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A quantum theory investigation on atmospheric oxidation mechanisms of acrylic acid by OH radical and its implication for atmospheric chemistry

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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 CH2CHCOOH 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 CH2CHCOOH by OH radical are the formation of reactive intermediates IM1 and IM2. Meanwhile, the further oxidation mechanisms of IM1 and IM2 by O3 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 × 10−11 cm3 molecule−1 s−1 at standard pressure and 298 K, which is very close to the laboratory data (1.75 ± 0.47 × 10−11 cm3 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.

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Acknowledgments

This work is supported by the National Natural Science Foundation of China (Nos. 21507027, 21707062, and 41775119). The authors acknowledge the Youth Fund Project of HuBei Provincial Department of Education (Q20132501) and Hubei Key Laboratory of Pollutant Analysis & Reuse Technology Open Fund (PA160204).

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Authors and Affiliations

  1. 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

    Han Chu, Yinfang Cheng, Fang Chen, Jiangyan Liu & Jingyu Sun

  2. College of Foreign Languages, Hubei Normal University, Cihu Road 11, Huangshi, Hubei, 435002, People’s Republic of China

    Wenzhong Wu

  3. 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

    Youxiang Shao

  4. School of Environmental and municipal Engineering, Qingdao Technological University, Fushun Road 11, Qingdao, Shandong, 266033, People’s Republic of China

    Yizhen Tang

  5. Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang, 621000, People’s Republic of China

    Yunju Zhang

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  1. Han Chu
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  9. Jingyu Sun
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Correspondence to Jingyu Sun.

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Chu, H., Wu, W., Shao, Y. et al. A quantum theory investigation on atmospheric oxidation mechanisms of acrylic acid by OH radical and its implication for atmospheric chemistry. Environ Sci Pollut Res 25, 24939–24950 (2018). https://doi.org/10.1007/s11356-018-2561-6

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