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Thermal decomposition of methyl nitrite in shock waves studied by laser probing
Author(s) -
Hsu D. S. Y.,
Burks G. L.,
Beebe M. D.,
Lin M. C.
Publication year - 1984
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.550160909
Subject(s) - chemistry , arrhenius equation , reaction rate constant , thermal decomposition , shock tube , decomposition , thermodynamics , atmospheric temperature range , yield (engineering) , kinetic energy , photodissociation , shock wave , kinetics , photochemistry , activation energy , organic chemistry , physics , quantum mechanics
The unimolecular decomposition of methyl nitrite in the temperature range 680–955 K and pressure range 0.64 to 2.0 atm has been studied in shock‐tube experiments employing real‐time absorption of CW CO laser radiation by the NO product. Computer kinetic modeling using a set of 23 reactions shows that NO product is relatively unreactive. Its initial rate of production can be used to yield directly the unimolecular rate constant, which in the fall‐off region, can be represented by the second‐order rate coefficient in the Arrhenius form:\documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 10^{17.90 \pm 0.21} \exp (- 17200 \pm 400/T){\rm cm}^{\rm 3} {\rm mol}^{ - 1} {\rm s}^{ - 1}$$\end{document}A RRKM model calculation, assuming a loose CH 3 ONO ≠ complex with two degrees of free internal rotation, gives good agreement with the experimental rate constants.