• Theoretical study on mechanism, kinetics, and thermochemistry of the gas phase reaction of 2,2,2-trifluoroethyl butyrate with OH radicals at 298 K

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      https://www.ias.ac.in/article/fulltext/jcsc/127/06/1015-1023

    • Keywords

       

      Fluoroesters; M06-2X; IRC; rate constant; atmospheric lifetime.

    • Abstract

       

      A theoretical investigation has been carried out on the mechanism, kinetics, and thermochemistry of gas-phase reaction of 2,2,2-trifluoroethyl butyrate (TFEB, CH3CH2CH2C(O)OCH2CF3) with OH radicals using a modern DFT functional. The involvement of pre- and post-reactive complexes was explored and the reaction profiles were modeled. Energetic calculations were performed using the M06-2X/6-31+G(d,p) method. The intrinsic reaction coordinate (IRC) calculation has been performed to confirm the smooth transition from the reactant to product through the respective transition state. It has been found that the dominant path of the H-atom abstraction takes place from the –CH2- position, which is attached with the methyl group at the one end of TFEB. Theoretically calculated rate constant at 298 K using canonical transition state theory (CTST) is found to be in reasonable agreement with the experimental data. Using group-balanced isodesmic procedure, the standard enthalpy of formation for TFEB is reported for the first time. The branching ratios of the different reaction channels are also determined. The atmospheric lifetime of TFEB is determined to be 6.8 days.

    • Author Affiliations

       

      Nand Kishor Gour1 Bhupesh Kumar Mishra2 3 Hari Ji Singh4

      1. Department of Chemistry, D.D.U. Gorakhpur University, Gorakhpur 273009, India
      2. Department of Chemical Sciences, Tezpur University, Tezpur 784 028, India
      3. Department of Chemistry, D. N. Government College, Itanagar 791113, India
      4. Department of Chemistry, D. D.U. Gorakhpur University, Gorakhpur 273009, India
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