Perchlorate, lithium

Data reported for the protolysis constant of water in lithium perchlorate media are listed in Table 5.25. The data are solely for a temperature of 25 °C, with the data being reported by Maeda et al. (1987). 

Recrystallization from water or aqueous methanol, followed by heating at 170-180 °C in an air oven (vacuum is also suitable) to remove waters of hydration. Subsequent crystallization from acetonitrile is also suggested to improve purity. 

Tompkins, Nonaqueous Electrolytes, Academic Press New York, 1972 and 1974, Vols. I and II. 

in Organic Electrochemistry, 3rd ed., H. Lund, M. M. Baizer, Eds., Marcel Dekker New York, 1991. 

CRC Handbook of Chemistry and Physics, 85th ed., CRC Press Boca Raton, FL, 2004. 

Despite its many advantages, the high oxidation state of chlorine (VII) in Cl04 results in problems. LiCl04 solutions are thermally unstable and show explosion risks, especially in ethers [64, 65]. 

---

In 1990 Grieco introduced a 5 molar solution of lithium perchlorate as a new medium for the Diels-Alder reaction that is capable of inducing not only an improvement of the rate but also of the endo-... 

Lithium Perchlorate. Lithium perchlorate [7791 -03-9], LiClO, is prepared from neutralization of perchloric acid using lithium hydroxide or... 

Alkali Metal Perchlorates. The anhydrous salts of the Group 1 (lA) or alkah metal perchlorates are isomorphous with one another as well as with ammonium perchlorate. Crystal stmctures have been determined by optical and x-ray methods (38). With the exception of lithium perchlorate, the compounds all exhibit dimorphism when undergoing transitions from rhombic to cubic forms at characteristic temperatures (33,34). Potassium perchlorate [7778-74-7] KCIO, the first such compound discovered, is used in pyrotechnics (qv) and has the highest percentage of oxygen (60.1%). 

The U.S. domestic capacity of ammonium perchlorate is roughly estimated at 31,250 t/yr. The actual production varies, based on the requirements for soHd propellants. The 1994 production ran at about 11,200 t/yr, 36% of name plate capacity. Environmental effects of the decomposition products, which result from using soHd rocket motors based on ammonium perchlorate-containing propellants, are expected to keep increasing pubHc pressure until consumption is reduced and alternatives are developed. The 1995 price of ammonium perchlorate is in the range of 1.05/kg. Approximately 450 t/yr of NH ClO -equivalent cell Hquor is sold to produce magnesium and lithium perchlorate for use in the production of batteries (113). Total U.S. domestic sales and exports for sodium perchlorate are about 900 t/yr. In 1995, a solution containing 64% NaClO was priced at ca 1.00/kg dry product was also available at 1.21/kg. 

The titanium sulfide is able to act as a lithium reservoir. On iatercalation with lithium, the titanium lattice expands from ca 570 to 620 pm as the iatercalation proceeds to completion on formation of TiI iS2. Small button cells have been developed, incorporating lithium perchlorate ia propyleae carboaate electrolyte, for use ia watches and pocket calculators (see Batteries). 

S-Substituted thiiranium ions react with water and alcohols to give trans ring opening (Scheme 72). A report that oxygen nucleophiles attack sulfur as well as carbon has been shown to be incorrect (79ACR282). The intermediate thiiranium ion (57) in the presence of lithium perchlorate readily yields the carbenium ion which undergoes a transannular hydride... 

S-Substituted thiiranium ions react with secondary amines to give ring-opened products. Nitriles also react with thiiranium ions, probably via an open carbenium ion whose formation is favored by increasing the polarity of the medium by the addition of lithium perchlorate (Scheme 79) (79ACR282). An intramolecular displacement by an amide nitrogen atom on an intermediate thiiranium ion has been invoked (80JA1954). 

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... 

Anhydrous lithium perchlorate (60 g.) obtained from Ventron Corporation was placed in a 500-ml. flask under dry nitrogen, and 85 ml. of anhydrous 1,2-dimethoxyethane was added. The mixture became... 

When the lithium perchlorate was dissolved initially in the entire 240 ml. of 1,2-dimethoxye thane and processed as above, the yield was considerably lower. The submitters report that, if less lithium perchlorate is used in the preparation of the octamethyltetraoxaquaterene, the 3neld of the product is lowered. 

The method described here gives higher yields of the macrocyclic tetraethers and allows the product from furan and cyclohexanone to be formed directly in 5-10% yield, whereas this product was previously obtained only by an indirect route. The added lithium perchlorate undoubtedly accelerates the reaction, since after short reaction times the product was isolated in 20% yield when the salt was present and in only 5% yield when the salt was absent. The lithium cation is presumably acting as a template which coordinates with the oxygen atoms of... 

These reactions are presumed to occur through aroyl triflate intermediates which dissociate to aiyl acylium ions. Lithium perchlorate and scandium triflate also promote acylation. ... 

The similarity between the cryptands and the first of these molecules is obvious. Compound 7 7 is a urethane equivalent of [2.2.2]-cryptand. The synthesis of 7 7 was accomplished using a diacyl halide and l,10-diaza-18-crown-6 (shown in Eq. 8.13). Since amidic nitrogen inverts less rapidly than a tertiary amine nitrogen, Vogtle and his coworkers who prepared 7 7, analyzed the proton and carbon magnetic resonance spectra to discern differences in conformational preferences. Compound 7 7 was found to form a lithium perchlorate complex. 

