Shock tube study of cyanogen oxidation kinetics

Mixtures of cyanogen and nitrous oxide diluted in argon were shock‐heated to measure the rate constants ofA broad‐band mercury lamp was used to measure CN in absorption at 388 nm [ B 2 Σ + ( v = 0) ← X 2 Σ + ( v = 0)], and the spectral coincidence of a CO infrared absorption line [ v (2 ← 1), J (37 ← 38)] with a CO laser line [ v (6 → 5), J (15 → 16)] was exploited to monitor CO in absorption. The CO measurement established that reaction (3) produces CO in excited vibrational states. A computer fit of the experiments near 2000 K led to\documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 \, = \,10^{11.70\left( { + 0.25, - 0.19} \right)} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 \, = \,10^{13.26 \pm 0.26} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document}An additional measurement of NO via infrared absorption led to an estimate of the ratio k 5 / k 6 :with k 5 / k 6 ≃ 10 3.36±0.27 at 2150 K. Mixtures of cyanogen and oxygen diluted in argon were shock heated to measure the rate constant ofand the ratio k 5 / k 6 by monitoring CN in absorption. We found near 2400 K:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 \, = \,10^{12.68\left( { + 0.27, - 0.19} \right)} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document}and\documentclass{article}\pagestyle{empty}\begin{document}$$ {{k_5 } \mathord{\left/ {\vphantom {{k_5 } {k_6 }}} \right. \kern-\nulldelimiterspace} {k_6 }}\, = \,10^{2.68 \pm 0.28} $$\end{document}The combined measurements of k 5 / k 6 lead to k 5 / k 6 ≃ 10 −3.07 exp(+31,800/ T ) (±60%) for 2150 ≤ T ≤ 2400 K.