Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCF=CF₂.

Abstract

Product formation in the reaction of perfluorinated methyl vinyl ether, CF3OCF=CF2, 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, CF3OCFO, and fluorinated glycolaldehyde, CFOCF2OH, both with CF2O 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 CFOCF2OH 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.

DOI: 10.1039/c5cp04839g

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Cite this paper

@article{Vereecken2015TheoreticalSO, title={Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCF=CF₂.}, author={Luc Vereecken and John N. Crowley and Damien Amedro}, journal={Physical chemistry chemical physics : PCCP}, year={2015}, volume={17 43}, pages={28697-704} }