- Title
- Theoretical study of reaction pathways of dibenzofuran and dibenzo-p-dioxin under reducing conditions
- Creator
- Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; Mackie, John C.
- Relation
- Journal of Physical Chemistry A Vol. 111, Issue 30, p. 7133-7140
- Publisher Link
- http://dx.doi.org/10.1021/jp071166q
- Publisher
- American Chemical Society
- Resource Type
- journal article
- Date
- 2007
- Description
- A density functional theory (DFT) study was carried out to investigate possible reactions of dibenzofuran (DF) and dibenzo-p-dioxin (DD) in a reducing environment. Reaction energies, barrier heights, and molecular parameters for reactants, intermediates, products, and transition states have been generated for a wide range of possible reactions. It was found that C−O β-scission in DF incurs a very large energy barrier (107 kcal/mol at 0 K), which is just 3 kcal/mol less than the direct H fission from C−H in DF to form dibenzofuranyl radicals. It was found that DF allows direct H addition to C1−C4 and C6−C9 as well as addition of two H atoms from a hydrogen molecule at sites 1 and 9 of DF. A bimolecular reaction of DF with H or H2 is found to have a significantly lower barrier than unimolecular decomposition through C−O β-scission. An explanation for the predominance of polychlorinated dibenzofurans (PCDF) over polychlorinated dibenzo-p-dioxins (PCDD) in municipal waste pyrolysis is presented in the view of the facile conversion of DD into DF through ipso-addition at the four C sites of the two C−O−C central bonds in DD.
- Subject
- density functional theory (DFT); dibenzofuran (DF); dibenzo-p-dioxin (DD)
- Identifier
- http://hdl.handle.net/1959.13/33953
- Identifier
- uon:3410
- Identifier
- ISSN:1089-5639
- Language
- eng
- Reviewed
- Hits: 1292
- Visitors: 1554
- Downloads: 0
| Thumbnail | File | Description | Size | Format |
|---|