Selective hydroxylation with osmium tetroxide (one equivalent in ether-pyridine at 0 ) converts (27) to a solid mixture of stereoisomeric diols (28a) which can be converted to the corresponding secondary monotoluene-sulfonate (28b) by treatment with /7-toluenesulfonyl chloride in methylene dichloride-pyridine and then by pinacol rearrangement in tetrahydrofuran-lithium perchlorate -calcium carbonate into the unconjugated cyclohepte-none (29) in 41-48 % over-all yield from (27). Mild acid-catalyzed hydrolysis of the ketal-ketone (29) removes the ketal more drastic conditions by heating at 100° in 2 hydrochloric acid for 24 hr gives the conjugated diketone (30). 

Strong acids or superacid systems generate stable fluorinated carbocations [40, 42] Treatment of tetrafluorobenzbarrelene with arenesulfonyl chlorides in nitro-methane-lithium perchlorate yields a crystalline salt with a rearranged benzo barrelene skeleton [43] Ionization of polycyclic adducts of difluorocarbene and derivatives of bornadiene with antimony pentafluonde in fluorosulfonyl chloride yields stable cations [44, 45]... 

A study of the Diels-Alder reaction was carried out by Earle et al. [42]. The rates and selectivities of reactions between ethyl acrylate (EA) and cyclopentadiene (CP) in water, 5 m lithium perchlorate in diethyl ether (5 m EPDE), and [BMIM][PE(3] were compared. The reactions in the ionic liquid [BMIM][PE(3] were marginally faster than in water, but both were slower than in 5 m EPDE [42, 43] (see Table 5.1-1 and Scheme 5.1-18). It should be noted that these three reactions give up to 98 % yields if left for 24 hours. The endo. exo selectivity in [BMIM][PE(3] was similar to that in 5 M EPDE, and considerably greater than that in water (Table 5.1-1). 

Reference electrodes are usually a calomel or a silver-silver chloride electrode. It is advisable that these be of the double-junction pattern so that potassium chloride solution from the electrode does not contaminate the test solution. Thus, for example, in titrations involving glacial acetic acid as solvent, the outer vessel of the double junction calomel electrode may be filled with glacial acetic acid containing a little lithium perchlorate to improve the conductance. 

Whilst some organic compounds can be investigated in aqueous solution, it is frequently necessary to add an organic solvent to improve the solubility suitable water-miscible solvents include ethanol, methanol, ethane-1,2-diol, dioxan, acetonitrile and acetic (ethanoic) acid. In some cases a purely organic solvent must be used and anhydrous materials such as acetic acid, formamide and diethylamine have been employed suitable supporting electrolytes in these solvents include lithium perchlorate and tetra-alkylammonium salts R4NX (R = ethyl or butyl X = iodide or perchlorate). 

The first two models are irrelevant to lithium-battery systems since the PEIs are not thermodynamically stable with respect to lithium. Perchlorate (and other anions but not halides) were found to be reduced to LiCl [15, 16, 22-27]. It is commonly accepted that in lithium batteries the anode is covered by SEI which consists of thermodynamically stable anions (such as 02, S2-, halides). Recently, Aurbach and Za-ban [25] suggested an SEI which consists of five different consecutive layers. They represented this model by a series of five... 

Lithium hexafluoroarsenate is thermally stable [54, 55] but shows environmental risks due to possible degradation products [56-58], even though it is itself not very toxic. Its LD 50 value is similar to that of lithium perchlorate [55]. Just like lithium hexafluorophosphate, it can initiate the polymerization of cyclic ethers. Polymerization may be inhibited by tertiary amines [59], or 2-methylfuran [60], yielding highly stable electrolytes. 

The equatorial selectivity observed with organolithium reagents is enhanced in diethyl ether as the reaction solvent by the addition of lithium perchlorate (Table l)12. I3C-NMR studies47 indicate that the formation of a complex between lithium perchlorate and the carbonyl group, which also leads to a dramatic enhancement of the rate of the addition reaction, accounts for the increased diastereoselectivity. 

Composite proplnts, which are used almost entirely in rocket propulsion, normally contain a solid phase oxidizer combined with a polymeric fuel binder with a -CH2—CH2— structure. Practically speaking AP is the only oxidizer which has achieved high volume production, although ammonium nitrate (AN) has limited special uses such as in gas generators. Other oxidizers which have been studied more or less as curiosities include hydrazinium nitrate, nitronium perchlorate, lithium perchlorate, lithium nitrate, potassium perchlorate and others. Among binders, the most used are polyurethanes, polybutadiene/acrylonitrile/acrylic acid terpolymers and hydroxy-terminated polybutadienes... 

The influence of metal type on the specific impulse of propints has been described previously in this article (Table 16). The max theoretical specific impulse and density impulses (ISp x p ) for the oxidizers AN, AP and hydrazinium nitrate with 15 weight percent -fCH2)- binder have been calculated for various fuels (Ref 24). These data are in Tables 49-51. The ISp performance of nitronium perchlorate, lithium perchlorate and potassium perchlorate and metallized fuels with 4CH2>- binder are given in Table 52 (Ref 43)... 

---