67-72-1 Hexachloroethane

Kominsky JR, Wisseman CL, Morse DL Hexachlorocyclopentadiene contamination of a municipal waste-water treatment plant. Am Ind Hyg Assoc J 41 552-6,1980 

Boogaard PJ, Rocchi, PSJ, van Sittert NJ Effects of exposure to low concentrations of chlorinated hydrocarbons on the kidney and liver of industrial workers. Br J Ind Med 50 331-339, 1993 

World Health Organization Hexachlorocyclopentadiene. Environmental Health Criteria 120. pp 1-126. Geneva, International Programme on Chemical Safety (IPCS), 1991 

Rand GM et ah Effects of inhalation exposure to hexachlorocyclopentadiene on rats and monkeys. 7 Toxicol Environ Health 9 743-760, 1982 

Abdo KM, Montgomery CA, Kluwe WM, et ah Toxicity of hexachlorocyclopentadiene Subchronic (13-week) administration by gavage to F344 rats and B6C3F1 mice. J Appl Tox/ro/4 75-81, 1984 

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The theory of sublimation, t.e. the direct conversion from the vapour to the sohd state without the intermediate formation of the liquid state, has been discussed in Section 1,19. The number of compounds which can be purified by sublimation under normal pressure is comparatively small (these include naphthalene, anthracene, benzoic acid, hexachloroethane, camphor, and the quinones). The process does, in general, yield products of high purity, but considerable loss of product may occur. 

Smoke-Generating Devices. Smoke generators are used by the military for daytime obscuration and signaling. For field use where portable stable systems ate requited, pyrotechnic devices are often employed. The primary composition since the 1940s has been HC smoke, which generates a cloud of zinc chloride, ZnCl, smoke by a series of reactions between hexachloroethane, C2Clg(HC), zinc oxide, and aluminum (3) (eq. 4—6). The zinc regenerated in... 

Hexachloroethane [67-72-1] has, like carbon tetrachloride [56-23-5], been used to remove Hver flukes from mminants. Also used are alben2adole, previously mentioned as a ben2imida2ole, and cHoxanide [144327-41-3], oxycho2anide [2277-92-1], or rafoxanide [22662-39-1]. Ciba s Ivomect is used for fluke control in Europe. 

Another type of smoke mixture, a volatile hygroscopic chloride for thermal generation, has the U.S. Army designation HC, type C. It is composed of ca 6.7 wt % grained aluminum, 46.7 wt % zinc oxide ZnO, and 46.7 wt % hexachloroethane [67-72-17, The ratio of zinc oxide to... 

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. 

Chlorination of Hydrocarbons or Chlorinated Hydrocarbons. Chlorination at pyrolytic temperatures is often referred to as chlorinolysis because it involves a simultaneous breakdown of the organics and chlorination of the molecular fragments. A number of processes have been described for the production of carbon tetrachloride by the chlorinolysis of various hydrocarbon or chlorinated hydrocarbon waste streams (22—24), but most hterature reports the use of methane as the primary feed. The quantity of carbon tetrachloride produced depends somewhat on the nature of the hydrocarbon starting material but more on the conditions of chlorination. The principal by-product is perchloroethylene with small amounts of hexachloroethane, hexachlorobutadiene, and hexachloroben2ene. In the Hbls process, a 5 1 mixture by volume of chlorine and methane reacts at 650°C the temperature is maintained by control of the gas flow rate. A heat exchanger cools the exit gas to 450°C, and more methane is added to the gas stream in a second reactor. The use of a fluidi2ed-bed-type reactor is known (25,26). Carbon can be chlorinated to carbon tetrachloride in a fluidi2ed bed (27). 

Miscellaneous Reactions. Chlorinolysis of mixtures containing 1,1,2-trichloroethane at 550°C was found to give primarily perchloroethylene and hexachloroethane (97). 

Dehydrochlorination and Chlorination. The simultaneous chlorination and dehydrochlorination of 1,1,2,2-tetrachloroethane proceeds via formation of labile intermediate, CI2CCHCI2 (123). Chlorination of tetrachloroethane to hexachloroethane is accelerated by 315—354 nm light (124). 

Various catalytic materials promote dehydrochlorination including AlCl (6,91), AICk-nitrohenzene complex (114), activated alumina (3), and FeCl (112). Chlorination in the presence of anhydrous aluminum chloride gives hexachloroethane. Dry pentachloroethane does not corrode iron at temperatures up to 100°C. It is slowly hydrolyzed by water at normal temperatures and oxidized in the presence of light to give trichloroacetyl chloride. 

