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Rates and equilibria in the reaction system Br + i-C4H10 ⇌ HBr + t-C4H9. The heat of formation of the t-butyl radical

✍ Scribed by Tajmeri S. A. Islam; Sidney W. Benson

Publisher
John Wiley and Sons
Year
1984
Tongue
English
Weight
635 KB
Volume
16
Category
Article
ISSN
0538-8066

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✦ Synopsis

The very low pressure reactor (VLPR) technique has been used to measure the bimolecular rate constant of the title reaction at 300 K. The rate constant is given by log k, (l/mol s) = (11.6 2 0.4) -(5.9 ? 0.6)/0 the equilibrium constant has also been measured at the same temperature and is given by K , = (5.6 ? 1) x and hence log k-, (l/mol s) = 9.5 ? 0.1. The results show that the reaction Br + t-C,H, 5

HBr + i-C,H, is unimportant under the present experimental conditions. Assigning the entropy of t-butyl radical to be 74 ? 2 eu which is in the possible range, the value of K , gives AH; (t-butyl) = 9.1 ? 0.6 kcal/mol-'. This yields for the bond dissociation, DH" (t-butyl-H) = 93.4 ? 0.6 kcal/mol. Both of these values are found to be in good agreement with recent VLPP studies.

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