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  Products and mechanism of the OH-initiated photo-oxidation of perfluoro ethyl vinyl ether, C2F5OCF=CF2

Bunkan, A. J. C., Gonu, S., Amedro, D., Vereecken, L., Wallington, T. J., & Crowley, J. N. (2018). Products and mechanism of the OH-initiated photo-oxidation of perfluoro ethyl vinyl ether, C2F5OCF=CF2. Physical Chemistry Chemical Physics, 20(16), 11306-11316. doi:10.1039/c8cp01392f.

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 Creators:
Bunkan, Arne Joakim C.1, Author              
Gonu, Srinivasulu1, Author              
Amedro, Damien1, Author              
Vereecken, L.2, Author
Wallington, T. J.2, Author
Crowley, J. N.1, Author              
Affiliations:
1Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society, ou_1826285              
2external, ou_persistent22              

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 Abstract: The OH-initiated photo-oxidation of perfluoro ethyl vinyl ether (C2F5OCF[double bond, length as m-dash]CF2, PEVE) in air (298 K, 50 and 750 Torr total pressure) was studied in a photochemical reactor using in situ detection of PEVE and its products by Fourier transform IR absorption spectroscopy. The relative rate technique was used to derive the rate coefficient, k1, for the reaction of PEVE with OH as k1 = (2.8 ± 0.3) × 10−12 cm3 molecule−1 s−1. The photo-oxidation of PEVE in the presence of NOx at 1 bar results in formation of C2F5OCFO, FC(O)C(O)F and CF2O in molar yields of 0.50 ± 0.07, 0.46 ± 0.07 and 1.50 ± 0.22, respectively. FC(O)C(O)F and CF2O are formed partially in secondary, most likely heterogeneous processes. At a reduced pressure of 50 Torr, the product distribution is shifted towards formation of FC(O)C(O)F, indicating the important role of collisional quenching of initially formed association complexes, and enabling details of the reaction mechanism to be elucidated. An atmospheric photo-oxidation mechanism for PEVE is presented and the environmental implications of PEVE release and degradation are discussed.

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Language(s): eng - English
 Dates: 2018
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: -
 Identifiers: ISI: 000431821800068
DOI: 10.1039/c8cp01392f
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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 20 (16) Sequence Number: - Start / End Page: 11306 - 11316 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1