화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.108, No.1, 74-79, 2004
Kinetics of the CCO+NO and CCO+NO2 reactions
The kinetics of the reaction of CCO radicals with NO and NO2 were studied using time-resolved infrared diode laser absorption spectroscopy. The rate constants were determined to be k(CCO)+(NO) = (5.36 +/- 0.5) x 10(-11) and k(CCO+NO2) = (6.89 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K. These rate constants have virtually no temperature dependence over the range 298-573 K, with Arrhenius fits given by k(CCO+NO) = (1.66 +/- 0.5) x 10(-10) exp[(-337 +/- 100)/T] and k(CCO+NO2) = (8.51 +/- 1.5) x 10(-11) exp[(-63 +/- 80)/T] (error bars represent one standard deviation). Product channel measurements were performed on the CCO + NO reaction. After consideration of secondary chemistry, we obtain the branching ratios phi(CN + CO2) = 0.13 +/- 0.05 and phi(CO + NCO) = 0.87 +/- 0.05 at 298 K. Ab initio quantum chemical calculations at the QCISD(T)/6-311G(2df,2pd) level of theory were used to examine probable reaction pathways.