipment, using soHd sorbents such as siUca gel and activated alurnina, or Hquid sorbents such as lithium chloride brine and triethylene glycol, may be used. The process is exothermic and may require cooling the exiting air stream to meet space requirements. Heat is also required for reactivation of the sorbent material. 

Terpoly(amide—imide—urethanes) have been synthesized in yields up to 50—75% by the reaction of 4-carhoxy-/V-(/)-hydroxypheny1)phtha1imide with diisocyanates in A/-meth5l-2-pyrrohdinone containing 5% lithium chloride (28). 

MPD-1 fibers may be obtained by the polymeriza tion of isophthaloyl chloride and y -phenylenediamine in dimethyl acetamide with 5% lithium chloride. The reactants must be very carefully dried since the presence of water would upset the stoichiometry and lead to low molecular weight products. Temperatures in the range of 0 to —40° C are desirable to avoid such side reactions as transamidation by the amide solvent and acylation of y -phenylenediamine by the amide solvent. Both reactions would lead to an imbalance in the stoichiometry and result in forming low molecular weight polymer. Fibers are dry spun direcdy from solution. 

Technora. In 1985, Teijin Ltd. introduced Technora fiber, previously known as HM-50, into the high performance fiber market. Technora is based on the 1 1 copolyterephthalamide of 3,4 -diaminodiphenyl ether and/ -phenylenediamine (8). Technora is a whoUy aromatic copolyamide of PPT, modified with a crankshaft-shaped comonomer, which results in the formation of isotropic solutions that then become anisotropic during the shear alignment during spinning. The polymer is synthesized by the low temperature polymerization of/ -phenylenediamine, 3,4 -diaminophenyl ether, and terephthaloyl chloride in an amide solvent containing a small amount of an alkaU salt. Calcium chloride or lithium chloride is used as the alkaU salt. The solvents used are hexamethylphosphoramide (HMPA), A/-methyl-2-pyrrohdinone (NMP), and dimethyl acetamide (DMAc). The stmcture of Technora is as follows ... 

Lithium Borohydride. Lithium borohydride [16949-15-8] LlBH, is made by metathesis between sodium borohydride and lithium chloride (20) ia isopropylamine. 

Stripping is accompHshed by dehydration using sulfuric acid (38), lithium chloride [7447-41-8] (39), and tertiary amines containing from 14—32 carbon atoms in an organic solvent immiscible with water followed by thermal treatment of the HCl—organic complex (40). 

Lithium Chloride. Lithium chloride [7447- 1-8], LiCl, is produced from the reaction of Hthium carbonate or hydroxide with hydrochloric acid. The salt melts at 608°C and bods at 1382°C. The 41-mol % LiCl—59-mol % KCl eutectic (melting point, 352°C) is employed as the electrolyte in the molten salt electrolysis production of Hthium metal. It is also used, often with other alkaH haHdes, in brazing flux eutectics and other molten salt appHcations such as electrolytes for high temperature Hthium batteries. 

Dog repeUents available commercially in the 1990s have been generally unsuccessful in laboratory tests. Por example, lithium chloride treatments were usually rejected immediately with no ingestion, and bone oil treatments that contained up to 0.1% of the active ingredient were stiH consumed (93). Oleoresin capsicum [8023-77-6], the essence of red pepper, did have an extended effect on coyotes, even though the deer repeUents mentioned above were attractive to coyotes (93). Although a capsicum-base aerosol repeUent has been described as potentially harmful (94), pepper spray is commercially available in the United States to repel humans, as is Mace. 

The first displacement reaction at C-2 position in carbohydrates was achieved during the study of sulfuryl chloride reaction with sucrose (92). Treatment of 3,4,6,3, 4, 6 -hexa-0-acetylsucrose 2,l -bis(chlorosulfate) with lithium chloride in hexamethylphosphoric triamide at 80°C for 20 h led to the corresponding 2,l -maimo derivative in 73% yield. 

Lithium Hypochlorite. Commercial lithium hypochlorite [13840-33-0], LiOCl, is a soHd with about 35% available chlorine. It is made from concentrated solutions of sodium hypochlorite and lithium chloride. It consists of 30% lithium hypochlorite and various other salts (34). 

The equihbrium shown in equation 3 normally ties far to the left. Usually the water formed is removed by azeotropic distillation with excess alcohol or a suitable azeotroping solvent such as benzene, toluene, or various petroleum distillate fractions. The procedure used depends on the specific ester desired. Preparation of methyl borate and ethyl borate is compHcated by the formation of low boiling azeotropes (Table 1) which are the lowest boiling constituents in these systems. Consequently, the ester—alcohol azeotrope must be prepared and then separated in another step. Some of the methods that have been used to separate methyl borate from the azeotrope are extraction with sulfuric acid and distillation of the enriched phase (18), treatment with calcium chloride or lithium chloride (19,20), washing with a hydrocarbon and distillation (21), fractional distillation at 709 kPa (7 atmospheres) (22), and addition of a third component that will form a low boiling methanol azeotrope (23). 

Aqueous salt solutions such as saturated 2inc chloride [7646-85-7] or calcium thiocyanate [2092-16-2] can dissolve limited amounts of cellulose (87). Two non-aqueous salt solutions are ammonium thiocyanate [1762-95-4]— uoamonia. and lithium chloride /744Z-4/A/—dimethyl acetamide [127-19-5]. Solutions up to about 15% can be made with these solvents. Trifluoroacetic acid [76-05-17—methylene chloride [75-09-2] and /V-methy1morpho1ine N-oxide [7529-22-8]—(92—94) are two other solvent systems that have been studied (95). 

The heHcoidal stmcture of such Hquid crystals can be carried to the soHd state by cross-linking (119,120) or by careful evaporation of solvent (121,122). Underivatized ceUulose can also form ordered mesophases (123,124), and gel films precipitated from lithium chloride—dimethyl acetamide retain some mesophase stmcture (122). 

Several derivatives of cellulose, including cellulose acetate, can be prepared in solution in dimethylacetamide—lithium chloride (65). Reportedly, this combination does not react with the hydroxy groups, thus leaving them free for esterification or etherification reactions. In another homogeneous-solution method, cellulose is treated with dinitrogen tetroxide in DMF to form the soluble cellulose nitrite ester this is then ester-interchanged with acetic anhydride (66). With pyridine as the catalyst, this method yields cellulose acetate with DS < 2.0. 

A third source of brine is found underground. Underground brines ate primarily the result of ancient terminal lakes that have dried up and left brine entrained in their salt beds. These deposits may be completely underground or start at the surface. Some of these beds ate hundreds of meters thick. The salt bed at the Salat de Atacama in Chile is over 300 m thick. Its bed is impregnated with brine that is being pumped to solar ponds and serves as feedstock to produce lithium chloride, potassium chloride, and magnesium chloride. Seades Lake in California is a similar ancient terminal lake. Brine from its deposit is processed to recover soda ash, borax, sodium sulfate, potassium chloride, and potassium sulfate. 

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