title: Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner.
abstract: Polychlorinated naphthalenes (PCNs) are dioxins-like compounds and are formed along with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in thermal and combustion procedures. Chlorophenols (CPs) are the most important forerunners of PCNs. A comprehensive comprehension of PCN formation procedure from CPs is a precondition for reducing the discharge of PCNs. Experiments on the formation of PCNs from CPs have been hindered by PCN toxicity and short of precise detection methods for active intermediate radicals. In this work, PCN formation mechanism in gas-phase condition from 2-chlorophenol (2-CP) as forerunner was studied by quantum chemistry calculations. Numbers of energetically advantaged formation routes were proposed. The rate constants of key elementary steps were calculated over 600-1200 K using canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT) method. This study illustrates formation of PCNs with one chlorine atom loss from 2-CP is preferred over that without chlorine atom loss. In comparison with formation of PCDFs from 2-CP, PCN products are less chlorinated and have lower formation potential.
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. xufei@sdu.edu.cn.
authors.forename: Fei
authors.initials: F
authors.lastname: Xu
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. zrm0118@163.com.
authors.forename: Ruiming
authors.initials: R
authors.lastname: Zhang
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. liyfeng1028@gmail.com.
authors.forename: Yunfeng
authors.initials: Y
authors.lastname: Li
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. zqz@sdu.edu.cn.
authors.forename: Qingzhu
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. wxwang@sdu.edu.cn.
authors.forename: Wenxing
authors.initials: W
authors.lastname: Wang
mesh_terms: D002733:Chlorophenols / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D054879:Halogenation; D009281:Naphthalenes / Q000737:chemistry*; D044367:Phase Transition
chemical_list: D002733:Chlorophenols; D005740:Gases; D009281:Naphthalenes; C030683:2-chlorophenol
keywords: 2-chlorophenol; and theoretical mechanistic and kinetic study; formation of polychlorinated naphthalene; rate constants; reaction mechanism