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The thermal unimolecular isomerization of cis-hepta-1,3-diene

✍ Scribed by H. E. O'Neal; H. M. Frey

Publisher
John Wiley and Sons
Year
1970
Tongue
English
Weight
230 KB
Volume
2
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The reversible isomerization of cis‐hepta‐1,3‐diene to cis‐2‐trans‐4‐heptadiene via a 1,5 hydrogen shift has been investigated kinetically at nine temperatures in the range of 475° to 531°K. Equilibrium is reached near 94% reaction. Some cis‐2‐cis‐4‐heptadiene is also formed, but at a rate some 60 times slower than the cis,trans isomer. A least‐squares analysis of the data yielded the Arrhenius equation for the isomerization of the cis‐hepta‐1,3‐diene:
Possible errors in the equilibrium constant measurements are discussed, and employing an equilibrium constant calculated by using group additivity estimates together with the values of k~1~, we obtained for the reverse reaction
where
.

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