Hexachloroethane [67-72-17, perchloroethane, CCl CCl, is a white crystalline soHd with a camphorlike odor. Hexachloroethane is nonflammable and has a number of minor industrial uses which are limited because of its toxic nature. Crystalline hexachloroethane is a minor product in many industrial chlorination processes of saturated and unsaturated hydrocarbons. 

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. 

Degradation of carbon tetrachloride by photochemical, x-ray, or ultrasonic energy produces the trichloromethyl free radical which on dimeri2ation gives hexachloroethane. Chloroform under strong x-ray irradiation also gives the trichloromethyl radical intermediate and hexachloroethane as final product. 

Hexachloroethane is formed in minor amounts in many industrial chlorination processes designed to produce lower chlorinated hydrocarbons, usually via a sequential chlorination step. Chlorination of tetrachloroethylene, in the presence of ferric chloride, at 100—140°C is one convenient method of preparing hexachloroethane (142). Oxychlorination of tetrachloroethylene, using a copper chloride catalyst (143) has also been used. Photochemical chlorination of tetrachloroethylene under pressure and below 60°C has been studied (144) and patented as a method of producing hexachloroethane (145), as has recovery of hexachloroethane from a mixture of other perchlorinated hydrocarbon derivatives via crystalH2ation in carbon tetrachloride. Chlorination of hexachlorobutadiene has also been used to produce hexachloroethane (146). 

Hexachloroethane is considered to be one of the more toxic chlorinated hydrocarbons. The 1991 ACGIH recommended time-weighted average (TWA) for hexachloroethane was 1 ppm or 10 mg /m of air. Skin adsorption is a route of possible exposure ha2ard. The primary effect of hexachloroethane is depression of the central nervous system (147). Pentachloroethane and tetrachloroethylene are primary metaboHtes of hexachloroethane in sheep (148). 

Hexachloroethane, like carbon tetrachloride and 1,1,1-trichloroethane, can be used to formulate extreme pressure lubricants (149,150). For example, lubricating oils containing 0.02—3.0 wt % (as halogen) of hexachloroethane reduce the abrasion of exhaust valve seats in internal combustion engines (151)... 

Hexachloroethane has been suggested as a degasifter in the manufacture of aluminum and magnesium metals. Hexachloroethane has been used as a chain-transfer agent in the radiochemical emulsion preparation of propylene tetrafluoroethylene copolymer (152). It has also been used as a chlorinating agent in the production of methyl chloride from methane (153). 

Other uses of hexachloroethane are as moth repellent, plasticizer for cellulose esters, anthelmintic in veterinary medicine, mbber accelerator, and as a component in fungicidal and insecticidal formulations. Hexachloroethane reacts with silumin (an aluminum /siUcon alloy) at 483 K to generate an intense white smoke, which is useful in certain pyrotechnics (154). 

In the presence of catalysts, trichloroethylene is readily chlorinated to pentachloro- and hexachloroethane. Bromination yields l,2-dibromo-l,l,2-trichloroethane [13749-38-7]. The analogous iodine derivative has not been reported. Fluorination with hydrogen fluoride in the presence of antimony trifluoride produces 2-chloro-l,l,l-trifluoroethane [75-88-7] (8). Elemental fluorine gives a mixture of chlorofluoro derivatives of ethane, ethylene, and butane. 

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. 

Photochlorination of tetrachloroethylene, observed by Faraday, yields hexachloroethane [67-72-1]. Reaction with aluminum bromide at 100°C forms a mixture of bromotrichloroethane and dibromodichloroethane [75-81-0] (6). Reaction with bromine results in an equiUbrium mixture of tetrabromoethylene [79-28-7] and tetrachloroethylene. Tetrachloroethylene reacts with a mixture of hydrogen fluoride and chlorine at 225—400°C in the presence of zirconium fluoride catalyst to yield l,2,2-trichloro-l,l,2-trifluoroethane [76-13-1] (CFG 113) (7). 

Chlorinated ethanesf (including 1,2-dichloroethane, 1,1,1-trichloroethane, and hexachloroethane)... 

Hexachloroethane [67-72-1] M 236.7, m 187°. Steam distd, then crystd from 95% EtOH. Dried in the dark under vacuum. 

The monomer may conveniently be produced from hexachloroethane via trichlorotrifluoroethane... 

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