Carbon tetrachloride, decomposition

Chemical initiation generates organic radicals, usually by decomposition of a2o (11) or peroxide compounds (12), to form radicals which then react with chlorine to initiate the radical-chain chlorination reaction (see Initiators). Chlorination of methane yields all four possible chlorinated derivatives methyl chloride, methylene chloride, chloroform, and carbon tetrachloride (13). The reaction proceeds by a radical-chain mechanism, as shown in equations 1 through. Chain initiation... 

As chlorination proceeds from methyl chloride to carbon tetrachloride, the length of the C—Cl bond is decreased from 0.1786 nm in the former to 0.1755 nm in the latter (3). At ca 400°C, thermal decomposition of carbon tetrachloride occurs very slowly, whereas at 900—1300°C dissociation is extensive, forming perchloroethylene and hexachloroethane and Hberating some chlorine. Subjecting the vapor to an electric arc also forms perchloroethylene and hexachloroethane, as well as hexachlorobenzene, elementary carbon, and chlorine. 

Although in the dry state carbon tetrachloride may be stored indefinitely in contact with some metal surfaces, its decomposition upon contact with water or on heating in air makes it desirable, if not always necessary, to add a smaH quantity of stabHizer to the commercial product. A number of compounds have been claimed to be effective stabHizers for carbon tetrachloride, eg, alkyl cyanamides such as diethyl cyanamide (39), 0.34—1% diphenylamine (40), ethyl acetate to protect copper (41), up to 1% ethyl cyanide (42), fatty acid derivatives to protect aluminum (43), hexamethylenetetramine (44), resins and amines (45), thiocarbamide (46), and a ureide, ie, guanidine (47). 

Physical properties of hexachloroethane are Hsted in Table 11. Hexachloroethane is thermally cracked in the gaseous phase at 400—500°C to give tetrachloroethylene, carbon tetrachloride, and chlorine (140). The thermal decomposition may occur by means of radical-chain mechanism involving -C,C1 -C1, or CCl radicals. The decomposition is inhibited by traces of nitric oxide. Powdered 2inc reacts violentiy with hexachloroethane in alcohoHc solutions to give the metal chloride and tetrachloroethylene aluminum gives a less violent reaction (141). Hexachloroethane is unreactive with aqueous alkali and acid at moderate temperatures. However, when heated with soHd caustic above 200°C or with alcohoHc alkaHs at 100°C, decomposition to oxaHc acid takes place. 

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. 

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. 

Carbon tetrachloride was also found to react with pyrryl potassium to give 3-chloropyridine, however the mechanism is obscure and would justify further investigation. In a preparatively useful reaction, pyrrole and chloroform in the vapor phase at 500-550° gave 3-chloro-pyridine (33%) and a little 2-chloropyridine (2-5%). No interconversion of the isomers occurred under these conditions, though pyrolytic rearrangement of N-alkylpyrrole to 3-substituted pyridines is considered to involve 2-alkylpyrroles as intermediates. There is some independent evidence that dichlorocarbene is formed in the vapor phase decomposition of chloroform. ... 

Although direct nitration was not possible, 2-amino-4-methylselena-zole can be directly brominated by treatment with bromine in carbon tetrachloride, the hydrogen bromide salt of 2-amino-4-methyl-5-bromoselenazole, mp 180°C (decomp.) is formed. However, all attempts to obtain the free base from this salt failed and led to complete decomposition. In this bromination, an equivalent quantity of bromine must be used excess also leads to complete destruction of the molecule. From the decomposition products an oily compound can be detected similar to bromoacetone. ... 

Absolute ethanol (400 ml.) is vigorously stirred in a 1-1. widenecked Erlenmeyer flask immersed in an ice bath (Note 4). The tropylium hexachlorophosphate-tropylium chloride double salt4 is separated from the reaction mixture by suction filtration, washed briefly with fresh carbon tetrachloride, and transferred as rapidly as possible into the cold, well-stirred ethanol (Note 5). The salt dissolves rapidly and exothermally to give a reddish solution. Fifty milliliters (0.39 mole) of 50% aqueous fluoboric acid is added rapidly to the cold stirred solution (Note 6). The dense white precipitate of tropylium fluoborate that forms is separated by suction filtration, washed with a little cold ethanol and with ether, and air-dried at room temperature (Note 7) weight 34-38 g. (80-89%) decomposition point about 200° A j, HC1 218 mja (log e 4.70), 274 m/i (log e 3.61). The product is 98-100% pure (Notes 8 and 9). 

