1,1,2,2-Tetrachloroethylene

Tetrachloroethylene [127-18-4] perchloroethylene, CCl2=CCl2, is commonly referred to as perc and sold under a variety of trade names. It is the most stable of the chloriaated ethylenes and ethanes, having no flash poiat and requiring only minor amounts of stabilizers. These two properties combiaed with its excellent solvent properties account for its dominant use ia the dry-cleaning iadustry as well as its appHcation ia metal cleaning and vapor degreasiag. 

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. 

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 27 

Stabilized tetrachloroethylene, as provided commercially, can be used in the presence of air, water, and light, in contact with common materials of constmction, at temperatures up to about 140°C. It resists hydrolysis at temperatures up to 150°C (2). However, the unstabilized compound, in the presence of water for prolonged periods, slowly hydrolyzes to yield trichloroacetic acid [76-03-9] and hydrochloric acid. In the absence of catalysts, air, or moisture, tetrachloroethylene is stable to about 500°C. Although it does not have a flash point or form flammable mixtures in air or oxygen, thermal decomposition results in the formation of hydrogen chloride and phosgene [75-44-5] (3). 

Reaction with hydrogen at 220°C in the presence of reduced nickel catalyst results in total decomposition to hydrogen chloride and carbon. An explosive reaction occurs with butylUthium in petroleum ether solution (4). Tetrachloroethylene also reacts explosively with metallic potassium at its melting point, however it does not react with sodium (5). 

Tetrachloroethylene is used as a solvent. It is highly volatile and, for this reason, has been found only in groundwaters. Its odor threshold in water is 300 pg L and it is classified by the EPA as a probable human carcinogen (Group B2). 

Dielectric constant, 1000 cycle Oielactric strength. 0,1 gap Explosive limits Firs point Plash point F reesing point 

Latent heat of vaporisation B. P. Nonvolatile matter Power factor. 1000 cycle Refractive index Residue on evaporation Solubility in water Q25 C Solubility of water in solvent 

Specific gravity QZS/Z5 C Specific heat Specific resistivity Vapor pressure Q30 C Viscosity QZ0 C Water contort Weight per gallon QZS C 

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This measurement provides a definition of the bitumen content in bitumen materials as the portion soluble in carbon disulfide (in France, in trichloroethylene, carbon tetrachloride or tetrachloroethylene). The method is defined by AFNOR NF T 66-012 or IP 47, or ASTM D 4 (the latter is not equivalent to the others). 

Carbon tetrachloride Ethylene chloride. Trichloroethylene. Propylene chloride. Ethylene chlorobromide 1 1 2-Trichloroethane Trimethylene chloride Tetrachloroethylene Trimethylene chlorobromide sym. Tetrachloroethane 1 4 Dichlorobutane 1 2 3-Trichloropropane Pentachloroothane. ... 

Chloroacetyl chloride is manufactured by reaction of chloroacetic acid with chlorinating agents such as phosphoms oxychloride, phosphoms trichloride, sulfuryl chloride, or phosgene (42—44). Various catalysts have been used to promote the reaction. Chloroacetyl chloride is also produced by chlorination of acetyl chloride (45—47), the oxidation of 1,1-dichloroethene (48,49), and the addition of chlorine to ketene (50,51). Dichloroacetyl and trichloroacetyl chloride are produced by oxidation of trichloroethylene or tetrachloroethylene, respectively. 

Solvent Resistance. Elastomeric fibers tend to swell in certain organic solvents mbber fibers swell in hydrocarbon solvents such as hexane. Spandex fibers become highly swollen in chlorinated solvents such as tetrachloroethylene [127-18-4] (Perclene). Although the physical properties of spandex fibers return to normal after the solvent evaporates, considerable amounts of its stabilizers may have been extracted. Therefore, the development of stabilizers that are more resistant to solvent extraction has become important as solvent scouring during mill processing replaces aqueous scouring at many mills, especially in Europe (26). 

The FlCFC-123 alternative to CFG-11 is made by the fluotination of tetrachloroethylene with either hquid or gaseous HF (41). Further reaction of HCFC-123 with HF provides the HCFC-124 and HFC-125 alternatives. 

