title: Mechanism and thermal rate constants for the complete series reactions of chlorophenols with H.
abstract: Reactions of chlorophenols with atomic H are important initial steps for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in incinerators. Detailed insight into the mechanism and kinetic properties of crucial elementary steps is a prerequisite for understanding the formation of PCDD/Fs. In this paper, the complete series reactions of 19 chlorophenol congeners with atomic H have been studied theoretically using the density functional theory (DFT) method and the direct dynamics method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+6(d,p) level. Modeling of the PCDD/Fs formation requires kinetic information aboutthe elemental reactions. The rate constants were deduced over a wide temperature range of 600-1200 K using canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT). The rate-temperature formulas were fitted for the first time. This study shows that the substitution pattern of the phenol has a significant effect on the strength and reactivity of the O-H bonds in chlorophenols. Intramolecular hydrogen bonding plays a decisive role in determining the reactivity of the O-H bonds for ortho-substituted phenols.
authors: Environment Research Institute, Shandong University, Jinan 250100, P. R. China. zqz@sdu.edu.cn
authors: Qingzhu
authors: Q
authors: Zhang
authors: Xiaohui
authors: X
authors: Qu
authors: Hui
authors: H
authors: Wang
authors: Fei
authors: F
authors: Xu
authors: Xiangyan
authors: X
authors: Shi
authors: Wenxing
authors: W
authors: Wang
mesh_terms: D002733:Chlorophenols / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure
chemical_list: D002733:Chlorophenols; D006859:Hydrogen