Kinetics and mechanisms of gas phase reactions of hexenols with ozone

被引：11

作者：

Lin, Xiaoxiao ^{[1
]}

Ma, Qiao ^{[1
,3
]}

Yang, Chengqiang ^{[1
,2
]}

Tang, Xiaofeng ^{[1
]}

Zhao, Weixiong ^{[1
]}

Hu, Changjin ^{[1
]}

Gu, Xuejun ^{[1
]}

Fang, Bo ^{[1
]}

Gai, Yanbo ^{[1
]}

Zhang, Weijun ^{[1
,2
]}

机构：

[1] Chinese Acad Sci, Anhui Inst Opt & Fine Mech, LabAtmospher Physicochem, Hefei 230031, Peoples R China

[2] Univ Sci & Technol China, Sch Environm Sci & Optoelect Technol, Hefei 230026, Anhui, Peoples R China

[3] Univ Sci & Technol China, Hefei 230026, Peoples R China

来源：

RSC ADVANCES | 2016年 / 6卷 / 87期

基金：

中国国家自然科学基金;

关键词：

VOLATILE ORGANIC-COMPOUNDS; RATE COEFFICIENTS; RATE CONSTANTS; UNSATURATED ALCOHOLS; OH RADICALS; (Z)-3-HEXEN-1-OL; EMISSIONS; SERIES; NO3; 1-PENTEN-3-OL;

D O I：

10.1039/c6ra17107a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An absolute kinetic study is reported for the reactions of O-3 with a series of C6 hexenols, (Z)-2-hexen-1-ol, (Z)-3-hexen-1-ol, (Z)-4-hexen-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, and (E)-4-hexen-1-ol. At 298 K and atmospheric pressure, the rate constants (in units of 10(-17) cm(3) molecule(-1) s(-1)) were measured to be 7.44 +/- 1.03, 5.47 +/- 0.71, 7.09 +/- 0.91, 16.6 +/- 2.2, 6.19 +/- 0.72 and 10.5 +/- 1.4, respectively. To gain a deeper insight into the reactivity and mechanism, theoretical calculations were also performed for the title reactions with the methods of density functional theory (DFT) and transition-state theory (TST). The geometries, energies, and harmonic vibrational frequencies of each stationary point were obtained at the BH&HLYP/6-31+G(d,p) level of theory. The calculated rate constants are in good agreement with the experimental data, and the reactivity of hexenols with O-3 shows a strong dependence on their chemical structure based on the theoretical results. Finally, lifetimes of the C6 hexenols, with respect to their reactions with some important atmospheric oxidants such as O-3, OH and NO3 radicals, have also been discussed in the article.

引用

页码：83573 / 83580

页数：8

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