Trichloroethylene reaction

Li T, Farrell J. Rate-limiting mechanisms for carbon tetrachloride and trichloroethylene reactions at iron surfaces. 221st National Meeting, San Diego, CA, American Chemical Society 2001 41 (1) 1154—1159. 

The ability of triethyl silyl radicals to remove the strongly bound vinylic chlorine from trichloroethylene (reaction 54) is a characteristic feature of the reactions of triethylsilyl radicals with other chloroethylenes. Radical addition to acetylenes is the method used most frequently to generate vinyl radicals. The formation of vinyl radicals by Cl atom transfer from chloroethylenes to silyl radicals thus offers an interesting alternative to this oaethod. 

On acetylation it gives acetanilide. Nitrated with some decomposition to a mixture of 2-and 4-nitroanilines. It is basic and gives water-soluble salts with mineral acids. Heating aniline sulphate at 190 C gives sulphanilic add. When heated with alkyl chlorides or aliphatic alcohols mono- and di-alkyl derivatives are obtained, e.g. dimethylaniline. Treatment with trichloroethylene gives phenylglycine. With glycerol and sulphuric acid (Skraup s reaction) quinoline is obtained, while quinaldine can be prepared by the reaction between aniline, paraldehyde and hydrochloric acid. 

Manufacture. Most chloroacetic acid is produced by the chlorination of acetic acid using a suitable catalyst such as acetic anhydride (9—12). The remainder is produced by the hydrolysis of trichloroethylene with sulfuric acid (13,14) or by reaction of chloroacetyl chloride with water. 

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. 

Chlorinated C2> Perchloroethylene (PCE) and trichloroethylene (TCE) can be produced either separately or as a mixture in varying proportions by reaction of C2-chlorinated hydrocarbons, eg, C2-chlorinated waste streams or ethylene dichloride, with a mixture of oxygen and chlorine or HCl. 

Unlike saUcyhc acid, > -hydroxyben2oic acid does not undergo the Friedel-Crafts reaction. It can be converted in 80% yield to y -aminophenol by the Schmidt reaction, which involves treating the acid with hydra2oic acid in trichloroethylene in the presence of sulfuric acid at 40°C (47). 

Many chlorinated hydrocarbons react readily with aluminum in the so-caHed bleeding reaction. A red aluminum chloride—chlorinated hydrocarbon complex is formed. Storage of uninhibited chlorinated solvents in aluminum vessels results in corrosion in a short period of time. Proprietary organic inhibitors permit commercial use of reactive solvents such as 1,1,1-trichloroethane and trichloroethylene for cleaning of aluminum. 

Thermal Cracking. Thermal chlorination of ethylene yields the two isomers of tetrachloroethane, 1,1,1,2 and 1,1,2,2. Introduction of these tetrachloroethane derivatives into a tubular-type furnace at temperatures of 425—455°C gives good yields of trichloroethylene (33). In the cracking of the tetrachloroethane stream, introduction of ferric chloride into the 460°C vapor-phase reaction zone improves the yield of trichloroethylene product. 

The properties of 1,1-dichloroethane are Hsted ia Table 1. 1,1-Dichloroethane decomposes at 356—453°C by a homogeneous first-order dehydrochlofination, giving vinyl chloride and hydrogen chloride (1,2). Dehydrochlofination can also occur on activated alumina (3,4), magnesium sulfate, or potassium carbonate (5). Dehydrochlofination ia the presence of anhydrous aluminum chloride (6) proceeds readily. The 48-h accelerated oxidation test with 1,1-dichloroethane at reflux temperatures gives a 0.025% yield of hydrogen chloride as compared to 0.4% HCl for trichloroethylene and 0.6% HCl for tetrachloroethylene. Reaction with an amine gives low yields of chloride ion and the dimer 2,3-dichlorobutane, CH CHCICHCICH. 2-Methyl-l,3-dioxaindan [14046-39-0] can be prepared by a reaction of catechol [120-80-9] with 1,1-dichloroethane (7). 

The most important reactions of trichloroethylene are atmospheric oxidation and degradation by aluminum chloride. Atmospheric oxidation is cataly2ed by free radicals and accelerated with heat and with light, especially ultraviolet. The addition of oxygen leads to intermediates (1) and (2). 

