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J Phys Chem A. 2019 Jun 13;123(23):4834-4843. doi: 10.1021/acs.jpca.9b02454. Epub 2019 May 31.

Rate Constants for the Reactions of OH Radicals with the ( E)/( Z) Isomers of CFCl=CFCl and ( E)-CHF=CHF.

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1
National Institute of Advanced Industrial Science and Technology (AIST) , 1-1-1 Higashi , Tsukuba Ibaraki 305-8565 , Japan.

Abstract

The rate constants for the OH radical reactions with halogenated ethenes were investigated experimentally and computationally. The rate constants for the reactions of OH radicals with ( E)-CFCl=CFCl ( k1), ( Z)-CFCl=CFCl ( k2), and ( E)-CHF=CHF ( k3) were measured using flash and laser photolysis methods. The temporal profile of the OH radical was monitored by a laser-induced fluorescence technique. Kinetic measurements were carried out over the temperature range of 250-430 K. Arrhenius rate constants were determined to be k1 = (1.67 ± 0.06) × 10-12·exp[(140 ± 10) K/ T], k2 = (1.75 ± 0.04) × 10-12·exp[(140 ± 10) K/ T], and k3 = (3.99 ± 0.15) × 10-12·exp[(260 ± 10) K/ T] cm3 molecule-1 s-1. The quoted uncertainties are 95% confidence levels and do not include systematic errors. Infrared absorption spectra were measured at room temperature. The atmospheric lifetimes and the global warming potentials of ( E)-CFCl=CFCl, ( Z)-CFCl=CFCl, and ( E)-CHF=CHF were estimated to be 4.3, 4.2, and 1.2 days and 0.035, 0.036, and 0.0056, respectively. The ozone depletion potentials of ( E)-CFCl=CFCl and ( Z)-CFCl=CFCl were determined to be 0.00011 and 0.00010, respectively. The photochemical ozone creation potentials of the halogenated ethenes were less than 1/4 that of ethene. In addition, the ( E)/( Z) differences in the energy and IR spectra of the CFCl=CFCl and CHF=CHF molecules were computationally examined. The reactivities of these halogenated ethenes toward OH radicals were investigated through the combination of DFT and ab initio computations. The rate constants calculated for the OH radical reactions of these halogenated ethenes showed reasonable agreement with the experimentally determined values. Our computational results for the CFCl=CFCl and CHF=CHF ( E)/( Z) isomeric pairs indicated that the rate constants toward OH radicals are larger for the higher-energy geometrical isomers than for the lower-energy counterparts.

PMID:
31117589
DOI:
10.1021/acs.jpca.9b02454

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