Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF_3OCF=CF_2

摘要

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.