Quantum chemical investigation of formation of polychlorodibenzo-p-dioxins and dibenzofurans from oxidation and pyrolysis of 2-chlorophenol

Mohammednoor Altarawneh, Bogdan Z. Dlugogorski, Eric M. Kennedy, John C. Mackie

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Density functional theory (DFT) calculations have been used to obtain thermochemical parameters for formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) from the oxidation of 2-chlorophenol. Formation mechanisms of PCDD through radical-radical coupling have been investigated in detail. The sequence of 2-chlorophenoxy radical coupling has been studied. The formation of chlorinated bis keto dimers which results from cross coupling of 2-chlorophenoxy at the ortho carbon bearing hydrogen (a known direct route for PCDF formation) passes through a tight transition structure whose barrier is 9.4 kcal/mol (0 K). Three routes for the formation of the most abundant PCDD/PCDF species (viz., 4,6-dichlorodibenzofuran, 4,6-DCDF, and 1-monochlorodibenzo-p- dioxin, 1-MCDD) in oxidation and pyrolysis of 2-chlorophenol are discussed. In the case of 4,6-DCDF, formation through H or HO + keto-keto ⇄ H 2 or H2O + keto-keto ⇄ H2 or H 2O + enol-keto ⇄ H2 or H2O + 4,6-DCDF + HO is shown to be the preferred route. The other two routes proceed via closed shell processes (keto-keto ⇄ enol-keto ⇄ enol-enol ⇄ H 2O + 4,6-DCDF) and (keto-keto ⇄ enol-keto ⇄ (H-,OH-) 4,6-DCDF ⇄ H2O + 4,6-DCDF). Results indicate that 1-MCDD should be the favored product in 2-chlorophenol pyrolysis in agreement with experimental findings. According to our results, tautomerization (inter-ring hydrogen transfer) and intra-annular displacement of HCl would not be competitive with paths deriving from H abstraction from the phenolic oxygen and the benzene ring followed by displacement of Cl in the formation of dibenzo-p-dioxin (DD) and 1-MCDD. The results presented here will assist in construction of detailed kinetic models to account for the formation of PCDD/PCDF from chlorophenols.

Original languageEnglish
Pages (from-to)2563-2573
Number of pages11
JournalJournal of Physical Chemistry A
Issue number13
Publication statusPublished - Apr 5 2007
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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