Organic chlorine

Can the byproduct be subjected to further reaction and its value upgraded For example, most organic chlorination reactions produce hydrogen chloride as a byproduct. If this cannot be sold, it... 

The equilibrium constant for this reaction decreases with increase in temperature but the higher temperature is required to achieve a reasonable rate of conversion. Hydrogen chloride is now being produced in increasing quantities as a by-product in organic chlorination reactions and it is economic to re-convert this to chlorine. 

Huntress, Organic Chlorine Compounds, Order III, 1948 (J. Wiley Chapman and HaU). 

Chlorine from HCl. Most organic chlorination reactions consume only half the CI2 to produce the desired product the other half is converted to HCl. Depending on demand and supply of CI2 vs HCl, chlorine recovery from hydrochloric acid is sometimes attractive. Two commercial routes are available electrolysis and oxidation (69). 

Hydrogen Chloride as By-Product from Chemical Processes. Over 90% of the hydrogen chloride produced in the United States is a by-product from various chemical processes. The cmde HCl generated in these processes is generally contaminated with impurities such as unreacted chlorine, organics, chlorinated organics, and entrained catalyst particles. A wide variety of techniques are employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric acid. Some of the processes in which HCl is produced as a by-product are the manufacture of chlorofluorohydrocarbons, manufacture of aUphatic and aromatic hydrocarbons, production of high surface area siUca (qv), and the manufacture of phosphoric acid [7664-38-2] and esters of phosphoric acid (see Phosphoric acid and phosphates). 

Calcium is a macronutrient essential for all organisms. Chlorine is a micronutrient essential for higher (ie, seed) plants but not considered essential for mammals. Above certain levels chloride is toxic to plants and animals, thus when considering calcium chloride, potentially large concentrations of calcium ion can be tolerated, but at these concentrations the chloride ion becomes toxic. 

Hydrochloric By-product of organic chlorination, salt process, and synthetic HCl HCl Absorption... 

Organic chlorinations are handled in lead where the presence of iron might produce catalyst substitution in an undesirable position. Hence, lead is the material most frequently specified for chlorinators. 

PEROX-GARD , hydrogen peroxide, 103 PERSEC , perchloroethylene, 103 PERSTABIL , organic chlorine, 103 Perstoi-p AB, 203 Perstoi"p Chemicals Division, 203 Persulfates, 103... 

We should also compare the scope of the technologies for different waste streams. With the exception of Brocat which only handles HBr, the systems can be used with HBr or metal salt streams. However, H2O2 has an advantage in terms of handling impurities in the steam such as low levels of organics. Chlorine and chlorate will suffer from reduced efficiency due to side reactions Brocat has potential problems with catalyst poisoning. H2O2 suffers no major drawbacks in this respect. 

Moore, N.W. and Walker, C.H. (1964). Organic chlorine insecticide residues in wild birds. Nature 201, 1072-1073. 

In addition to making organic chlorine compounds, a significant fraction of CI2 production is used to make inorganic halides. One important use, described in Chapter 20, is in the metallurgy of titanium, in which molecular chlorine is used to convert Ti02 into TiCl4, which is easy to purify by distillation. 

The chloride anion is a major species in the oceans and plays an essential role in biochemistry. Compounds containing carbon-chlorine bonds occur much less frequently in nature. Volcanos emit some halocarbons, and marine algae generate chloromethane. Other marine species produce toxic organohalogen molecules that protect them from predators. Nevertheless, organic chlorine compounds are uncommon, and consequently there are few mechanisms that degrade them. 

More recently, another class of organic chlorine compounds has emerged as an environmental hazard. These are the dioxins, which, like DDT, contain ring compounds with chlorine substituents. A relatively simple example is 2,3,7,8-tetrachlorodibenzo-p-dioxin ... 

A number of organic chlorine, or chloramine, compounds are now available for disinfection and antisepsis. These are the N-chloro (=N-C1) derivatives of, for example, sulphonamides giving compounds such as chloramine-T and dichloramine-T and halazone (Fig. 10.5), which may be used for the disinfection of contaminated drinking water. 

Ogata M, Takatsuka Y, Tomokuni K. 1971. Excretion of organic chlorine compounds in the urine of persons exposed to vapours of trichloroethylene and tetrachloroethylene. Br J Ind Med 28 386. 

The methods of analysis for the chlorinated hydrocarbons may be divided into five classes—determination of total organic chlorine, determination of hydrolyzable or labile chlorine, colorimetric methods, physical methods, and bioassays. The last mentioned is beyond the scope of this manuscript and is not considered. 

