1. Theoretical studies on the mechanisms and rate constants for the hydroxylation of n-butyl, iso-butyl and tert-butyl vinyl ethers in atmosphere.
- Author
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Han, Dandan, Cao, Haijie, Li, Jing, Li, Mingyue, Li, Xin, He, Maoxia, and Hu, Jingtian
- Subjects
HYDROXYLATION ,BUTYL group ,CHEMICAL reactions ,ISOMERS ,ETHERS - 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, 9.32 × 10 and 5.75 × 10cmmolecules, respectively. Additionally, the lifetimes of the three isomers with respect to OH radical are $$\tau$$ = 1.13 h, $$\tau$$ = 1.49 h, and $$\tau$$ = 2.41 h. [ABSTRACT FROM AUTHOR]
- Published
- 2015
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