Shock tube study of the reaction of CH with N2: overall rate and branching ratio.

Abstract

We have studied the reaction between CH and N2, (1) CH + N2 --> products, in shock tube experiments using CH and NCN laser absorption. CH was monitored by continuous-wave, narrow-line-width laser absorption at 431.1 nm. The overall rate coefficient of the CH + N2 reaction was measured between 1943 and 3543 K, in the 0.9-1.4 atm pressure range, using a CH perturbation approach. CH profiles recorded upon shock-heating dilute mixtures of ethane in argon and acetic anhydride in argon were perturbed by the addition of nitrogen. The perturbation in the CH concentration was principally due to the reaction between CH and N2. Rate coefficients for the overall reaction were inferred by kinetically modeling the perturbed CH profiles. A least-squares, two-parameter fit of the current overall rate coefficient measurements was k1 = 6.03 x 1012 exp(-11150/T [K]) (cm3 mol-1 s-1). The uncertainty in k1 was estimated to be approximately +/-25% and approximately +/-35% at approximately 3350 and approximately 2100 K, respectively. At high temperatures, there are two possible product channels for the reaction between CH and N2, (1a) CH + N2 --> HCN + N and (1b) CH + N2 --> H + NCN. The large difference in the rates of the reverse reactions enabled inference of the branching ratio of reaction 1, k1b/(k1b + k1a), in the 2228-2905 K temperature range by CH laser absorption in experiments in a nitrogen bath. The current CH measurements are consistent with a branching ratio of 1 and establish NCN and H as the primary products of the CH + N2 reaction. A detailed and systematic uncertainty analysis, taking into account experimental and mechanism-induced contributions, yields a conservative lower bound of 0.70 for the branching ratio. NCN was also detected by continuous-wave, narrow-line-width laser absorption at 329.13 nm. The measured NCN time histories were used to infer the rate coefficient of the reaction between H and NCN, H + NCN --> HCN + N, and to estimate an absorption coefficient for the NCN radical.

• Authors: Venkatesh Vasudevan, Ronald K Hanson, Craig T Bowman, David M Golden, David F Davidson
• Journal: The journal of physical chemistry. A (J Phys Chem A) Vol. 111 Issue 46 Pg. 11818-30 (Nov 22 2007) ISSN: 1089-5639 [Print] United States
• PMID: 17958405 (Publication Type: Journal Article)