- Optimization of Perchlorination Conditions for Some Representative Polychlorinated Biphenyls
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The yield of decachlorobiphenyl (DCB) from representative Aroclors (50 to 6000 ng) using antimony pentachloride as perchlorinating agent was extremely temperature dependent below 236 deg C for a reaction period of 2 h.At 288 deg C, a 35-min reaction period was sufficient to obtain DCB yields >80percent for Aroclors 1016, 1242, 1254, and 1268.The perchlorination process was shown to be first order.The temperature dependence of the reaction times below 236 deg C was largely responsible for the inconsistent perchlorination yields reported previously in the literature.The extraction of DCB with hexane form a HCl-acidified perchlorinated solution and the subsequent column chromatography on silica gel were also essential after the perchlorination to quantitate the DCB by (63)Ni electron capture/gas chromatography.The structures of the two nonachlorobiphenyls, which were the penultimate stable intermediates before DCB, were found.The methodology to use the technique for air and blood samples was described.
- Lin, Jia Ming,Hee, Shane S, Que
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- Mechanism of PCBs formation from the pyrolysis of chlorobenzenes
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Polychlorinated biphenyls (PCBs) were formed by pyrolysis of chlorobenzenes in a HCl atmosphere. Varieties of substituted chlorobenzenes were used as model compounds to optimize the condensation reaction. Lower chlorinated benzenes produce more PCBs than that of higher ones. Up to 0.7 μg PCBs/mg 1,2,3-trichlorobenzene was produced through the condensation reaction.
- Liu, Peng-Yan,Zheng, Ming-Hui,Zhang, Bing,Xu, Xiao-Bai
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Read Online
- Electrophilic phosphonium cations (EPCs) with perchlorinated-aryl substituents: Towards air-stable phosphorus-based Lewis acid catalysts
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A series of phosphines incorporating (C6Cl5) substituents, Ph2P(C6Cl5) 1, PhP(C6Cl5)22, P(C6Cl5)33 and (C6F5)P(C6Cl5)24 were prepared. In the case of 1, 2 and 4, these were converted to the corresponding aryl-difluorophosphoranes 5-7via reaction with XeF2, whereas reaction of 3 with XeF2 afforded only an inseparable mixture of products. The compounds 5-7 were converted to the fluorophosphonium cations 8-10, whereas the reaction of 3 with Selectfluor afforded (C6Cl5)2POF and (C6Cl5)2. The fluorophosphonium salts showed evidence of improved air stability as well as Lewis acid catalytic activity in hydrodefluorination, hydrosilylation, deoxygenation and dehydrocoupling chemistry.
- Postle, Shawn,Podgorny, Vitali,Stephan, Douglas W.
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p. 14651 - 14657
(2016/10/03)
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- On assembling polychlorinated aromatic hydrocarbons from carbon tetrachloride via dichlorocarbene intermediary by a solvothermal reaction: A reaction pattern from carbene-ylide interconversion
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(Chemical Equation Presented) The forced one-electron reduction of carbon tetrachloride with sodium in a sealed steel vessel is shown to have a narrow window of conditions to arrest the reaction at the polychlorinated aromatic hydrocarbons (PCAHs), as well as to prevent the reaction from proceeding all the way to the final stage of graphite and other carbon solids. The intermediates are quenched with toluene or benzene to give electrophilic substitution products and with water to give a quinomethine as the major product. The product pattern leads us to propose the carbene, perchlorobenzo[c,d]pyren-6-ylidene, or its reversible dimer as the major intermediate among others, that survives the severe conditions until coming into contact with these nucleophiles. Mainly from aromatic resonance stabilization, the carbene is proposed to have a delocalized singlet state analogous to a ylide electronic structure and, thus, undergoes observed ionic reactions instead of typical carbene reactions. This work serves as a mechanistic link on the structural evolution of carbon networks between molecular chemistry and nanomaterial chemistry.
