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The pyrolysis of 2‐nitrosoisobutane and the bond dissociation energies of nitroso compounds
Author(s) -
Choo K. Y.,
Mendenhall G. D.,
Golden D. M.,
Benson S. W.
Publication year - 1974
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.550060605
Subject(s) - chemistry , arrhenius equation , activation energy , dissociation (chemistry) , bond dissociation energy , reaction rate constant , pyrolysis , mole , torr , thermodynamics , kinetics , organic chemistry , physics , quantum mechanics
Study of the reaction by very‐low‐pressure pyrolysis (VLPP) in the temperature range of 550–850°K yields for the high‐pressure Arrhenius parameters\documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303 RT in kcal/mole. These in turn yield for the high‐pressure second‐order recombination of t Bu + NO, k −1 = (3.5 ± 1.7) × 10 9 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E 4 ≥ 4.2 kcal/mole. The bond dissociation energy DH o ( tBu ‐NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free‐volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8–200 torr showed an extremely rapid inhibition by products and a very complex set of products.