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Kinetic and Mechanistic Study of the Gas-Phase Reactions of a Series of Vinyl Ethers withthe Nitrate Radical
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dcterms:abstract
NO3 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. NO3 was producedinside the reactor by thermal decomposition of N2O5 previously added to the air−VOC mixture, andconcentrations were monitored using FTIR spectrometry. All the kinetic experiments were carried out byrelative rate technique using isoprene as reference compound, leading to the rate constants k1 = (7.2 ± 1.5)× 10-13, k2 = (13.1 ± 2.7) × 10-13, k3 = (13.3 ± 3.0) × 10-13, and k4 = (17.0 ± 3.7) × 10-13 cm3 molecule-1s-1 for methyl, ethyl, propyl, and butyl vinyl ethers, respectively. Main oxidation products have been identifiedlike being formaldehyde and respectively methyl, ethyl, propyl, and butyl formates. Production yields ofoxidation products were close to 50%. Oxygenated nitrates and peroxynitrates were also detected.
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