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 O3-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O3 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 (CH3CH2CH2CH2OCHO for n-BVE, (CH3)2CHCH2OCHO for i-BVE and (CH3)3COCHO 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 298K and 101kPa, the calculated total rate constants are 2.50×10−16, 3.41×10−16 and 4.17×10−16cm3molecule−1s−1 for n-BVE+O3, i-BVE+O3 and t-BVE+O3, respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001–101kPa but obviously positive temperature dependent over the whole study temperature range (200–400K). 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.