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Simultaneous laser absorption measurements of CN and OH in a shock tube study of HCN + OH → products
Author(s) -
Wooldridge Steven T.,
Hanson Ronald K.,
Bowman Craig T.
Publication year - 1995
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550271105
Subject(s) - chemistry , shock tube , dissociation (chemistry) , analytical chemistry (journal) , atmospheric temperature range , thermal decomposition , isomerization , argon , absorption (acoustics) , attenuation coefficient , shock wave , kinetics , combustion , reaction rate constant , laser , thermodynamics , organic chemistry , optics , physics , quantum mechanics , catalysis
Simultaneous, quantitative, narrow‐line laser absorption measurements of CN time‐histories at 388.444 nm and OH time‐histories at 306.687 nm have been made in incident and reflected shock wave experiments using dilute mixtures of nitiric acid (HNO 3 ) and HCN in argon. The thermal decomposition of HNO 3 serves as a rapid source of OH upon shock‐heating, and the OH subsequently reacts predominantly with the HCN in the test gas mixture. The rate coefficient for the reactionwas determined in the temperature range 1120–1960 K via detailed kinetics modeling of the simultaneously acquired CN and OH measurements. These data are in good agreement with lower temperature measurements of the rate of the reverse reaction (−1a) when recent values of the heats of formation of CN and HCN are used. The expression\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1a} \, = \,3.90\, \times \,10^6 T^{1.83} \exp (- 5179/T)cm^3 mol^{ - 1} s^{ - 1}, $$\end{document}valid for temperatures 500 to 2000 K, effectively represents the experimental measurements. The estimated uncertainty of the expression for k 1a is ±30%, based on the experimental uncertainties of the individual rate coefficient studies. Analysis of the decay region of the experimental OH time‐histories yielded the total rate coefficient k 1 (all product channels) for the reaction of HCN with OH for temperatures ranging from 1490 to 1950 K. These measurements are consistent with a previous theoretical analysis of the three primary addition‐isomerization‐dissociation processes for the HCN + OH reaction at combustion temperatures when the contribution to k 1 from reaction (1a) is included. © 1995 John Wiley & Sons, Inc.