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Gas Phase Kinetics of 2,2,2-Trifluoroethylbutyrate with the Cl Atom: An Experimental and Theoretical Study
Gonu Srinivasulu,
Published in American Chemical Society
2015
Volume: 119
   
Issue: 35
Pages: 9294 - 9306
Abstract
The gas phase temperature dependent rate coefficients of Cl atoms with 2,2,2-trifluoroethylbutyrate, CH3CH2CH2C(O)OCH2CF3, were measured in the temperature range 268-343 K, at atmospheric pressures using the relative rate method, with ethyl acetate and ethane as reference compounds. The temperature dependent rate coefficients for the reaction of 2,2,2-TFEB + Cl were measured and were used to deduce the Arrhenius expression: k268-343K = [(4.42 ± 0.01) × 10-19]T2.6 exp{(1132 ± 566)/T} cm3 molecule-1 s-1. At 298 K, the rate coefficient for the title reaction is (4.54 ± 2.87) × 10-11 cm3 molecule-1 s-1, which is in good agreement with a previously reported value at 298 K. To complement our experimental results over the studied temperature range, theoretical kinetic calculations were also performed for the title reaction using canonical variational transition state theory (CVT) with small curvature tunneling (SCT) corrections in combination with the CCSD(T)/cc-pVDZ//M062X/6-31+g(d,p) level of theory. The temperature dependent Arrhenius expression was obtained to be k(T) = (1.89 ± 2.64) × 10-21T3.4 exp{(1321 ± 111)/T} cm3 molecule-1 s-1. The branching ratios, atmospheric implications, and degradation mechanism of 2,2,2-trifluoroethylbutyrate, CH3CH2CH2C(O)OCH2CF3, were discussed in detail in this manuscript. (Graph Presented). © 2015 American Chemical Society.
About the journal
JournalData powered by TypesetJournal of Physical Chemistry A
PublisherData powered by TypesetAmerican Chemical Society
ISSN10895639
Open AccessNo
Concepts (16)
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    Atmospheric pressure
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    Degradation
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    Electronic states
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    Gases
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    Ionization of gases
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    Molecules
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    Reaction kinetics
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    Arrhenius expressions
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    ATMOSPHERIC IMPLICATIONS
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    CANONICAL VARIATIONAL TRANSITION-STATE THEORIES
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    Degradation mechanism
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    Gas phase temperature
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    RELATIVE RATE METHOD
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    SMALL-CURVATURE TUNNELING
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    Temperature dependent
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    Atmospheric temperature