New Insight into the Formation Mechanism of PCDD/Fs from 2-Chlorophenol Precursor
- 10 July 2013
- journal article
- Published by American Chemical Society (ACS) in Environmental Science & Technology
- Vol. 47 (15), 8489-98
- https://doi.org/10.1021/es400632j
Abstract
Chlorophenols are known as precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The widely accepted formation mechanism of PCDD/Fs always assumes chlorophenoxy radicals as key and important intermediates. Based on the results of density functional theory calculations, the present work reports new insight into the formation mechanism of PCDD/Fs from chlorophenol precursors. Using 2-chlorophenol as a model compound of chlorophenols, we find that apart from the chlorinated phenoxy radical, the chlorinated phenyl radical and the chlorinated α-ketocarbene also have great potential for PCDD/F formation, which has scarcely been considered in previous literature. The calculations on the self- and cross-coupling reactions of the chlorophenoxy radical, the chlorinated phenyl radical and the chlorinated α-ketocarbene show that the formations of 1-MCDD, 1,6-DCDD, 4,6-DCDF, and 4-MCDF are both thermodynamically and kinetically favorable. In particular, some pathways involving the chlorinated phenyl radicals and the chlorinated α-ketocarbene are even energetically more favorable than those involving the chlorophenoxy radical. The calculated results may improve our understanding for the formation mechanism of PCDD/Fs from chlorophenol precursors and be informative to environmental scientists.Keywords
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