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Criegee Intermediate Reaction with Alcohol Is Enhanced by a Single Water Molecule
Yen-Hsiu Lin1,2, Cangtao Yin1, Wei-Hong Lin1
1Institute of Atomic and Molecular Sciences , Academia Sinica , Taipei 10617 , Taiwan.
Abstract:
The role of water in gas-phase reactions has gained considerable interest. Here we report a direct kinetic measurement of the reaction of syn-CH3CHOO (a Criegee intermediate or carbonyl oxide) with methanol at various relative humidity (RH = 0-80%) under near-ambient conditions (298 K, 250-755 Torr). The data indicate that a single water molecule expedites the reaction by up to a factor of three. The rate coefficient of the corresponding reaction, syn-CH3CHOO + CH3OH + H2O → products, has been determined to be (1.95 ± 0.11) × 10-32 cm6 s-1 at 298 K, with no observable pressure dependence for 250-755 Torr. Quantum chemistry calculation shows that the dominating pathway involves a hydrogen-bonded ring structure, in which methanol is donating a hydrogen atom to water, water is donating a hydrogen atom to the terminal oxygen atom of the Criegee intermediate, and, on the product side, H2O is reformed and acts as a catalyst.
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