Experimental and Computational Studies of Criegee Intermediate syn-CH3CHOO Reaction with Hydrogen Chloride
Siyue Liu1,2, Xiaohu Zhou2,3,4, Yang Chen2,5,6
1Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams, Chinese Ministry of Education, School of Physics, Dalian University of Technology, Dalian 116024, China.
Abstract:
Hydrogen chloride (HCl) contributes substantially to the atmospheric Cl; both species could affect the composition of Earth's atmosphere and the fate of pollutants. Here, we present the kinetics study for syn-CH3CHOO reaction with HCl using experimental measurement and theoretical calculations. The experiment was conducted in a flow tube reactor at a pressure of 10 Torr and temperatures ranging from 283 to 318 K by using the OH laser-induced fluorescence (LIF) method. Transition-state theory and quantum chemistry calculations with QCISD(T) were used to calculate the rate coefficients. Weak negative temperature dependence was observed with a measured activation energy of -(2.98 ± 0.12) kcal mol-1 and a calculated zero-point-corrected barrier energy of -3.29 kcal mol-1. At 298 K, the rate coefficient was measured to be (4.77 ± 0.95) × 10-11 cm3 s-1, which was in reasonable agreement with 2.2 × 10-11 cm3 s-1 from the theoretical calculation.
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