Hydrocarbons, saturated, chlorination

Interaction of chlorine with methane is explosive at ambient temperature over yellow mercury oxide [1], and mixtures containing above 20 vol% of chlorine are explosive [2], Mixtures of acetylene and chlorine may explode on initiation by sunlight, other UV source, or high temperatures, sometimes very violently [3], Mixtures with ethylene explode on initiation by sunlight, etc., or over mercury, mercury oxide or silver oxide at ambient temperature, or over lead oxide at 100°C [1,4], Interaction with ethane over activated carbon at 350°C has caused explosions, but added carbon dioxide reduces the risk [5], Accidental introduction of gasoline into a cylinder of liquid chlorine caused a slow exothermic reaction which accelerated to detonation. This effect was verified [6], Injection of liquid chlorine into a naphtha-sodium hydroxide mixture (to generate hypochlorite in situ) caused a violent explosion. Several other incidents involving violent reactions of saturated hydrocarbons with chlorine were noted [7],... 

Bromine generally is much less reactive toward hydrocarbons than chlorine is, both at high temperatures and with activation by light. Nonetheless, it usually is possible to brominate saturated hydrocarbons successfully. Iodine is unreactive. 

Chlorinated Hydrocarbons Other Chlorinated Compounds. The substitution of chlorine atom for hydrogen in a compd greatly increases the anesthetic action of the derivative. In addn, the chlorine deriv is less specific than the parent hydrocarbon in its action, and may affect other tissues along with those of the central nervous system of this body. The chlorine deriv is generally quite toxic and may cause liver, heart Sc kidney damage. As a rule, unsaturated chlorine derivs are highly narcotic but less toxic than saturated derivs. Sax(Ref 4) has discussed in detail the toxicities Sc hazards of a number of chlorinated compds, including Chlorinated Diphenyls Chlorinated Hydrocarbons, Aromatic Aliphatic Chlorinated Naphthalenes Chlorinated Phenols Chlorinated Triphenyls others. 

The product mixture does not contain equal numbers of moles of the dichloroethanes so we do not show a stoichiometricaUy balanced equation. Because reactions of saturated hydrocarbons with chlorine can produce many products, the reactions are not always as useful as might be desired. 

Extracts were methylated to facilitate the analysis of fatty acids (results not reported In this paper). Derlvatlzed extracts were subjected to preparatory thin layer chromatography (TLC) on Analtech silica GHL plates the elution solvent was 6.6Z diethyl ether/hexane. Bands were visualized by exposing the plates to Iodine vapor. Saturated hydrocarbons and chlorinated compounds were collected together In a broad band directly beneath the solvent front. These hydrocarbon/PCB fractions were dissolved In hexane and treated with metallic mercury to remove elemental sulfur prior to gas chromatographic analysis. 

Saturated Hydrocarbons. Saturated hydrocarbons, like chlorinated hydrocarbons, tended to distribute predominantly In the FL fractions of sediments (Table IV). Similar quantitative results were reported In studies of estuarine (43) and lacustrine (44) sediments. 

The dependences shown in Fig. 3 reveal that employing a catalyst with a larger specific surface area with rising temperature would, probably, lead to the deep oxidation of vinyl chloride and, to a lesser extent, of ethylene, resulting in a decrease in the total yield of ethylene and vinyl chloride. A certain increase in the overall yield of COx products, which was observed for catalyst 2, is accompanied with an increase in the total yield of ethylene and vinyl chloride. This suggests that saturated chlorinated hydrocarbons — ethyl chloride and 1,2-dichloroethane — are oxidized predominantly and that the rate of oxidation is lower rate compared to that of the dehydrochlorination of these compounds. 