System analysis techniques have been used to generate input functions for PB-PK models. Oral administration of carbon tetrachloride in different vehicles was successfully described by absorption input functions obtained by deconvolution and disposition decomposition methods [25,26],... 

A violent reaction occurred when cleaning lump metal under carbon tetrachloride [1], Finely divided barium, slurried with trichlorotrifluoroethane, exploded during transfer owing to frictional initiation [2], Granular barium in contact with fluo-rotrichloromethane, carbon tetrachloride, 1,1,2-trichlorotrifluoroethane, tetrachloro-ethylene or trichloroethylene is suceptible to detonation [3]. Thermodynamic calculations indicated a heat of decomposition of 2.60 kJ/g of mixture and a likely adiabatic temperature approaching 3000°C, accompanied by a 30-fold increase in pressure [4],... 

Mixtures of ethylene and carbon tetrachloride can be initiated to explode at temperatures betwen 25 and 105°C and pressures of 30-80 bar, causing a six-fold pressure increase. At 100°C and 61 bar, explosion initiated in the gas phase propagated into the liquid phase. Increase of halocarbon cone, in the gas phase decreased the limiting decomposition pressure. 

Dining chlorination of styrene in carbon tetrachloride at 50°C, a violent reaction occurred when some 10% of the chlorine gas had been fed in. Laboratory examination showed that the eruption was caused by a rapid decomposition reaction catalysed by ferric chloride [1], Various aromatic monomers decomposed in this way when treated with gaseous chlorine or hydrogen chloride (either neat, or in a solvent) in the presence of steel or iron(III) chloride. Exotherms of 90°C (in 50% solvent) to 200°C (no solvent) were observed, and much gas and polymeric residue was forcibly ejected. 

The carbon tetrachloride vapor carries with it any moisture that may be present. If this were not removed at a relatively low temperature, hydrolysis of the chloride would take place, with the formation of sulfonic acid which would promote decomposition of the sulfochloride during its distillation. 

B,j3,B"-Trichloroborazine forms white crystalline needles, m.p. 83.9 to 84.5°. It is extremely sensitive to moisture and decomposes violently in water. It is soluble without decomposition in anhydrous nonprotonic organic solvents such as benzene, ethyl ether, and carbon tetrachloride. 

Crude sulfur vesicants are relatively stable and stability increases with purity Distilled materials show very little decomposition on storage. Solvents such as carbon tetrachloride and chlorobenzene have been added to enhance stability of crude material. Agents can be stored in glass or steel containers, although pressure may develop in steel containers. Sulfur vesicants rapidly corrode brass and cast iron, and permeate into ordinary rubber. 

Shusterman and coworkers20 studied the decomposition of 7,7-dimethyl-l,4,5,6-te-traphenyl-7-germabenzonorbornadiene (8) by monitoring the disappearance of the absorbance at 320 nm in the UV. They found that the rate of formation of dimethylgermylene was not affected by the addition of trapping agents such as styrene, 2,3-dimethylbutadiene or carbon tetrachloride. This suggested to the authors that either... 

Shushunov and Pavlova158 have investigated the thermal decomposition of nitrogen trichloride at a concentration of 0.7 mole.l-1 in liquid carbon tetrachloride. In the absence of light and air the reaction was first order up to at least 50 % decomposition, and the rate coefficients fitted the Arrhenius expression... 

Laser flash photolysis at wavelengths within the charge-transfer absorption bands of 2,2,6,6-tetramethylpiperidine-./V-oxyl (TEMPO) and carbon tetrachloride yields theoxoam-monium chloride of TEMPO 291 (Xmax = 460 nm) and the trichloromethyl radical in an essentially instantaneous 18 ps) process152. The primary photochemical reaction is an electron transfer from TEMPO to carbon tetrachloride followed by immediate decomposition of the carbon tetrachloride anion radical to chloride and trichloromethyl radical (equation 140). The laser flash photolysis of TEMPO and of other nitroxides in a variety of halogenated solvents have confirmed the generality of these photoreactions152. 

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