Chlorinated compound data

The kinetics of thermal decomposition and depolymerisation of various polymers is discussed. The aim of the study was to find reaction conditions where different polymers can be separated from mixtures by decomposing them into their monomers or into pyrolysis products and where chlorine and/or nitrogen are eliminated from the polymers without forming toxic compounds. Data are given for PVC, PS, PE, and PR 13 refs. 

Ti(R2 fc)3Cl is a seven coordinated monomeric species, as is suggested from the spectral data and the non-electrolytic character and confirmed by an X-ray diffraction study (6). Apart from the chlorine compounds the bromine analogues are reported (9). 

The authors of primary Reference 80 present their own and selected literature values for the R—NO bond enthalpies for the hydrocarbyl cases of Me, Et, t-Bu, allyl and benzyl, as well as mixed fluorinated, chlorinated methyl radicals. We now wish to compare nitroso species with the corresponding amino and nitro compounds. Choosing what we consider the most reliable and relevant nitroso compound data, and accompanying them with the corresponding radical data, we derive enthalpies of formation of gaseous nitrosomethane, 2-methyl-2-nitrosopropane and o -nitrosotoluene81 to be 65 2, —29 4 and 174 7 kJmol-1. (By comparison, the earlier values recommended8 for nitrosomethane and 2-methyl-2-nitrosopropane were 70 and —42 kJmol-1 respectively.)... 

In interpreting the data for the total petroleum hydrocarbons in a sample, the amount of moisture cannot be ignored because moistme blocks the extraction of petroleum hydrocarbons by another hydrocarbon (Freon). Potentially, sulfm or phthalate compounds also interfere with total petroleum hydrocarbons analyses. This is similar to the problem of strong interferences from phthalate esters or chlorinated solvents when one is using electron capture methods to look for chlorinated compounds such as polycholorbiphenyls or pesticides. 

The oxidation of chlorinated compounds produces hydrogen chloride (HCl) along with the carbon dioxide and water vapor. Some catalyst aging data suggest that HCl exposure over 10,000 parts per million by volume (ppmv) for extended periods may lead to catalyst deactivation over time. 

Bromine compounds reduced flame speeds in all cases, but chloroform increased them in most cases. Although the promoting effect of chloroform has not been reported before and the view generally is that chlorine compounds reduce flame speeds, a close examination of previous data (4, 6,7,9) reveals that under certain conditions, chlorine and methyl chloride had increased flame speeds. 

The following table shows selected examples from the collection of the data for all gaseous or volatile chlorine compounds. 

The number of compounds which contain carbon-bromine bonds and which have been studied in the gas phase is again smaller than the number of corresponding chlorine compounds. Sufficient data, however, are available for compounds with only one bromine bonded to carbon, to discuss the effects of various substituents on the C—Br bond distance. Only very limited structural results exist for compounds with more than one bromine atom bonded to carbon, i.e. for compounds with CBr2 or CBr3 groups. 

They conclude that, "in view of the world-wide use of organo-chlorine insecticides and the extensive distribution of their residues in soil, together with the foregoing evidence, it is possible that they might now contaminate the atmosphere continuously. This conclusion is entirely consistent with their data and with the evidence of organo-chlorine compounds in the rainfall samples reported by Weibel (11) and Cohen (4). Similar results were obtained from rain samples collected in the metropolitan area of London by Abbott et al. (1). These authors were also able to demonstrate the presence of pesticides in the atmosphere (2). 

DOT CLASSIFICATION 6.1 Label KEEP AWAY FROM FOOD SAFETY PROFILE Suspected carcinogen with experimental carcinogenic and mmorigenic data. Poison by intraperitoneal route. Moderately toxic by ingestion. Experimental teratogenic effects. Human mutation data reported. A skin and eye irritant. Combustible when exposed to heat or flame. When heated to decomposition or on contact with acid or acid fumes, it emits highly toxic fumes of aniline and chlorine compounds. Reacts explosively with aniline... 

Special works on summarizing information concerning halogen compounds are noteworthy. Outstanding is the compilation of data on organic chlorine compounds, which presents their preparation, properties, chemical behavior, and identification, The chemistry of fluorine compounds has been reviewed in several excellent works. ... 

The discussion focused on Nickel catalysts. Commercial availability is very good as in Europe alone at least 4 manufacturers provide these catalysts. The pellet catalysts are less expensive than monolith supported catalysts. One of the large uncertainties of these catalysts is their deactivation rate under practical conditions. Deactivation occurs due to reactions with (heavy) metal-, sulfur- and chlorine compounds. Due to the lack of extensive data the costs for applying Ni-catalysed for tar removal in commercial biomass CHP systems are still unknown. 

