title: Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether.
abstract: Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Dandan
authors.initials: D
authors.lastname: Han
authors.forename: Haijie
authors.initials: H
authors.lastname: Cao
authors.forename: Yanhui
authors.initials: Y
authors.lastname: Sun
authors.forename: Ruilian
authors.initials: R
authors.lastname: Sun
authors.forename: Maoxia
authors.initials: M
authors.lastname: He
mesh_terms: D004987:Ethers / Q000737:chemistry*; D007536:Isomerism; D007700:Kinetics; D010126:Ozone / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D004987:Ethers; D014753:Vinyl Compounds; C521980:butyl vinyl ether; D010126:Ozone