화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.102, No.39, 7668-7673, 1998
Rate constants for CF3+H-2 -> CF3H+H and CF3H+H -> CF3+H-2 reactions in the temperature range 1100-1600 K
The shock tube technique coupled with H-atom atomic resonance absorption spectrometry has been used to study the reactions (1) CF3 + H-2 --> CF3H + H and (2) CF3H + H --> CF3 + H-2 over the temperature ranges 1168-1673 K and 1111-1550 K, respectively. The results can be represented by the Arrhenius expressions k(1) = 2.56 x 10(-11) exp(-8549K/T) and k(2) = 6.13 x 10(-11) exp(-7364K/T), both in cm(3) molecule(-1) s(-1) Equilibrium constants were calculated from the two Arrhenius expressions in the overlapping temperature range, and good agreement was obtained with the literature values. The rate constants for reaction 2 were converted into rate constants for reaction 1 using literature equilibrium constants. These data are indistinguishable from direct k(1) measurements, and an Arrhenius fit for the joint set is k(1) = 1.88 x 10(-11) exp(-8185K/T) cm(3) molecule(-1) s(-1). The CF3 + H-2 --> CF3H + H reaction was further modeled using conventional transition-state theory, which included ab initio electronic structure determinations of reactants, transition state, and products.