Kinetic and Mechanistic Study of the Gas-Phase Reactions of a Series of Vinyl Ethers with the Nitrate Radical

Abstract

NO(3) oxidation of methyl, ethyl, propyl, and butyl vinyl ethers has been studied under tropospheric conditions (atmospheric pressure and T = 293 +/- 3 K) in the LISA indoor simulation chamber. NO(3) was produced inside the reactor by thermal decomposition of N(2)O(5) previously added to the air-VOC mixture, and concentrations were monitored using FTIR spectrometry. All the kinetic experiments were carried out by relative rate technique using isoprene as reference compound, leading to the rate constants k(1) = (7.2 +/- 1.5) x 10(-13), k(2) = (13.1 +/- 2.7) x 10(-13), k(3) = (13.3 +/- 3.0) x 10(-13), and k(4) = (17.0 +/- 3.7) x 10(-13) cm(3) molecule(-1) s(-1) for methyl, ethyl, propyl, and butyl vinyl ethers, respectively. Main oxidation products have been identified like being formaldehyde and respectively methyl, ethyl, propyl, and butyl formates. Production yields of oxidation products were close to 50%. Oxygenated nitrates and peroxynitrates were also detected.