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Thermal dimerization of 1,3‐butadiene: Kinetics of the formation of cis , cis ‐cycloocta‐1,5‐diene
Author(s) -
Huybrechts G.,
Luyckx L.,
Vandenboom Th.,
Van Mele B.
Publication year - 1977
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.550090211
Subject(s) - chemistry , torr , reaction rate constant , diene , kinetics , thermal , 1,3 butadiene , standard enthalpy of formation , entropy (arrow of time) , thermodynamics , medicinal chemistry , computational chemistry , organic chemistry , catalysis , physics , quantum mechanics , natural rubber
The thermal reaction of 1,3‐butadiene (BD) has been studied between 464 and 557°K at pressures between 49 and 450 torr. The products are 4‐vinylcyclohexene (VCH) and cis , cis ‐cycloocta‐1,5‐diene (COD), and their formations are second order. The rate constant (in 1/mol · sec) for VCH is given by\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm V} = - (24,530 \pm 120)/4.576T + (6.95 \pm 0.05) $$\end{document}and that for COD by\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm C} = - (28,440 \pm 100)/4.576T + (7.65 \pm 0.04) $$\end{document}The thermal reaction of COD has also been studied. The temperature was varied from 505 to 586°K and the pressure from 15 to 51 torr. The rate constants (in sec −1 ) for the formations of VCH and BD are given by\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm log}_{10} k_{{\rm VCH}} = - (51,780 \pm 120)/4.576T + (15.34 \pm 0.05) \\ {\rm log}_{10} k_{{\rm BD}} = - (56,380 \pm 100)/4.576T + (16.46 \pm 0.04) \\ \end{array} $$\end{document}A biradical mechanism seems to fit these results. The heat of formation and the entropy of COD are estimated.