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Experimental and Computational Studies of Criegee Intermediate <i>syn</i>-CH<sub>3</sub>CHOO Reaction with Hydrogen Chloride

Siyue Liu, Xiao-Hu Zhou, Yang Chen, Yiqiang Liu, Shengrui Yu, Kaito Takahashi, Hongbin Ding, Zhenfeng Ding, Xueming Yang, Wenrui Dong

2021The Journal of Physical Chemistry A16 citationsDOI

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 -CH 3 CHOO 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 cm 3 s –1, which was in reasonable agreement with 2.2 × 10 –11 cm 3 s –1 from the theoretical calculation.

Topics & Concepts

ChemistryHydrogen chlorideTransition state theoryHydrogenChlorideTorrActivation energyKineticsAnalytical Chemistry (journal)Reaction rate constantPhysical chemistryThermodynamicsInorganic chemistryOrganic chemistryQuantum mechanicsPhysicsSpectroscopy and Laser ApplicationsAtmospheric chemistry and aerosolsAdvanced Chemical Physics Studies
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