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

Pāla, Subrata; Mishra, Bhupesh Kumar; Baruah, Satyajit Dey; Deka, Ramesh Chandra; Gour, Nand Kishor

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

2020

Pāla, Subrata | Mishra, Bhupesh Kumar | Baruah, Satyajit Dey | Deka, Ramesh Chandra | Gour, Nand Kishor

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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