Kinetics of the C3H7O2 + NO reaction: Temperature dependence of the overall rate constant and the i-C3H7ONO2 branching channel
The temperature dependence of the overall rate constant for the C3H7O2 + NO reaction and the rate constant for the minor branching channel resulting in the production of i-C3H7ONO2 have been measured using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. The temperature dependence of the overall rate constant for the C3H7O2 + NO reaction was investigated between 298 and 213 K at 100 Torr pressure, and the data were fit by the following Arrhenius expression (with 2 standard deviation error limits indicated): × 10-12 exp[(268 ± 56)/T] cm3 molecule-1 s-1. This expression agrees well with previous isomer-specific measurements of the n-C3H7ONO2 and i-C3H7O2 + NO rate constants made at lower pressures. The temperature dependence of the rate constant for the minor reaction channel i-C3H7O2 + NO → i-C3H7ONO2 was investigated between 298 and 213 K at 100 Torr pressure. The following Arrhenius expression was determined for the minor channel: × 10-16 exp[(1380 ± 230)/T] cm3 molecule-1 s-1. The Arrhenius expressions for the overall rate and the i-C3H7ONO2 producing channel indicate a branching ratio of about 0.006 at 298 K and 0.020 at 213 K at 100 Torr pressure, which is in good agreement with the predictions of a recently revised empirical model for alkyl nitrate branching ratios.
Chow, J.M., A.M. Miller, and M.J. Elrod. 2003. "Kinetics of the C3H7O2 + NO Reaction: Temperature Dependence of the Overall Rate Constant and the i-C3H7ONO2 Branching Channel." Journal of Physical Chemistry A 107(17): 3040-3047.
American Chemical Society
Journal of Physical Chemistry A
Chemistry and Biochemistry
Nox-air photooxidations, Alkyl nitrate formation, Peroxy radicals, N-alkanes