We can suppose on the strength of the data listed in Table 2 that at the short times-on-stream, the major contribution to the formation of deep oxidation products is made by saturated chlorinated hydrocarbons 1,2 dichloroethane and ethyl chloride. On increasing time-on-stream to more than 6 s, we observed a sharp increase in the yield of deep oxidation products together with the decrease in the yield of vinyl chloride. It is likely that at the longer times-on-stream, the rate of deep oxidation of vinyl chloride would increase and become higher than the rate of dichloroethane dehydrochlorination. Taking into account this fact, we believe that the optimum time-on-stream assuring the best total yield of ethylene and vinyl chloride would be 3—5 s. 

The chlorination of pentane is accomplished in equipment represented diagrammatically in Fig. 6-10, as follows pentane (normal or iso) is introduced into the system and is saturated with hydrogen chloride from the cycle of operations. The hydrocarbon is pumped at 75 psig pressure through a heater and vaporized at 85°C. It then passes into a venturi throat where it comes into contact with chlorine vapors which are supplied at 50 C and 60 lb pressure. At this point, the velocity of the pentane vapors should be above 60 mph and the volume ratio of hydrocarbon to chlorine about 15 1. 

Observation (2) indicates that the compound is a monohalogen derivative of a hydrocarbon, as chlorine compounds which contain more than one halogen atom are heavier than water. Observations (3) and (4) indicate that no oxygen is present, and that the substance is saturated. The boiling point of the substances was found to be 46°, and its specific gravity 0.89. As these are the constants for propyl chloride, the conclusion is drawn that the substance is this compound. 

SAN exhibits higher chemical and stress cracking resistance than polystyrene. This resistance increases with its acrylonitrile content. At room temperature, SAN is resistant to saturated hydrocarbons, fuels and mineral oils with low aromatics content, vegetable and animal fats and oils, water, aqueous salt solutions, dilute acids and alkalis. SAN is attacked by concentrated mineral acids, aromatic hydrocarbons, and chlorinated hydrocarbons, esters, ethers, and ketones. 

Like chlorine, bromine can displace hydrogen from saturated hydrocarbons, though not as readily, and adds on to unsaturated ones. 

Iodine does not replace hydrogen from saturated hydrocarbons directly, as do both chlorine and iodine. 

The most abundant natural steroid is cholesterol. It can be obtained in large quantides from wool fat (15%) or from brain or spinal chord tissues of fat stock (2-4%) by extraction with chlorinated hydrocarbons. Its saturated side-chain can be removed by chromium trioxide oxidation, but the yield of such reactions could never be raised above 8% (see page 118f.). 

Chlorine reacts with saturated hydrocarbons either by substitution or by addition to form chlorinated hydrocarbons and HCl. Thus methanol or methane is chlorinated to produce CH Cl, which can be further chlorinated to form methylene chloride, chloroform, and carbon tetrachloride. Reaction of CI2 with unsaturated hydrocarbons results in the destmction of the double or triple bond. This is a very important reaction during the production of ethylene dichloride, which is an intermediate in the manufacture of vinyl chloride ... 

The physical properties of vinyl chloride are Hsted in Table 1 (12). Vinyl chloride and water [7732-18-5] are nearly immiscible. The equiUbrium concentration of vinyl chloride at 1 atm partial pressure in water is 0.276 wt % at 25°C, whereas the solubiUty of water in vinyl chloride is 0.0983 wt % at 25°C and saturated pressure (13). Vinyl chloride is soluble in hydrocarbons, oil, alcohol, chlorinated solvents, and most common organic Hquids. 

Saturated hydrocarbons can be chlorinated in moderate yields under mild conditions in a biphasic system consisting of alkaline hypochlorite solution and CH2CI2 containing Ni(Il) bis(saHcyHdene)ethylenediamine as chlorination catalyst and bexadecyltrimetbylammonium bromide as phase-transfer catalyst (166). 

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. 

Groundwater contaminated with chlorinated hydrocarbons is being remediated by a conventional air stripper or a rotary stripper, producing an air stream containing the halogenated hydrocarbon vapors and saturated with water vapor (45), which is then passed through a catalyst bed. 

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