Computational
Study on the Mechanisms and Rate Constants of the Cl-Initiated Oxidation
of Methyl Vinyl Ether in the Atmosphere
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Abstract
The
Cl-initiated oxidation reactions of methyl vinyl ether (MVE) are analyzed
by using the high-level composite method CBS-QB3. Detailed chemistry
for the reactions of MVE with chlorine atoms is proposed according
to the calculated thermodynamic data. The primary eight channels,
including two Cl-addition reactions and six H-abstraction reactions,
are discussed. In accordance with the further investigation of the
two dominant additional routes, formyl chloride and formaldehyde are
the major products. Over the temperature range of 200–400 K
and the pressure range of 100–2000 Torr, the rate constants
of primary reactions are calculated by employing the MESMER program.
H-abstraction channels are negligible according to the value of rate
constants. During the studied temperature range, the Arrhenius equation
is obtained as <i>k</i><sub>tot</sub> = 5.64 × 10<sup>–11</sup> exp(215.1/<i>T</i>). The total
rate coefficient is <i>k</i><sub>tot</sub> = 1.25 ×
10<sup>–10</sup> cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup> at 298 K and 760 Torr. Finally, the atmospheric
lifetime of MVE with respect to Cl is estimated to be 2.23 h
