Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF_3OCF=CF_2
- Creators
- Vereecken, L.
- Crowley, J. N.
- Amedro, D.
Abstract
Product formation in the reaction of perfluorinated methyl vinyl ether, CF_3OCF=CF_2, with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) levels of theory. The stable end-products in an oxidative atmosphere are predicted to be perfluorinated methyl formate, CF_3OCFO, and fluorinated glycolaldehyde, CFOCF_2OH, both with CF_2O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF_2OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in earlier work appear unlikely, and are not supported by theoretical or related experimental work.
Additional Information
© 2015 the Owner Societies. Received 14th August 2015, Accepted 30th September 2015, First published online 30 Sep 2015. L.V. is supported by the Max Planck Graduate Center with the Johannes Gutenberg-Universität Mainz (MPGC), Germany.Attached Files
Published - c5cp04839g.pdf
Supplemental Material - c5cp04839g1_si.pdf
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Additional details
- Eprint ID
- 61764
- Resolver ID
- CaltechAUTHORS:20151102-100820336
- Max Planck Graduate Center
- Created
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2015-11-02Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field