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The absolute rate constant for the metathesis t-C4H9• + DI → C4H9D + I• and the heat of formation of the t-butyl radical

✍ Scribed by Michel Rossi; David M. Golden

Publisher
John Wiley and Sons
Year
1979
Tongue
English
Weight
419 KB
Volume
11
Category
Article
ISSN
0538-8066

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✦ Synopsis

The Arrhenius parameters for the title reaction have been measured in a very-low-pressure pyrolysis apparatus in the temperature range 644-722 K and are given by log kZ (A4-I. sec-I) = 9.68 -2.12/8, where 0 = 2.303RT in kcal/mol. Together with the published Arrhenius parameters for the reverse reaction from iodination studies, they result in a standard heat of formation of the t-butyl radical of 8.4 kcal/mol, accepting So(C4Hg-) = 72.2 e.u. a t 300 K from other kinetic data, and thus confirm the accepted value for AHY(t-C,Hy), a t variance with recent investigations which yielded significantly higher values. This value for AH?(t -C4Hy) results in a bond-dissociation energy (BDE) for isobutane of 92.7 kcal/mol.

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