• Environmental Engineering Research
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• v.11 no.4
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• pp.232-240
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• 2006

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at $600^{\circ}C$ were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same interemediate. Tautomerization of the intermediate and $H_2O$ elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.

• Journal of Environmental Science International
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• v.21 no.8
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• pp.891-899
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• 2012

The chlorination pattern of naphthalene vapor when passed through a 1 cm particle bed of 0.5% (mass) copper (II) chloride ($CuCl_2$) mixed with silicon dioxide ($SiO_2$) was studied. Gas streams consisting of 92% (molar) $N_2$, 8% $O_2$ and 0.1% naphthalene vapor were introduced to an isothermal flow reactor containing the $CuCl_2/SiO_2$ particle bed. Chlorination of naphthalene was studied from 100 to $400^{\circ}C$ at a gas velocity of 2.7 cm/s. Mono through hexachlorinated naphthalene congeners were observed at $250^{\circ}C$ whereas a broader distribution of polychlorinated naphthalenes (PCNs) including hepta and octachlorinated naphthalenes was observed at $300^{\circ}C$. PCN production was peak at $250^{\circ}C$ with 3.07% (molar) yield, and monochloronaphthalene (MCN) congeners were the major products at two different temperatures. In order to assess the effect of a residence time on naphthalene chlorination, an experiment was also conducted at $300^{\circ}C$ with a gas velocity of 0.32 cm/s. The degree of naphthalene chlorination increased as a gas velocity decreased.

• Environmental Engineering Research
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• v.11 no.4
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• pp.217-231
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• 2006

The gas-phase formation of polychlorinated naphthalenes (PCNs) and dibenzofurans (PCDFs) was experimentally investigated by slow combustion of the three chlorophenols (CPs): 2-chlorophenol (2-CP), 3-chlorophenol (3-CP) and 4-chlorophenol (4-CP), in a laminar flow reactor over the range of 550 to $750^{\circ}C$ under oxidative condition. Contrary to the a priori hypothesis, different distributions of PCN isomers were produced from each CP. To explain the distributions of polychlorinated dibenzofuran (PCDF) and PCN congeners, a pathway is proposed that builds on published mechanisms of PCDF formation from chlorinated phenols and naphthalene formation from dihydrofulvalene. This pathway involves phenoxy radical coupling at unsubstituted ortho-carbon sites followed by CO elimination to produce dichloro-9, 10-dihydrofulvalene intermediates. Naphthalene products are formed by loss of H and/or Cl atoms and rearrangement. The degree of chlorination of naphthalene and dibenzofuran products decreased as temperature increased, and, on average, the naphthalene congeners were less chlorinated than the dibenzofuran congeners. PCDF isomers were found to be weakly dependent to temperature, suggesting that phenoxy radical coupling is a low activation energy process. Different PCN isomers, on the other hand, are formed by alternative fusion routes from the same phenoxy radical coupling intermediate. PCN isomer distributions were found to be more temperature sensitive, with selectivity to particular isomers decreasing with increasing temperature.