Atmospheric oxidation of C-10 similar to 14 n-alkanes initiated by Cl atoms: Kinetics and mechanism
Atmospheric oxidation of C-10 similar to 14 n-alkanes initiated by Cl atoms: Kinetics and mechanism
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Cl 原子引发的 C10-14 正构烷烃的大气氧化：动力学和机理
DOI：
10.1016/j.atmosenv.2019.117166
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发表时间：
2020
影响因子：
5
通讯作者：
Maofa Ge
中科院分区：
文献类型：
--
作者：
Bo Shi;Weigang Wang;Li Zhou;Zheng Sun;Cici Fan;Yan Chen;Wenyu Zhang;Yanyang Qiao;Yanliu Qiao;Maofa Ge
本文采用质子转移反应质谱法研究了正构烷烃C10~C14在雾霾室内的光氧化反应，首次给出了Cl原子与C11~14正构烷烃反应的动力学参数。以反式-2-丁烯、间二甲苯和乙苯为参考，用相对速率法在（298±1）K和760 Torr下得到了K（正癸烷）=（4.82±0.32）× 10−10，K（正十一烷）=（5.02±0.33）× 10−10，K（正十二烷）=（5.12±0.29）× 10−10，K（正三烷）=（5.30±0.30）× 10−10，K（正十四烷）=（5.68±0.34）× 10−10的速率常数（单位为cm3分子- 1s−1）。测定的速率常数也被用来计算这些化合物（C10, C11, C12, C13, C14）的对流层寿命，每个正构烷烃分别为11.5,11.1,10.9,10.5和9.8小时。此外，还测定了反应的气相光氧化产物。在此基础上，提出了Cl原子与这5种烷烃的反应机理。
The Cl-initiated photo-oxidation reactions of n-alkanes: C10~C14, were investigated by using Proton-Transfer-Reaction Mass Spectrometry in the smog chamber, and the present work provided the kinetic parameters of the reactions of Cl atoms with C11~14n-alkanes for the first time. The rate constants (in units of cm3molecule−1s−1) were obtained using relative rate method with trans-2-butene, m-xylene and ethylbenzene as references at (298 ± 1)K and 760 Torr were k(n-decane)=(4.82 ± 0.32) × 10−10, k(n-undecane)=(5.02 ± 0.33) × 10−10, k(n-dodecane)=(5.12 ± 0.29) × 10−10, k(n-tridecane)=(5.30 ± 0.30) × 10−10, k(n-tetradecane)=(5.68 ± 0.34) × 10−10, respectively. The measured rate constants have also been used to calculate tropospheric lifetimes of these compounds (C10, C11, C12, C13, C14), which were 11.5, 11.1, 10.9 10.5 and 9.8 h for each n-alkane. In addition, the gas-phase photooxidation products of the reactions were also measured. Based on the obtained results, the reaction mechanisms of Cl atoms with these five alkanes were proposed.