The total-chlorine method has been used extensively in the determination of spray residues of the chlorinated hydrocarbons 56). Usually the kind of insecticide applied has been known, and by means of the proper factor the chlorine values could be calculated to the insecticide originally used. This calculation is not entirely valid, as the determinations do not differentiate between the insecticide and its degradation products or other contaminants containing organic chlorine. The values obtained by the total-chlorine method are useful, however, because they indicate the magnitude of the residue and the analysis can be made in a short time with standard laboratory equipment. 

The total-chlorine method for determining residues of benzene hexachloride, chlordan, and toxaphene has also been used 55) in experiments where it was known that these insecticides had been applied. With benzene hexachloride, which is known to give off-flavor to some crops, it has not been demonstrated that a relation between organic chlorine values and off-flavor exists. In fact, in most cases where off-flavor was attributed to benzene hexachloride, it has not been possible to detect organically bound chlorine. 

Recently it was shown that when DDT, benzene hexachloride, or toxaphene is fed or applied to cattle, such organic chlorine residue as may be present in the fatty tissues consists essentially of unchanged insecticide. Carter (12) demonstrated their presence by separating the fats and other oxygenated products with sulfuric acid-sodium sulfate mixture and determining total chlorine. In experiments with DDT Schechter (46) demonstrated its presence in fatty tissue and in butterfat by the Schechter-Haller colorimetric method (47). The residues were then tested for toxicity to houseflies in comparison with the known insecticides of the same concentration. In both cases the known insecticide gave the same mortality as the residue. 

Organic-Chlorine Determinations as a Measure of Insecticide Residues in Agricultural Products... 

Because the results obtained reflect the presence, not only of the insecticide in question, but also of any of its decomposition products or other organic compounds containing halogen, confirmatory evidence of the identity and amount of the residues was desired, Therefore, studies to correlate the results of organic-chlorine determinations with insecticidal activity were undertaken. 

A sample of alfalfa hay from Bozeman, Mont., that had received two spray applications, each of 4 pounds of technical toxaphene per acre, was found by the method recommended by Carter and Hubanks (3) to contain 225 p.p.m. of organic chlorine, equivalent to 331 p.p.m. of toxaphene. This sample was obtained from a bale approximately 5 months after the last spray application. A similar sample of untreated hay was found to contain 1.2 p.p.m. of organic chlorine. 

Samples of abdominal fat from a steer that had been fed hay containing toxaphene residues and from a steer that had been fed untreated hay were analyzed for their organic-chlorine content by the method recommended by Carter (i). The organic-chlorine content of the fat from the treated steer in excess of the amount found in the untreated steer was equivalent to approximately 700 p.p.m. of toxaphene. 

Extracts of these fat samples were treated with sodium sulfate-concentrated sulfuric acid mixture and fuming acid by the method described by Schechter et al. 5) in order to separate the organic-chlorine compound from the fatty materials. An infrared spectrum from 7 to 15 microns on carbon disulfide solutions of the residues from the fat qualitatively identified the organic-chlorine compound as toxaphene. All the bands of toxaphene in this spectral region were plainly seen in the treated steer extract, whereas none of the absorption bands were visible in the untreated steer extract. 

Different samples of chlorinated camphene containing from 62 to 72% of chlorine all give the same infrared spectra. However, the toxicity to flies reaches a maximum at a chlorine content of 67 to 69% and drops off rapidly below 60% and above 72%. From the results of both the infrared spectroscopic examination and the fly-toxicity tests given below, it is concluded that the organic-chlorine compound in the fat was essentially unchanged toxaphene. 

CARTER, NELSON, AND GERSDORFF—ORGANIC-CHLORINE DETERMINATIONS... 

The tests reported in this paper were intended only to show general agreement between the insecticide level calculated from organic-chlorine determinations and fly mortality. 

It is also shown that organic-chlorine residues on alfalfa hay resulting from insecticide applications of toxaphene and the organic-chlorine content of beef fat from animals fed alfalfa hay containing toxaphene residues or sprayed with benzene hexachloride or DDT approximate a true measure of the amounts of these compounds present. 

The goal of setting operating requirements for hazardous waste combustion units is to ensure that the unit will operate in a way that meets the performance standards for organics, chlorine, particulate matter, and metal pollutants. The unit s permit will specify the operating conditions that have been shown to meet the performance standards for organics, chlorine gas, particulate matter, and metals. 

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