Journal of Physical Chemistry A, Vol.108, No.14, 2666-2674, 2004
Kinetic study for the reactions of several hydrofluoroethers with chlorine atoms
The reaction kinetics of chlorine atoms with the hydrofluoroethers CHF2CF2OCH3 (1), CHF2CF2OCH2CH3 (2), CHF2CF2OCH2CF3 (3), CF3CHFCF2OCH3 (4), and CH2=CHCH2OCF2CHF2 (5) were studied in the gas phase over the temperature range 273-363 K. The experiments were performed at very low pressures (<3 mTorr) in a molecular flow system equipped with a quadrupole mass spectrometer by monitoring both reactants. The proposed Arrhenius expressions for the studied reactions are (in cm(3) molecule(-1) s(-1), 2sigma uncertainties): k(1) = (5.49 +/- 1.51) x 10(-12) exp(-928 +/- 155/T), k(2) = (1.99 +/- 0.12) x 10(-12) exp(-36 +/- 33/T), k(3) = (1.95 +/- 0.72) x 10(-12) exp(-1616 +/- 202/T), k(4) = (8.72 +/- 2.93) x 10(-12) exp(-1112 +/- 186/7), and k(5) = (5.54 +/- 1.96) x 10(-13) exp(821 +/- 214/T). The title reactions proceed via hydrogen atom metathesis, with the exception of the unsaturated CH2=CHCH2OCF2CHF2 ether, where the Cl-atom addition pathway leading to CH2=CHCl is also present. The C-H bond strengths in several hydrofluoroethers were calculated at the B3P86/6-311++G(3df,2p) level of theory, and they show an increase in the order -OCH(CH3)-H < -OCH(CF3)-H < -CH2OCH2-H < -CF2OCH2-H < -OCH2CH2-H < -OCF2CF2-H < -OCF2-H. Furthermore, their room-temperature rate coefficients correlate with the weakest C-H bond strengths in each molecule, according to the expression log(k, in cm(3) molecule(-1) s(-1)) = (23.6 +/- 7.4) - (0.09 +/- 0.02) x [C-H bond strength (in kJ mol(-1))]. In addition, their vertical ionization potentials were calculated at the B3LYP/6-311++G(3df,2p) level of theory, and they also correlate with the room-temperature rate coefficients according to the expression log(k, in cm(3) molecule(-1) s(-1)) = (4.0 +/- 1.7) - (1.42 +/- 0.15) x [ionization potential (in eV)].