ISSN:
0538-8068
Keywords:
Chemistry
;
Physics Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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: \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log k_1 } \mathord{\left/ {\vphantom {{\log k_1 } {\sec ^{ - 1} = {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \mathord{\left/ {\vphantom {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \theta }} \right. \kern-\nulldelimiterspace} \theta }}}} \right. \kern-\nulldelimiterspace} {\sec ^{ - 1} = {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \mathord{\left/ {\vphantom {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \theta }} \right. \kern-\nulldelimiterspace} \theta }}} $$\end{document} 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 k1, we obtained for the reverse reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log k_2 } \mathord{\left/ {\vphantom {{\log k_2 } {\sec ^{ - 1} = (11.1 \pm 0.15) - ([35,800 \pm 300])}}} \right. \kern-\nulldelimiterspace} {\sec ^{ - 1} = (11.1 \pm 0.15) - ([35,800 \pm 300])}}{{{\rm cal mole}^{ - {\rm 1}} )} \mathord{\left/ {\vphantom {{{\rm cal mole}^{ - {\rm 1}} )} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} where \documentclass{article}\pagestyle{empty}\begin{document}$$ \theta = 2.303RT $$\end{document}.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550020502
Permalink
