Citation: FENG Li-Xia, JIN Ling-Xia, WANG Wei-Na, WANG Wen-Liang. Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C₂H₃ with CH₃F[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1623-1629. doi: 10.3866/PKU.WHXB201204112 shu

Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C₂H₃ with CH₃F

1.
1. Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China;
2. Department of Chemistry, Taiyuan Normal University, Taiyuan 030031, P. R. China

Received Date: 9 February 2012
Available Online: 11 April 2012
Fund Project: 国家自然科学基金(20873079)资助项目 (20873079)

A dual-level direct dynamics method was employed to study the hydrogen abstraction reaction of C₂H₃ with CH₃F. The calculated potential barriers (ΔE^≠) of reaction channels R1, R2, and R3 are 43.2, 43.9, and 44.1 kJ·mol^-1, respectively, and the reaction energy is -38.2 kJ·mol^-1 at the QCISD(T)/6-311++ G(d, p)//B3LYP/6-311G(d, p) level. In addition, the rate constants of the reaction were evaluated by means of the conventional transition-state theory (TST) and canonical variational transition-state theory (CVT) with or without small curvature tunneling corrections (SCT) over a wide temperature range of 200-3000 K. The results indicate that the rate constants of the three hydrogen abstraction reaction channels exhibit a positive temperature dependence, in which the variational effect is negligible for all the channels, whereas the tunneling effect is considerable at lower temperatures. Moreover, the reaction R1 is the dominant channel. Reaction R2 competes kinetically with R1 as the temperature increases, whereas the contribution from R3 is small.
- C₂H₃,
- CH₃F,
- Hydrogen abstraction reaction,
- QCISD(T)//B3LYP,
- Rate constant
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Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C2H3 with CH3F

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Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C₂H₃ with CH₃F