In the presence of aluminum, oxidative degradation or dimerization supply HCl for the formation of aluminum chloride, which catalyzes further dimerization to hexachlorobutene. The latter is decomposed by heat to give more HCl. The result is a self-sustaining pathway to solvent decomposition. Sufficient quantities of aluminum can cause violent decomposition, which can lead to mnaway reactions (1,2). Commercial grades of trichloroethylene are stabilized to prevent these reactions in normal storage and use conditions. 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

Chlorination of Ethylene Dichloride. Tetrachloroethylene and trichloroethylene can be produced by the noncatalytic chlorination of ethylene dichloride [107-06-2] (EDC) or other two-carbon (C2) chlorinated hydrocarbons. This process is advantageous when there is a feedstock source of mixed C2 chlorinated hydrocarbons from other processes and an outlet for the by-product HCl stream. Product ratios of tri- and tetrachloroethylene are controlled by adjusting the CI2 type="subscript">2 EDC ratio to the reactor. Partially chlorinated by-products are recycled to the chlorinator. The primary reactions are... 

Oxychlorination of G2 Chlorinated Hydrocarbons. Tetrachloroethylene and trichloroethylene can be produced by reaction of EDC with chlorine or HCl and oxygen in the presence of a catalyst. When hydrochloric acid is used, additional oxygen is requked. Product distribution is varied by controlling reactant ratios. This process is advantageous in that no by-product HCl is produced, and it can be integrated with other processes as a net HCl consumer. The reactions may be represented as follows ... 

Ethers, esters, amides and imidazolidines containing an epithio group are said to be effective in enhancing the antiwear and extreme pressure peiformance of lubricants. Other uses of thiiranes are as follows fuel gas odorant (2-methylthiirane), improvement of antistatic and wetting properties of fibers and films [poly(ethyleneglycol) ethers of 2-hydroxymethyl thiirane], inhibition of alkene metathesis (2-methylthiirane), stabilizers for poly(thiirane) (halogen adducts of thiiranes), enhancement of respiration of tobacco leaves (thiirane), tobacco additives to reduce nicotine and to reduce phenol levels in smoke [2-(methoxymethyl)thiirane], stabilizers for trichloroethylene and 1,1,1-trichloroethane (2-methylthiirane, 2-hydroxymethylthiirane) and stabilizers for organic compounds (0,0-dialkyldithiophosphate esters of 2-mercaptomethylthiirane). The product of the reaction of aniline with thiirane is reported to be useful in the flotation of zinc sulfide. 

The destruction and removal of trichloroethylene (TCE) by reaction with OXITOX , (sodium carbonate activated by Mg and Mn oxides and carbonates), proceeds through the following stoichiometric reaction ... 

Typical precautions with trichloroethylene are summarized in Table 5.52. An important factor is that the vapours are much heavier than air they will therefore spread and may accumulate at low levels, particularly in undisturbed areas. Because of its volatility, releases to the environment usually reach the atmosphere. Here it reacts with hydroxyl or other radicals (estimated half-life for reaction with hydroxyl radicals is less than a week) and is not therefore expected to diffuse to the stratosphere to any significant extent. There is some evidence for both aerobic and anaerobic biodegradation of trichloroethylene. 

The prepared photocatal3rsts were tested to know the reactivity and quantum efficiency in the aqueous solution with trichloroethylene(TCE) as a reactant in photocatalytic batch reactor. Also these results were compared the reactivity to the case of P25 catalyst. The liquid phase photocatalytic reaction system was shown in Fig. 1. 

The photocatalytic decomposition of TCE was carried out and the results were shown in Fig. 3. Photocatalytic reaction has been found to be less sensitive to the conditions such as the concentration of trichloroethylene, and the stoichiometric decomposition (Cl2C=CHCl + 3/2O2 + H2O 2CO2+ 3HC1) proceeds with fairly good reproducibility by prepared photocatalysts. 

C04-0158. CF3 CH2 F (HFC-134a) has replaced chlorofluorocarbon compounds for use as refrigerants. HFC-134a is produced from trichloroethylene by the following reactions ... 

Both these conversion processes involve the addition of electrons to the toxic substances. The trichloroethylene molecule is electrically neutral and must gain electrons in reactions that generate negatively charged chloride anions, hi addition, water or hydronium ions must supply hydrogen atoms that replace the chlorine atoms in the organic substance. The detailed reaction is complicated, but the net reaction is relatively simple CI2 C I CHCl + 3 H3 + 6 H2 C CH2 + 3 Cr + 3 H2 O... 

Stevens-Johnson syndrome, a severe erythema, was seen in five people occupationally exposed to trichloroethylene for 2-5 weeks at levels ranging from 19 to 164 ppm (Phoon et al. 1984). The study authors suggested that the erythema was caused by a hypersensitivity reaction to trichloroethylene. An exfoliative dermatitis (Goh and Ng 1988) and scleroderma (Czirjak et al. 1993), also thought to have an immune component, have been reported in persons occupationally exposed to trichloroethylene. 

It has been suggested that in some eases dermal effeets in persons oeeupationally exposed to trichloroethylene may be a sensitivity reaction (Cziijak et al. 1993 Gob and Ng 1988 Phoon et al. 1984). 

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