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Termolecular reaction of nitrogen monoxide and oxygen: A still unsolved problem
Author(s) -
Olbregts J.
Publication year - 1985
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.550170805
Subject(s) - chemistry , carbon monoxide , torr , nitrogen , monoxide , reaction rate constant , oxygen , thermodynamics , nitrogen dioxide , inorganic chemistry , kinetics , organic chemistry , catalysis , quantum mechanics , physics
The oxidation of nitrogen monoxide has been studied extensively between 226 and 758 K at pressures of NO and O 2 ranging from about 0.2 to 30 torr. It has been shown that (i) the reaction is properly first order against oxygen and second order against nitrogen monoxide, as well under initial conditions as during the course of the reaction; (ii) the termolecular rate constant, k , first decreases with increasing temperature and reaches a minimum value at 600 K; (iii) the transition state theory is unable to describe this behavior correctly, (iv) under the present experimental conditions k can be represented either by\documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} k({\rm l}^{\rm 2} {\rm mol}^{ - 2} {\rm s}^{ - 1}) = - (5.18 \pm 1.00) + (2.70 \pm 0.25){\rm log}_{{\rm 10}} T + (700 \pm 50)/T $$\end{document}or by\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm l}^{\rm 2} {\rm mol}^{ - 2} {\rm s}^{ - 1}) = (350 \pm 100)10^{(390 \pm 50)/T} + (8000 \pm 2000)10^{ - (440 \pm 50)/T} $$\end{document}The latter equation is compatabile with a multiple‐step mechanism.