- Xie, Su-Yuan,Peng, Yin,Chen, Meng,Huang, Rong-Bin,Chow, Yuan L.,Zheng, Lan-Sun
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p. 1400 - 1407
(2007/10/03)
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- Effects of oxygen on formation of PCB and PCDD/F on extracted fly ash in the presence of carbon and cupric salt
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The effect of oxygen-nitrogen atmosphere (N2 + 10%O2, N2 + 1%O2 and 99.999% N2) on the formation of PCB, PCDD and PCDF by the de novo synthetic reactions in the system consisting of extracted fly ash
- Pekarek,Grabic,Marklund,Puncochar,Ullrich
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p. 777 - 782
(2007/10/03)
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- Organochlorine formation in magnesium electrowinning cells
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The formation of organochlorines during the electrolytic production of magnesium was investigated using a laboratory-scale electrolytic cell having a graphite anode, a liquid aluminium alloy cathode, and a molten chloride electrolyte. The cell was operated at current densities ranging from 3000 to 10,000 A m-2 and at temperatures ranging from 660°C to 750°C. Organochlorines were adsorbed from the cell off-gases onto silica gel, extracted with hexane, and determined by gas chromatography. All compounds identified were fully chlorinated aliphatic and aromatic compounds, the major components being hexachlorobutadiene, hexachlorobenzene, hexachloroethylene, and octachlorostyrene. The total amount of organochlorines per tonne of magnesium produced decreased with electrolysis time and with current density and increased with operating temperature; it was also dependent on the type of graphite employed. The output of organochlorines Varied from 5 to 20 g t-1 of magnesium.
- Deutscher,Cathro
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p. 147 - 155
(2007/10/03)
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- Removal of dioxins and related aromatic hydrocarbons from flue gas streams by adsorption and catalytic destruction
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The dioxin removing capacity of the shell dedioxin system (SDDS a - Ti/V oxidative type catalyst) has been tested using the Umefa lab-scale incinerator over the temperature range 100 -230°C and at space velocities of 8000 and 40,000 h-1. Other analogous organic compounds, such as PCBs, PAHs, chlorobenzenes and chlorophenols have also been investigated. Results show a high degree of dioxin removal already at 100°C (82%), which occurs mainly by adsorption. When the temperature is raised a transition towards destruction is seen and at 150°C, gas hour space velocity (GHSV) 8000 and at 230°C, GHSV 40,000 virtually all removal is by destruction. High PCDD/F destruction efficiencies are reported (> 99.9%, based on I-TEQ); the other dioxin-related species and PAHs are also removed and destroyed to a significant extent. The SDDS has proved to be an effective means of destroying organic compounds in the gas phase, particularly dioxins, at temperatures as low as 150°C.
- Liljelind, Per,Unsworth, John,Maaskant, Onno,Marklund, Stellan
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p. 615 - 623
(2007/10/03)
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- Influence of variation in combustion conditions on the primary formation of chlorinated organic micropollutants during municipal solid waste combustion
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The aim of this study was to investigate the influence of variation in combustion conditions on the primary formation of organic micropollutants (OMPs). The flue gas samples were taken at a relatively high flue gas temperature (650°C), to enable mechanistic studies on the high temperature formation (primary formation). Eleven experiments were performed in a laboratory scale fluidized bed reactor fed with an artificial municipal solid waste (MSW). The samples were analyzed for mono- to octachlorinated dibenzo- p-dioxins and dibenzofurans (CDDs/Fs), tri- to decachlorinated biphenyls (CBs), di- to hexachlorinated benzenes (CBzs), and di- to pentachlorinated phenols (CPhs). In addition to chlorinated OMPs, nonchlorinated dibenzo-p- dioxin (DD), dibenzofuran (DF), and biphenyl (BP) were analyzed. The experiments show that variations in the CE influence the degree of chlorination of the organic micropollutants. A correlation between low CE and formation of non- and low-chlorinated DMPs was seen and a distinct relationship of higher chlorinated homologues and efficient combustion condition. Thus, the DiCDFs and DiCBzs are formed during low combustion efficiency (CE), while the PeCDF and PeCBzs formation take place at higher CE. The distribution between primary and secondary air is important for the formation of higher CDD/Fs and CBzs. The primary formation of CDDs and CDFs is through different mechanisms. The CDDs are mainly formed by condensation of CPhs, while the CDFs are formed through a non- or a low-chlorinated precursor followed by further chlorination reactions.
