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Atmospheric oxidation of HFE-7300 [n-C2F5CF(OCH3)CF(CF3)2] initiated by •OH/Cl oxidants and subsequent degradation of its product radical: a DFT approach

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Abstract

To understand the atmospheric chemistry of hydrofluoroethers, we have studied the oxidation of a highly fluorinated compound n-C2F5CF(OCH3)CF(CF3)2 (HFE-7300) by OH/Cl oxidants. Here, we have employed M06-2X functional along with a 6-31 + G(d,p) basis set to obtain the optimized structures, various forms of energies, and different modes of frequencies for all species. We have characterized energies of all species on the potential energy surface, and it indicates that H-abstraction from n-C2F5CF(OCH3)CF(CF3)2 by Cl atom is kinetically more dominant than the H-abstraction reaction initiated by OH radical. In contrast, the calculated energy change (ΔrH°298 and ΔrG°298) results govern that OH-initiated H-abstraction reaction is highly exothermic and spontaneous compared to the Cl-initiated H-abstraction reaction. Rate constants are estimated using transition state theory as well as canonical variation transition state theory at the temperature range 200–1000 K and 1 atm pressure. The calculated rate constants of the H-abstraction channels are found to be in good agreement with the reported experimental rate constant at 298 K. Moreover, we have estimated the atmospheric lifetimes of HFE-7300 for the reaction with OH radical and Cl atom and are found to be 1.75 and 153.93 years, respectively. Additionally, the global warming potentials for HFE-7300 molecule are also estimated for 20-, 100-, and 500-year time horizons. Further, subsequent aerial oxidation of product radical (n-C2F5CF(OCH2)CF(CF3)2) in the presence of NO radical is performed, and it produced alkoxy radical via formation of peroxy radical. This alkoxy radical undergoes unimolecular decompositions via two different ways and formed n-C2F5CF(OCHO)CF(CF3)2 and n-C2F5CF(OH) CF(CF3)2 products.

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Acknowledgments

Dr. SP is thankful to the University Grant Commission (UGC), New Delhi, for providing financial support from Dr. D. S. Kothari Post-Doctoral Fellowship (Award letter no: F.4-2/2006(BSR)/CH/16-17/0152). S. D. Baruah is thankful to the Department of Science and Technology (DST), New Delhi, for providing him INSPIRE fellowship (No.IF160658).

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  1. Department of Chemical Sciences, Tezpur University Tezpur, Tezpur, Assam, 784028, India

    Subrata Paul, Satyajit Dey Baruah, Ramesh Chandra Deka & Nand Kishor Gour

  2. Department of Chemistry, D. N. Government College, Itanagar, Arunachal Pradesh, 791113, India

    Bhupesh Kumar Mishra

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Paul, S., Mishra, B.K., Baruah, S.D. et al. Atmospheric oxidation of HFE-7300 [n-C2F5CF(OCH3)CF(CF3)2] initiated by •OH/Cl oxidants and subsequent degradation of its product radical: a DFT approach. Environ Sci Pollut Res 27, 907–920 (2020). https://doi.org/10.1007/s11356-019-06975-1

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