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The rate of the gas phase iodination of cyclobutane. The heat of formation of the cyclobutyl radical

✍ Scribed by D. F. McMillen; D. M. Golden; S. W. Benson

Publisher: John Wiley and Sons
Year: 1972
Tongue: English
Weight: 381 KB
Volume: 4
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550040503

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✦ Synopsis

The gas phase iodination of cyclobutane was studied spectrophotometrically in a

The early stage of the reaction static system over the temperature range 589" to 662°K.

was found to correspond to the general mechanism

where the Arrenius parameters describing kl are given by log kl/M-' sec-' = 1 1.66 f 0.1 1 -26.83 f .31/0, e = 2.303RT in kcal/mole. The measured value of El, together with the fact that E-l = 1 f 1 kcal/mole, provides AH&~(c-C~H,.) = 51.14 f 1.0 kcal/mole, and the corresponding bond dissociation energy, D(c-CdH7-H) = 96.8 f 1.0 kcal/mole. A bond dissociation energy of 1.8 kcal/mole higher than that for a normal secondary C-H bond corresponds to one half of the extra strain energy in cyclobutene compared to cyclobutane and is in excellent agreement with the recent value of Whittle, determined in a completely different system. Estimates of AH! and entropy of cyclobutyl iodide are in very good agreement with the equilibrium constant XI, deduced from the kinetic data. Also in good agreement with estimates of Arrhenius parameters is the rate of H I elimination from cyclobutyl iodide.

KI, (fast)

1 RH + 1. + R . + HI R -+ 1 2 4 R I + 1 .

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