- Wikstroem,Tysklind,Marklund
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p. 4263 - 4269
(2007/10/03)
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- Physical, spectral and chromatographic properties of all 209 individual PCB congeners
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Through the use of two capillary GC columns: 40% octadecyl/ 15% phenyl methyl siloxane and 50% phenyl methyl siloxane, it was possible to separate 201 PCB congeners with only four unresolved pairs. The data compiled in this study for all 209 congeners will aid in the identification of selected individual components of these environmental pollutants. The use of this data also presents the opportunity for the improved quantification of the commercial PCB formulations. -from Authors
- Bolgar,et al.
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p. 2687 - 2705
(2007/10/03)
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- Thermolysis of phenoxyaluminum compounds and formation of PCDD/F and their precursors
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Within the study of the formation of chlorinated dioxins and dibenzofurans and their precursors the thermolysis of hexachloroethane over the aluminum melt was investigated. "De novo" synthesis of precursors of PCDD/F was studied in the model system AlCl3/elemental carbon. Totally chlorinated heterocyclic compounds have been detected parallel with the formation of organochlorine compounds. The possibility of inserting oxygen to aluminum organyls was presented. In order to gain more detailed knowledge of the catalytic behaviour of fly ash the chemistry of thermolysis of phenoxy- and chlorophenoxy aluminum compounds at 300°C with the presence and absence of Al2O3 was investigated. Reagent compounds and products of thermolysis were followed by mass spectrometry.
- Voncina,Medved,Zerjal
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p. 2029 - 2038
(2007/10/03)
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- IS THE ORTHOGONALITY OF PARTIALLY FILLED ORBITALS IN AREGULAR CHAIN A PROPER STRATEGY TOWARDS HIGH SPIN MOLECULES?
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The Hartree-Fock band theory predicts that the FM state would be energetically favored over the AF and M states at the limit case where the over lap between the interacting semiocuped orbitals is really zero (orthogonality).In order to test experimentally this strategy towards organic high spin molecules, we addressed ourselves to salts of polyradical-cations 1.Mono- and di- radical-cation generated from perchlorobiphenyl/SbF5 have been studied at several temperatures with UV-Vis and ESR spectroscopies.The spectral data agree with a D2d ground-state triplet with two localized electrons, each one placed (and delocalized) only on one phenyl moiety.
- Veciana, Jaume,Vidal, Jose,Jullian, Nathalie
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p. 443 - 450
(2007/10/02)
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- Polyhalogenoaromatic Compounds. Part 43. Inter- and Intra-molecular Reactions of Polychloroaromatic Compounds with Copper
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The reaction of polychloroiodoarenes with copper in dimethylformamide gives good yields of the biaryls. 4-Bromotetrachloropyridine gives products of halogen exchange and reduction as well as coupling.Pentachloropyridine gave only tetrachloropyridines.Evidence against free radical or pyridyne intermediates is presented, and it is postulated that the reactions proceed via pyridylcopper compounds, although an electron transfer mechanism is not excluded.On reaction with copper, some 4-(o-halogenophenoxy)- and 4-(o-halogenothiophenoxy)-tetrahalogenopyridines give products of cyclisation, reduction, and halogen transfer.Copper reacts initially, at least in part, with the pyridyl group rather than with the o-halogenoaryl group.The results are again consistent with a reaction pathway involving a pyridylcopper intermediate.The products of nucleophilic substitution in pentahalogenopyridines by some phenols, thiophenols, and anilines are reported.
- Mack, Arthur G.,Suschitzky, Hans,Wakefield, Basil J.
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p. 1682 - 1687
(2007/10/02)
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