The growth mechanism of polycyclic aromatic hydrocarbons from the reactions of anthracene and phenanthrene with cyclopentadienyl and indenyl

被引：27

作者：

Zhu, Ledong ^{[1
]}

Shi, Xiangli ^{[1
]}

Sun, Yanhui ^{[2
]}

Zhang, Qingzhu ^{[1
]}

Wang, Wenxing ^{[1
]}

机构：

[1] Shandong Univ, Environm Res Inst, Jinan 250100, Shandong, Peoples R China

[2] Qingdao Univ Sci & Technol, Coll Environm & Safety Engn, Qingdao 266042, Peoples R China

来源：

CHEMOSPHERE | 2017年 / 189卷

基金：

中国国家自然科学基金;

关键词：

PAH growth mechanism; Formation reactions; Anthracene; Phenanthrene; Cyclopentadienyl; Indenyl; ATMOSPHERIC CHEMICAL-REACTIONS; DENSITY-FUNCTIONAL THEORY; TRANSITION-STATE THEORY; DEGRADATION-PRODUCTS; VIBRATIONAL-SPECTRA; FORMATION PATHWAYS; RISK-ASSESSMENT; CANCER RISK; OH RADICALS; PAH;

D O I：

10.1016/j.chemosphere.2017.09.004

中图分类号：

X [环境科学、安全科学];

学科分类号：

08 ; 0830 ;

摘要：

Polycyclic aromatic hydrocarbons (PAHs) are highly toxic, mutagenic and/or carcinogenic to humans. To reduce the emission of PAHs, it's significant and indispensable to explore the PAH formation mechanism. In the present work, the growth mechanism of PAHs from the reactions of anthracene and phenanthrene with cyclopentadienyl and indenyl radicals was investigated with the aid of high-accuracy quantum chemistry calculation. The rate constants of key elementary steps were calculated by meaning of the canonical variation transition-state (CVT) theory with the small curvature tunneling (SCT) correction over the temperature range of 400-1400 K. The mechanism of the PAH formation involves in six elementary steps, addition reaction, ring closure, intramolecular H-shift, cleavage of C-C bond, intramolecular H-shift and unimolecular elimination of CH3 or H. The cleavage of C-C bond is the rate determining step due to the high barrier. The formation of PAHs from the reactions of anthracene with cyclopentadienyl and indenyl radicals is easier than that from the reactions of phenanthrene. (C) 2017 Elsevier Ltd. All rights reserved.

引用

页码：265 / 276

页数：12

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