Decomposition carbonate solvents

The decomposition reactions of the preferred organic carbonate solvents are [152,192] ... 

Since VC has a smaller lowest unoccupied molecular orbital (LUMO) energy due to the presence of a double bond in its structure, it is considered to be more susceptible to reduction than other carbonates such as EC and DMC. The reduction potential of VC is higher than those of other carbonate solvents, as given in Eig. 4.2, which were measured on a gold electrode in tetrahydrofuran (THE) solvent. " It is interpreted that the reductive decomposition of VC precedes the carbonate solvent decomposition, and the resultant good SEI film on the anode protects the further solvent decomposition and the graphite exfoliation by solvent co-intercalation. ... 

In 2003, Shima and Ue from Mitsubishi Chanical Corporation and Yamaki from Kyushu University presented the mechanism behind the overcharge prevention. According to the description in the relevant reference, the aromatic compounds without hydrogen at the benzylic position (e.g., t rt-butylbenzene) evolve mainly carbon dioxide (CO2) gas, which is generated by the indirect decomposition of carbonate solvents. The CO2 gas evolution reaction using a redox mediator is expected as a new overcharge protection method [3]. 

However, the main problem with this material is that it generates gas during cycling, combined with a loss of capacity, particularly at high temperature, which is an obstacle to its commercial use [BEL 12, WU 12]. The gas emitted is partly made up of hydrogen and CO2, involving a decomposition of the carbonated solvents and the participation of traces of water present in the electrolyte [BER 14]. The reason for this reactivity of Li4Ti50i2 is due to its surface state, especially to the presence of holes in the (111) oriented surfaces electronic structure, responsible for the oxidation of solvent molecules that leads to the emission of CO2 [KIT 14]. Recent studies show that the problem of reactivity with the electrolyte can in part be... 

Characterization of the structure of the decomposition products of LiPFs-based electrolytes (Figure 17.7, bottom insert) along with the rates of formation have eventually led to the elucidation of the thermal decomposition mechanism [30] Campion et al. [30] reported that during the thermal decomposition of LiPFe-based electrolytes PF5 reacted rapidly with trace protic impurities in the electrolyte, such as water and alcohol, to form OPF3, which then initiated an auto-catalytic decomposition of the electrolyte (Figure 17.7). Density functional theory calculations and molecular dynamics simulations also supported the reactivity of PF5 toward carbonate solvents [31]. The auto-catalytic cycle relied upon the formation of the reactive Lewis acids PF5 and POF3. Several studies indicated that the addition of a Lewis base or a... 

Stability region. Electrochemical reduction of both the solvent and salt of the electrolyte can cause the formation of a film on the surface of the anode. This film is composed of insoluble reduction products of the electrolyte. The presence of this film, the SEl, has been known to be an important feature of graphite anodes that allows for reversible cycling and long-term stability due to surface passivation. " The components of the SEl on graphite electrodes have been well studied and have shown that the decomposition products of the ethylene carbonate solvent, namely Li allg l carbonates and Li carbonate, dominate the SEl layer. -... 

The heavy metal salts, ia contrast to the alkah metal salts, have lower melting points and are more soluble ia organic solvents, eg, methylene chloride, chloroform, tetrahydrofiiran, and benzene. They are slightly soluble ia water, alcohol, ahphatic hydrocarbons, and ethyl ether (18). Their thermal decompositions have been extensively studied by dta and tga (thermal gravimetric analysis) methods. They decompose to the metal sulfides and gaseous products, which are primarily carbonyl sulfide and carbon disulfide ia varying ratios. In some cases, the dialkyl xanthate forms. Solvent extraction studies of a large number of elements as their xanthate salts have been reported (19). 

Reactions. The chemistry of the xanthates is essentially that of the dithio acids. The free xanthic acids readily decompose in polar solvents, the rate being 10 times greater in methanol than in hexane. The acids decompose at room temperature to carbon disulfide and the corresponding alcohol the resulting alcohol autocatalyticaHy faciUtates the decomposition. 

Cesium forms simple alkyl and aryl compounds that are similar to those of the other alkah metals (6). They are colorless, sohd, amorphous, nonvolatile, and insoluble, except by decomposition, in most solvents except diethylzinc. As a result of exceptional reactivity, cesium aryls should be effective in alkylations wherever other alkaline alkyls or Grignard reagents have failed (see Grignard reactions). Cesium reacts with hydrocarbons in which the activity of a C—H link is increased by attachment to the carbon atom of doubly linked or aromatic radicals. A brown, sohd addition product is formed when cesium reacts with ethylene, and a very reactive dark red powder, triphenylmethylcesium [76-83-5] (C H )2CCs, is formed by the reaction of cesium amalgam and a solution of triphenylmethyl chloride in anhydrous ether. 

