Chlorine hazards

Technical and trade organizations are concerned with safety and the environment. The Chlorine Institute in North America and Euro Chlor in Western Europe are examples of organizations dedicated to the safe production, transport, and use of chlorine. Hazard and operability studies (HAZOP) reviews for new designs, plants, and expansions (135) have become required by policy in many operating companies. Papers on safety and environmental subjects are given at most technical meetings (136—138). 

Chlorine Hazard Division 2.3 (toxic gas) Toxic exposure to people located along transportation routes High... 

Precautbn Incompat. with strong oxidizing agents, acids corrodes mild steel, aluminum, copper, and other metals reacts vigorously with sodium hypochlorite, may evolve chlorine Hazardous Decomp. Prods. Hazardous combustion prods. CO NO ammonia, SO,... 

In a single reaction (where selectivity is not a problem), the usual choice of excess reactant is to eliminate the component which is more difficult to separate in the downstream separation system. Alternatively, if one of the components is more hazardous (as is chlorine in this example), again we try to ensure complete conversion. 

The hazards of human poisoning by the parathions have stimulated the development of safer analogues. Two chlorinated derivatives have gready reduced mammalian toxicides. Dicapthon [2463-84-5], 0,0-dimethyl 0-(2-chloro-4-nitrophenyl) phosphorothioate (63) (mp 53°C), has rat LD qS of 400, 330 (oral) and 790, 1250 (dermal) mg/kg. Chlorthion [500-20-8], 0,0-dimethyl 0-(3-chloro-4-nitrophenyl) phosphorothioate (64) (mp 21°C, <71.437), has rat LD qS of 890, 980 (oral) and 4500, 4100 (dermal) mg/kg. These compounds have been used as household insecticides. 

Organic compounds of bromine usually resemble their chlorine analogues but have higher densities and lower vapor pressures. The bromo compounds are more reactive toward alkaUes and metals brominated solvents should generally be kept from contact with active metals such as aluminum. On the other hand, they present less fire hazard one bromine atom per molecule reduces flammabiUty about as much as two chlorine atoms. 

AH volatile organic solvents are toxic to some degree. Excessive vapor inhalation of the volatile chloriaated solveats, and the central nervous system depression that results, is the greatest hazard for iadustrial use of these solvents. Proper protective equipment and operating procedures permit safe use of solvents such as methylene chloride, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene ia both cold and hot metal-cleaning operations. The toxicity of a solvent cannot be predicted from its chlorine content or chemical stmcture. For example, 1,1,1-trichloroethane is one of the least toxic metal-cleaning solvents and has a recommended threshold limit value (TLV) of 350 ppm. However, the 1,1,2-trichloroethane isomer is one of the more toxic chloriaated hydrocarboas, with a TLV of only 10 ppm. 

Further dechlorination may occur with the formation of substituted diphenyhnethanes. If enough aluminum metal is present, the Friedel-Crafts reactions involved may generate considerable heat and smoke and substantial amounts of hydrogen chloride, which reacts with more aluminum metal, rapidly forming AlCl. The addition of an epoxide inhibits the initiation of this reaction by consuming HCl. Alkali, alkaline-earth, magnesium, and zinc metals also present a potential reactivity hazard with chlorinated solvents such as methylene chloride. 

Benzene chlorination reactors are subject to design and operating hazards. Stagnant areas must be avoided in reactor design as they allow chlorination to the tetra- and pentachlorobenzenes. These compounds have low solubiUty in the Hquid and can cause plugging. Another hazard is the... 

An 80% yield of benzyl chloride is obtained with sulfuryl chloride as chlorinating agent. Yields of >70% of benzyl chloride are obtained by the zinc chloride-catalyzed chloromethylation of benzene but formation of bis-chloromethyl ether presents a health hazard for this reaction pathway. 

Acryhc elastomers are normally stable and not reactive with water. The material must be preheated before ignition can occur, and fire conditions offer no hazard beyond that of ordinary combustible material (56). Above 300°C these elastomers may pyrolize to release ethyl acrylate and other alkyl acrylates. Otherwise, thermal decomposition or combustion may produce carbon monoxide, carbon dioxide, and hydrogen chloride, and/or other chloiinated compounds if chlorine containing monomers are present ia the polymer. 

Explosion Hazards. The electrolysis of aqueous solutions often lead to the formation of gaseous products at both the anode and cathode. Examples are hydrogen and chlorine from electrolysis of NaCl solutions and hydrogen and oxygen from electrolysis of water. The electrode reactions. 

Attenuation Another alternative to intensification is attenuation, using a hazardous material under the least hazardous conditions. Thus large quantities of liquefied chlorine, ammonia, and petroleum gas can be stored as refrigerated liquids at atmospheric pressure instead of storing them under pressure at ambient temperature. (Leaks from the refrigeration eqmpment should also be considered, so there is probably no net gain in refrigerating quantities less than a few hundred tons.) Dyestuffs which form explosive dusts can be handled as slurries. 

A material that has a high toxicity does not necessarily present a severe toxic hazard. For example, a ton of lead arsenate spilled in a busy street is unhkely to poison members of the public just a short distance from the spiU, because it is not mobile. It could be carefully recovered and removed and would present a low risk to the gener pubhc, even though it is extremely toxic. On the other hand, a ton of liquefied chlorine spilled on the same street could become about 11,000 fF of pure gas. The IDLH for chlorine is 25 ppm. This is a concentration such that immediate action is required. Thus, the one ton of chlorine, if mixed uniformly with air, could create a cloud of considerable concern, having a volume of about 4.4 X 10 fF or a sphere 770 ft in diameter. This could quickly spread over downwind areas and... 

Consider refrigerated. storage at atmospheric pressure. A BLEXT] cannot occur with the liquid at its atmospheric boiling point (no superheat), although a fire hazard may still exist. The Dow Chemical Company in Texas stores chlorine as a liquid at atmospheric pressure at about —34°C (Englund, ibid. 1991). 

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