| Title: | A quantum theory investigation on atmospheric oxidation mechanisms of acrylic acid by OH radical and its implication for atmospheric chemistry |
| Author(s): | Chu H; Wu W; Shao Y; Tang Y; Zhang Y; Cheng Y; Chen F; Liu J; Sun J; |
| Address: | "Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Cihu Road 11, Huangshi, Hubei, 435002, People's Republic of China. College of Foreign Languages, Hubei Normal University, Cihu Road 11, Huangshi, Hubei, 435002, People's Republic of China. School of Materials Science and Engineering, MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Sun Yat-sen University, Guangzhou, 510275, People's Republic of China. School of Environmental and municipal Engineering, Qingdao Technological University, Fushun Road 11, Qingdao, Shandong, 266033, People's Republic of China. Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, People's Republic of China. Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Cihu Road 11, Huangshi, Hubei, 435002, People's Republic of China. sunjy231@gmail.com" |
| Journal Title: | Environ Sci Pollut Res Int |
| DOI: | 10.1007/s11356-018-2561-6 |
| ISSN/ISBN: | 1614-7499 (Electronic) 0944-1344 (Linking) |
| Abstract: | "The hydroxyl radical, as the most important oxidant, controls the removal of some volatile organic compounds (VOCs) in the atmosphere. In this work, the atmospheric oxidation processes of acrylic acid by OH radical have been investigated by density functional theory (DFT). The energetic routes of the reaction of CH(2)CHCOOH with OH radical have been calculated accurately at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level. It is implicated that the oxidation has five elementary reaction pathways mostly hinging on how hydroxyl radical approaches to the carbon skeleton of acrylic acid. The atmospheric degradation mechanisms of the CH(2)CHCOOH by OH radical are the formation of reactive intermediates IM1 and IM2. Meanwhile, the further oxidation mechanisms of IM1 and IM2 by O(3) and NO are also investigated. The rate coefficients have been computed using tight transition state theory of the variflex code. The calculated rate coefficient is 2.3 x 10(-11) cm(3) molecule(-1) s(-1) at standard pressure and 298 K, which is very close to the laboratory data (1.75 +/- 0.47 x 10(-11) cm(3) molecule(-1) s(-1)). Moreover, the atmospheric lifetime of acrylic acid is about 6 h at 298 K and 1 atm, implying that the fast sinks of acrylic acid by hydroxyl radical" |
| Keywords: | Acrylates/*chemistry Atmosphere/*chemistry Hydroxyl Radical/*chemistry Kinetics Oxidation-Reduction *Quantum Theory Acrylic acid Atmospheric lifetime Mechanism Potential energy surface Rate coefficient Tddft Tight transition state theory; |
| Notes: | "MedlineChu, Han Wu, Wenzhong Shao, Youxiang Tang, Yizhen Zhang, Yunju Cheng, Yinfang Chen, Fang Liu, Jiangyan Sun, Jingyu eng 21507027/National Natural Science Foundation of China/ Germany 2018/06/23 Environ Sci Pollut Res Int. 2018 Sep; 25(25):24939-24950. doi: 10.1007/s11356-018-2561-6. Epub 2018 Jun 21" |
