Kinetics of CH2OO and syn-CH3CHOO reaction with acrolein

Abstract

The kinetics for the reactions of CH₂OO and syn-CH₃CHOO with acrolein, a typical unsaturated aldehyde in the atmosphere, were studied in a flash photolysis flow reactor using the OH laser-induced fluorescence (LIF) method. The bimolecular reaction rate coefficients were measured at temperatures ranging from 281 to 318 K, and pressures ranging from 5 to 200 Torr. No obvious dependence of the rate coefficients on pressure was observed under the current experimental conditions. Both reactions exhibit negative temperature-dependence, with an activation energy of (−1.70 ± 0.19) and (−1.47 ± 0.24) kcal mol⁻¹ for CH₂OO and syn-CH₃CHOO reacting with acrolein, derived from the Arrhenius equation. At 298 K, the measured rate coefficients for CH₂OO/syn-CH₃CHOO + acrolein reactions are (1.63 ± 0.19) × 10⁻¹² cm³ s⁻¹ and (1.17 ± 0.16) × 10⁻¹³ cm³ s⁻¹, respectively. The rate coefficient of the former reaction is in reasonable agreement with a recent theoretical result.