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Thermal dimerization of 1,3-butadiene: Kinetics of the formation of cis, cis-cycloocta-1,5-diene

✍ Scribed by G. Huybrechts; L. Luyckx; Th. Vandenboom; B. Van Mele

Publisher
John Wiley and Sons
Year
1977
Tongue
English
Weight
478 KB
Volume
9
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

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
and that for COD by

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

A biradical mechanism seems to fit these results. The heat of formation and the entropy of COD are estimated.

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