Please use this identifier to cite or link to this item: http://hdl.handle.net/1959.13/39541
- Computational study of the oxidation and decomposition of dibenzofuran under atmospheric conditions
Kennedy, Eric M.;
Dlugogorski, Bogdan Z.;
Mackie, John C.
- The University of Newcastle. Faculty of Engineering & Built Environment, School of Engineering
- The atmospheric degradation of dibenzofuran (DF) initiated by OH addition has been studied by using density functional theory (B3LYP method). Site C1 in DF is predicted to be the favored site for OH addition, with a branching ratio of 0.61 to produce a DF-OH(1) adduct. The calculated reaction rate constant for OH addition to DF has been used to predict the atmospheric lifetime of DF to be 0.45 day. Three different modes of attack of O₂(³∑g) on DF-OH(1) have been examined. Abstraction of hydrogen gem to OH in DF-OH(1) by O₂(³∑g) (producing 1-dibenzofuranol I) and dioxygen addition in the three radical sites in cis and trans orientation (relative to the ispo-added OH) of the π-delocalized electron system of DF-OH(1) are feasible under atmospheric conditions. The free energy of activation (at 298.15 K) for the formation of 1-dibenzofuranol is 15.1 kcal/ mol with a free energy change of -36.3 kcal/mol, while the formation of DF-OH(1)-O₂adducts are endergonic by 9.2-21.8 kcal/mol with a 16.3-23.6 kcal/mol free energy of activation. On the basis of the calculated reaction rate constants, the formation of 1-dibenzofuranol is more important than the formation of DF-OH-O₂adducts. The results presented here are a first attempt to gain a better understanding of the atmospheric oxidation of dioxin-like compounds on a precise molecular basis.
- Journal of Physical Chemistry A Vol. 112, Issue 30, p. 6960-6967
- Publisher Link
- American Chemical Society
- Resource Type
- journal article