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Kinetics of the thermal decomposition of trans ‐1,2‐dicyanocyclobutane
Author(s) -
King Keith D.,
Goddard Richard D.
Publication year - 1978
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.550100504
Subject(s) - arrhenius equation , chemistry , activation energy , kinetics , thermal decomposition , reaction rate constant , thermodynamics , decomposition , atmospheric temperature range , homogeneous , organic chemistry , physics , quantum mechanics
The kinetics of the thermal decomposition of trans ‐1,2‐dicyanocyclobutane, which yields only vinyl cyanide, have been studied in the temperature range of 570°‐660°K using a stirred‐flow reactor. The reaction was found to be first order and homogeneous with rate constants represented by the Arrhenius equation\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k{\rm (sec}^{- 1} {\rm) =}{{{\rm (16}{\rm .0} \pm {\rm 0}{\rm .3)} - {\rm (52}{\rm .9} \pm {\rm 0}{\rm .8)}} \mathord{\left/ {\vphantom {{{\rm (16}{\rm .0} \pm {\rm 0}{\rm .3)} - {\rm (52}{\rm .9} \pm {\rm 0}{\rm .8)}} \theta}} \right. \kern-\nulldelimiterspace} \theta} $$\end{document} where θ = 2.303 RT kcal/mol. The Arrhenius parameters are considerably higher than previously reported. On the assumption of a biradical mechanism the results are consistent with a cyano stabilization energy of ∼5 kcal/mol, in good agreement with the results of recent studies of related systems.