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Theoretical studies on the mechanisms and rate constants for the hydroxylation of n-butyl, iso-butyl and tert-butyl vinyl ethers in atmosphere

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Abstract

The reaction mechanisms for the atmospheric hydroxylation of n-butyl vinyl ether (n-BVE), iso-butyl vinyl ether (i-BVE), and tert-butyl vinyl ether (t-BVE) were investigated by using quantum chemical method in this paper. The geometry optimizations and frequency calculations were carried out at the MPWB1K/6-31+G(d,p) level, and the accurate energetic parameters were obtained by the MPWB1K/6-311++g(3df,2p) method. The reaction mechanisms for the title reactions have been presented. Ten possible reaction channels were discussed for the primary hydroxylation of n-BVE and t-BVE, while fourteen pathways for i-BVE. Three favorable reaction pathways were chosen for each isomer to undergo further investigation. Major products are n-butyl formate, iso-butyl formate, tert-butyl formate, and HCHO. The rate constants of the primary reactions were calculated over the temperature range of 200–400 K and the pressure range of 100–2,000 Torr by employing MESMER program. At 298 K and 760 Torr, the whole rate constants of n-BVE + OH, i-BVE + OH, and t-BVE + OH are 12.3 × 10−11, 9.32 × 10−11 and 5.75 × 10−11 cm3 molecule−1 s−1, respectively. Additionally, the lifetimes of the three isomers with respect to OH radical are \(\tau\) (n-BVE) = 1.13 h, \(\tau\) (i-BVE) = 1.49 h, and \(\tau\) (t-BVE) = 2.41 h.

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Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (21477065, 21337001, 20877049 and 21103147) and the Fundamental Research Funds of Shandong University (2014JC014). We thank Dr. Struan H. Robertson for providing the MESMER program.

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  1. Environment Research Institute, Shandong University, Jinan, 250100, People’s Republic of China

    Dandan Han, Haijie Cao, Jing Li, Mingyue Li, Xin Li, Maoxia He & Jingtian Hu

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Correspondence to Maoxia He.

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Han, D., Cao, H., Li, J. et al. Theoretical studies on the mechanisms and rate constants for the hydroxylation of n-butyl, iso-butyl and tert-butyl vinyl ethers in atmosphere. Struct Chem 26, 713–729 (2015). https://doi.org/10.1007/s11224-014-0517-0

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