Decomposition with Bases. Alkaline decomposition of poUucite can be carried out by roasting poUucite with either a calcium carbonate—calcium chloride mix at 800—900°C or a sodium carbonate—sodium chloride mix at 600—800°C foUowed by a water leach of the roasted mass, to give an impure cesium chloride solution that is separated from the gangue by filtration (22). The solution can then be converted to cesium alum [7784-17-OJ, CS2SO4 Al2(S0 2 24H20. Extraction of cesium from the poUucite is almost complete. Solvent extraction of cesium carbonate from the cesium chloride solution using a phenol in kerosene has also been developed (23). 

Tetrachloroethylene was first prepared ia 1821 by Faraday by thermal decomposition of hexachloroethane. Tetrachloroethylene is typically produced as a coproduct with either trichloroethylene or carbon tetrachloride from hydrocarbons, partially chloriaated hydrocarbons, and chlorine. Although production of tetrachloroethylene and trichloroethylene from acetylene was once the dominant process, it is now obsolete because of the high cost of acetylene. Demand for tetrachloroethylene peaked ia the 1980s. The decline ia demand can be attributed to use of tighter equipment and solvent recovery ia the dry-cleaning and metal cleaning iadustries and the phaseout of CFG 113 (trichlorotrifluoroethane) under the Montreal Protocol. 

These can be converted to their uranyl nitrate addition compounds. The crude or partially purified ester is saturated with uranyl nitrate solution and the adduct filtered off. It is recrystallised from -hexane, toluene or ethanol. For the more soluble members crystallisation from hexane using low temperatures (-40°) has been successful. The adduct is decomposed by shaking with sodium carbonate solution and water, the solvent is steam distilled (if hexane or toluene is used) and the ester is collected by filtration. Alternatively, after decomposition, the organic layer is separated, dried with CaCl or BaO, filtered, and fractionally distilled under high vacuum. 

The submitters report that both l,4-diazabicyclo[2.2.2]octane and triethylamine have been used to catalyze this decomposition. Tri-ethylamine was less satisfactory as a catalyst because of its relatively rapid reaction with the solvent, carbon tetrachloride, to form triethylamine hydrochloride and because of difficulty encountered in separating triethylamine from the dicarbonate pi oduct. The 1,4-diazabicyclo-[2.2.2]octane was efficiently separated from the dicarbonate product by the procedure described in which the crude product was washed with very dilute aqueous acid. 

The nitrites aie most conveniently prepared from the corresponding alcohols by treatment with nitrosyl chloride in pyridine. The crude nitrites can be precipitated by addition of water and recrystallized from appropriate solvents. However nitrites prepared from carbinols in which the adjacent carbon is substituted by halogen, free or esterified hydroxyl or a carbonyl function are very readily hydrolyzed and must be recrystallized with great care. In general the photolysis gives higher yields if purified and dried nitrites are used which do not contain acids or pyridine, although occasionally the addition of small amounts of pyridine is recommended in order to prevent hydrolysis of the nitrite. Traces of acids do in fact catalyze the thermal decomposition of secondary nitrites to equimolar amounts of alcohol and ketone. ... 

To a suspension of 3.0 g of 7-[D-(-)-a-amino-p-hydroxyphenylacetamido] -3-[5-(1-methyl-1,2,3,4-tetrazolyl)thiomethyl] -A3arboxylic acid in 29 ml of water was added 0.95 g of anhydrous potassium carbonate. After the solution was formed, 15 ml of ethyl acetate was added to the solution, and 1.35 g of 4-ethyl-2,3-dioxo-1 -piperazinocarbonyl chloride was added to the resulting solution at 0°C to 5°C over a period of 15 minutes, and then the mixture was reacted at 0°C to 5°C for 30 minutes. After the reaction, an aqueous layer was separated off, 40 ml of ethyl acetate and 10 ml of acetone were added to the aqueous layer, and then the resulting solution was adjusted to a pH of 2.0 by addition of dilute hydrochloric acid. Thereafter, an organic layer was separated off, the organic layer was washed two times with 10 ml of water, dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The residue was dissolved in 10 mi of acetone, and 60 ml of 2-propanol was added to the solution to deposit crystals. The deposited crystals were collected by filtration, washed with 2-propanol, and then dried to obtain 3.27 g of 7-[D-(-)-a-(4-ethyl-2,3-dioxo)-1 -piperazinocarbonylamino)-p-hydroxyphenylacetamido] -3-[5-(1 -methyl-1,2,3,4-tetrazolyl)thiomethyl]-A product forms crystals, MP 1BB°C to 190°C (with decomposition). 

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