Atmospheric reactivity of vinyl acetate: kinetic and mechanistic study of its gas-phase oxidation by OH, O3, and NO3.
Vinyl acetate is widely used in industry. It has been classified as a high-production volume (HPV) chemical in the United States. To evaluate its impact on the environment and air quality, its atmospheric reactivity toward the three main tropospheric oxidants (OH, NO(3), and O(3)) has been investigated. Kinetic and mechanistic experiments have been conducted at room temperature and atmospheric pressure using an indoor Pyrex simulation chamber coupled to Fourier transform infrared (FTIR) and UV-visible spectrometers. Rate constants for the reactions of vinyl acetate with OH, NO(3), and O(3) were equal to (2.3 +/- 0.3) x 10(-11), (7.3 +/- 1.8) x 10(-15), and (3.0 +/- 0.4) x 10(-18) cm(3) molecule(-1) s(-1), respectively. From these data, tropospheric lifetimes of vinyl acetate have been estimated as follows: tau(OH) = 6 h, tau(NO(3)) = 6 days, and tau(O(3)) = 5 days. This demonstrates that reaction with OH radicals is the main tropospheric loss process of this compound. From the mechanistic experiments, main oxidation products have been identified and quantified and oxidation schemes have been proposed for each studied reaction.
Picquet-Varrault
B
B
Laboratoire Interuniversitaire des Systemes Atmospheriques, UMR-CNRS 7583, Universite Paris-Est et Universite Paris Diderot, Institut Pierre Simon Laplace, Creteil, France. picquet@lisa.univ-paris12.fr
Scarfogliero
M
M
Doussin
J-F
JF
D000475:Alkenes / Q000737:chemistry; D001272:Atmosphere / Q000737:chemistry*; D005740:Gases / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D009566:Nitrates / Q000737:chemistry*; D010084:Oxidation-Reduction; D010126:Ozone / Q000737:chemistry*; D044367:Phase Transition; D012015:Reference Standards; D014753:Vinyl Compounds / Q000737:chemistry*
D000475:Alkenes; D005740:Gases; D009566:Nitrates; D014753:Vinyl Compounds; D017665:Hydroxyl Radical; D010126:Ozone; C013658:propylene; C011566:vinyl acetate