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The Kinetics of the gas-phase isomerization of 1,trans-3,trans-5-heptatriene into the cis-5-isomer catalyzed by Nitric Oxide and the stabilization energy in the pentadienyl radical

✍ Scribed by Kurt W. Egger; M. Jola

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

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✦ Synopsis

The kinetics of the nitric oxide catalyzed, homogeneous, gas-phase isomerizatioil of 1 ,trans-3,trans-5-heptatriene have been studied for temperatures ranging between 130°C and 241°C. The very clean reaction involves exclusive geometrical isomerization about the 5,6-x-bond. The observed rate constants for NO + trans-3,trans-5 + trans-3,cis-5 + NO can be represented (with standard errors) by log k, = (7.18 =t 0.06) -(16.75 f O.lZ)/O, where 8 = 2.303 R T in kcal/mole. The consecutive-step reaction mechanism involves addition of N O to the double bond (Ka,tl = k,/k,), followed by rotation of the 5,6-C-C bond in the adduct radical (k,). Analysis of the observed activation parameters shows, that k , is rate-controlling and consequently k, = k,Ka,, . Estimates of k , and Ka,b lead to a value of k, in good agreement with experiment.

Comparing our data with those previously obtained for the similar 1,3-pentadiene system results in a value for the extra stabilization energy generated in the 1,3-heptadienyl radical of 18.5 & 1.7 kcal/mole. This value is discussed in view of comparable data in the literature.

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