Tetrachloroethylene can be prepared direcdy from tetrachloroethane by a high temperature chlorination or, more simply, by passing acetylene and chlorine over a catalyst at 250—400°C or by controlled combustion of the mixture without a catalyst at 600—950°C (32). Oxychl orin a tion of ethylene and ethane has displaced most of this use of acetylene. 

Reaction with cold nitric acid results primarily ia the formation of 5-nitrosahcyhc acid [96-97-9]. However, reaction with fuming nitric acid results ia decarboxylation as well as the formation of 2,4,6-trinitrophenol [88-89-1] (picric acid). Sulfonation with chlorosulfonic acid at 160°C yields 5-sulfosahcyhc acid [56507-30-3]. At higher temperatures (180°C) and with an excess of chlorosulfonic acid, 3,5-disulfosahcyhc acid forms. Sulfonation with hquid sulfur trioxide ia tetrachloroethylene leads to a nearly quantitative yield of 5-sulfosahcylc acid (1). 

Sulfosahcyhc acid is prepared by heating 10 parts of sahcyhc acid with 50 parts of concentrated sulfuric acid, by chlorosulfonation of sahcyhc acid and subsequent hydrolysis of the acid chloride, or by sulfonation with hquid sulfur trioxide in tetrachloroethylene. It is used as an intermediate in the production of dyestuffs, grease additives, catalysts, and surfactants. It is also useful as a colorimetric reagent for ferric iron and as a reagent for albumin. Table 9 shows the physical properties of sahcyhc acid derivatives. 

Vinyl chloride has gained worldwide importance because of its industrial use as the precursor to PVC. It is also used in a wide variety of copolymers. The inherent flame-retardant properties, wide range of plastici2ed compounds, and low cost of polymers from vinyl chloride have made it a major industrial chemical. About 95% of current vinyl chloride production worldwide ends up in polymer or copolymer appHcations (83). Vinyl chloride also serves as a starting material for the synthesis of a variety of industrial compounds, as suggested by the number of reactions in which it can participate, although none of these appHcations will likely ever come anywhere near PVC in terms of volume. The primary nonpolymeric uses of vinyl chloride are in the manufacture of vinyHdene chloride and tri- and tetrachloroethylene [127-18-4] (83). 

Common examples of compounds that are amenable to carbon adsorption are aromatics (benzene, toluene) and chlorinated organics (trichloroethylene, trichloroethane [71-55-6, 75 -(9(9-j5y, tetrachloroethylene, polychlorinated biphenyls (PCBs), DDT /T(9-77-77, pentachlorophenol [87-86-5J. Compounds that are not adsorbed effectively by carbon include ethanol [64-17-5], diethylene glycol [111-46-6], and numerous amines (butylamine [109-73-9, 13952-84-6, 75-64-9], triethanolamine [102-71-6], cyclohexylamine [108-91-8], hexamethylenediamine [108-91-8] (1). Wastewater concentrations that are suitable for carbon adsorption are generally less than 5000 mg/L. 

Nonaqueous phase Hquids (NAPLs) present special problems for soil and ground water cleanup. Contaminant transport through ground water depends in part on the water solubiHty of the compound. Because NAPLs cling to subsurface particles and are slow to dissolve in ground water, they hinder cleanups and prolong cleanup times. Dense nonaqueous phase Hquids (DNAPLs) migrate downward in the aquifer and can coUect in pools or pockets of the substmcture. Examples of DNAPLs are the common solvents tetrachloroethylene (PCE) and trichloroethylene (TCE) which were used extensively at many faciHties before the extent of subsurface contamination problems was realized. 

Aerobic, Anaerobic, and Combined Systems. The vast majority of in situ bioremediations ate conducted under aerobic conditions because most organics can be degraded aerobically and more rapidly than under anaerobic conditions. Some synthetic chemicals are highly resistant to aerobic biodegradation, such as highly oxidized, chlorinated hydrocarbons and polynuclear aromatic hydrocarbons (PAHs). Examples of such compounds are tetrachloroethylene, TCE, benzo(a)pyrene [50-32-8] PCBs, and pesticides. 

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