ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550090211
Permalink