Table 10.12 lists the Ea of aromatic nitrocompounds determined by both the TCT and ECD methods. The values are the weighted averages. The ECD and TCT values agree within the uncertainty. They are confirmed by reduction potential data and CURES-EC calculations (not fisted). This is the largest number of Ea for related compounds that have been measured by any two techniques [15, 16, 63-68]. The ECD Ea for the dimethyl-nitrobenzenes, m-Cl-nitrobenzene, p-Cl-nitrobenzene, and 2-Cl-6-Me-nitrobenzene are not published elsewhere. The Ea for the dimethyl-nitrobenzenes are obtained from data in the linear region. Those for the chlorinated compounds are obtained from the fit to the data in both regions. The Ea for m-Cl-nitrobenzene is a lower limit because there are no data in the a region. These confirm the TCT values. 

The electron affinities of the chlorinated biphenyls are lower than those of the chlorinated napthalenes. Nominal values are taken from Table 11.12. The temperature dependence of the three isomers of the monchlorobiphenyl will be similar to meta, ortho, and para dichlorobenzene data. Likewise, the temperature dependence of the compounds with two chlorines on the same ring will be similar to that of the trichlorobenzenes. The response of the fully chlorinated compound will be similar to that of hexachlorobenzene. The isomers with eight and nine chlorines only show nondissociative capture. Approximate curves for the chlorinated biphenyls are illustrated in Figure 11.13 and compared with experimental data obtained using the PDECD [45]. 

In the last twenty years, PCDD and PCDF were identified as by-products in many industrial processes which involve chlorine or chlorinated compounds. Additionally both groups of compounds were found to be formed in a broad range of combustion processes, including accidental fires. Municipal waste incineration is particularly considered to be a very important, if not the most important, of the identified source of environmental dibenzo-p-dioxin and dibenzofuran contamination. As a consequence, the evaluation and close control of new and existing installations for their dioxin releases has become a major concern. Based on this relative importance of municipal waste incinerators, and taking into account the relative toxicity data actually available for PCDD and PCDF, it was decided to prepare and certify a crude fly ash extract (CRM 429) for the twelve more toxic PCDD and PCDF [18,19]. 

Comparatively few data are available on the conformational behavior of bicyclo[3.3.1]nonanes devoid of skeletal heteroatoms and containing substituents at the 2-, 4-, 6-, or 8-positions. Compounds containing an exo-2-chlorine (compound 82, X-ray diffraction data (61)), two exo-methoxy-groups or one exo-acetoxy and one exo-methyl-group at the 2- and 4-positions (compounds 83 (62,63) and 84 (64), respectively, 1H- and 13C-NMR... 

Figure 11-5. Reaction kinetics of chlorine compounds by the hot-wire technique. 1,3 IK Benzyl chloride. 2 1% Hexachloroethane. 4 1% Chlorinated paraffin. 5 1% Pentachlorodiphenyl. a Carrier oil without additive. From data by Sakurai, Sato and Yamamoto [37].

Systematic data on the relation between chemical structure or reactivity of chlorine compounds and lubricant additive performance are sparse. Table 11-11 gives some four-ball test data obtained by Mould, Silver and Syrett [35], with the additives listed in order of increasing effectiveness in terms of the wear/load index. The results show numerous departures from expectations based on chemical structure. For example, there is practically as much difference between the wear/load indices for the two primary chlorides, n-hexadecyl (16.2 kg) and n-hexyl (30.4 kg), as for n-hexyl chloride and t-butyl chloride (46.1 kg). A large difference would be expected on the basis of chemical reactivity between the additive effectiveness of primary and tertiary alkyl chlorides, but only a small difference for the two primary aliphatic chlorides. The overall trends are what would be expected in general, primary and aromatic chlorides are less efficacious than secondary chlorides, which in turn... 

Solid-state chlorine NMR data are available for several other simple metal salts. Silver chloride was studied by Kanda/ its chemical shift was reported as intermediate between that of sodium and cesium chlorides. Hayashi and Hayamizu also included this compound in a study along with alkali metal and cuprous halides, reporting iso( Cl) as —12.82 ppm (w.r.t. solid KCl), and found a negative temperature dependence of the chemical shift. Several studies in the... 

Compound 1 47.5 mass % sulfur and 52.5 mass % chlorine Compound 2 31.1 mass % sulfur and 68.9 mass % chlorine 2.16 Show, with calculations, how the following data illustrate the law of multiple proportions ... 

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