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The reaction mechanisms and kinetics of CF3CHFOCH3 and CHF2CHFOCF3 with atomic chlorine: a computational study

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Abstract

Due to their lack of effect on the ozone depletion, hydrofluoroethers are considered as potential candidates for third generation refrigerants. In the present work, the mechanisms and kinetics of reaction of the Cl atom with CF3CHFOCH3 and CHF2CHFOCF3 were investigated theoretically using quantum chemical methods and transition state theory. Four reaction pathways for the title reaction were explored. By using conventional transition state theory with Eckart tunneling correction, the rate constants of the title reaction were obtained over the temperature range 200–300 K. Kinetic calculations demonstrate that H-abstraction from the –CH3 group in CF3CHFOCH3 and H-abstraction from the –CHF2 group in CHF2CHFOCF3 are major reaction pathways, with the barrier heights of the two paths calculated to be −1.04 and 4.33 kcal mol−1, respectively. However, the contribution of H-abstraction from the –CHFO– group for the two reactions should also be taken into account with increased temperature. At 298 K, the calculated overall rate constants of the reaction of CHF2CHFOCF3 with the Cl atom are 4.27 × 10−15 cm3 molecule−1 s−1, which is consistent with the experimental value of (1.2 ± 2.0) × 10−15 cm3 molecule−1 s−1.

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Acknowledgments

This work is supported by National Natural Science Foundation of China (Grant No. 41165007), Science and Technology Foundation of GuiZhou Province, China (No.[2011]2107 and [2012]2189) and Open Research Fund of Key Laboratory of Atmospheric Composition and Optical Radiation, Chinese Academy of Sciences, China (JJ1107).

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  1. Department of Physics, Guizhou University, Guiyang, 550025, China

    Fang-Yu Liu & Zheng-Wen Long

  2. College of Computer and Information Engineering, Guizhou MinZu University, Guiyang, 550025, China

    Xing-Feng Tan & Bo Long

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Correspondence to Bo Long.

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Liu, FY., Long, ZW., Tan, XF. et al. The reaction mechanisms and kinetics of CF3CHFOCH3 and CHF2CHFOCF3 with atomic chlorine: a computational study. J Mol Model 20, 2435 (2014). https://doi.org/10.1007/s00894-014-2435-x

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