Rate constants for CF3+H2→CF3H+H and CF3H+H→CF3+H2 reactions in the temperature range 1100-1600 K

被引:23
作者
Hranisavljevic, J [1 ]
Michael, JV [1 ]
机构
[1] Argonne Natl Lab, Div Chem, Argonne, IL 60439 USA
关键词
D O I
10.1021/jp982432q
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
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页码:7668 / 7673
页数:6
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