Reaction between Criegee Intermediate CH2OO and Isobutyraldehyde: Kinetics and Atmospheric Implications

Abstract

AbstractIn the present work, we have investigated the 1,3‐cycloaddition reaction of isobutyraldehyde ((CH3)2CHCHO) with the simplest Criegee intermediate CH2OO using the OH laser‐induced fluorescence (LIF) method in a reaction tube. The experiments were conducted at temperatures and pressures ranging from 280 to 338 K and 5 to 150 Torr. We found that the bimolecular rate coefficient of the reaction is temperature‐ and pressure‐dependent. The measured rate coefficients at 100 Torr are (4.93±0.89), (4.46±0.80), (3.99±0.72), (3.56±0.64), (3.34±0.60), (2.98±0.54), (2.78±0.50)×10−12 cm3 molecule−1 s−1 at 280, 288, 298, 308, 318, 328, and 338 K, respectively. A high‐pressure limit rate coefficient of (4.47±0.80)×10−12 cm3 molecule−1 s−1 was obtained at 298 K by fitting the pressure‐dependent rate coefficients according to the Lindemann mechanism. The Arrhenius plot of the temperature‐dependent rate coefficients results in an activation energy of (−1.86±0.33) kcal mol−1 and a preexponential factor of (1.72±0.31)×10−13 cm3 molecule−1 s−1. In the atmosphere, the reaction of CH2OO with isobutyraldehyde may contribute to the sink of CH2OO in regions where isobutyraldehyde emission is intense under low temperature and low relative humidity conditions.