Theoretical studies on the mechanisms and rate constants for the hydroxylation of n-butyl, iso-butyl and tert-butyl vinyl ethers in atmosphere

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

“…There are some experimental kinetic studies of many different unsaturated ethers with OH radicals (Perry et al, 1977;Thiault et al, 2002;Thiault and Mellouki, 2006;Zhou et al, 2006aZhou et al, , b, 2009Zhou et al, , 2012Peirone et al, 2011), with NO 3 (Scarfogliero et al, 2006Zhou et al, 2006aZhou et al, ,b, 2009Zhou et al, , 2012, and with O 3 (Grosjean and Grosjean, 1998;Zhou et al, 2006aZhou et al, ,b, 2009Zhou et al, , 2012. Moreover, the reactivity between OH radicals and several vinyl ethers has been theoretically investigated as well (Han et al, 2014(Han et al, , 2015. Particularly, for 2ClEVE, allyl ether ((CH 2 ]CHCH 2 ) 2 O, AE), and AEE scarce kinetic information is currently available in the literature.…”

OH-initiated oxidation of vinyl butyrate: ab initio insights

“…From related systems to vinyl esters, Han et al 25 theoretically studied a homologous series of n-butyl, iso-butyl and tertbutyl vinyl ethers initiated by OH radicals calculated at the MPWB1K/6-31+G(d,p) level at T = 298 K to investigate the contribution of H-abstraction to the vinyl compound + OH radical reaction. In the study, they pointed out that both OH-addition and H-abstraction channels could contribute equally to the chemical conversion, in contrast to the experimental hypothesis of the dominance of the OH addition by Rivela et al 17 H-abstraction channels at the terminal methyl group of n-butyl vinyl ether possessed a low barrier height (i.e., 0.97 kcal mol À1 ) compared to two OH-addition reactions at the double-bond (i.e., 2.19 and 0.49 kcal mol À1 ).…”