✦ LIBER ✦

The kinetics of the thermal gas-phase reaction Br2 + C6F5I → BrI + C6F5Br. An attempt to determine the bond dissociation energy D(C6F5-I)

✍ Scribed by Ernest N. Okafo; Eric Whittle

Publisher: John Wiley and Sons
Year: 1978
Tongue: English
Weight: 372 KB
Volume: 10
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550100606

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✦ Synopsis

The kinetics of the thermal bromination reaction ( 3 ) have been studied in the range of 26lo-391"C. The observed rate law is compatible with initiation by the step (6) for which we obtain Brz + CsFsI -BrI + C6FsBr Br + C6FJ -BrI + C6F5 log k6(cm3/mol. sec) = (13.41 f 0.26) -(11700 f 700)/6 where 8 = 2.303RT cal/mol. Using the above value of &, we have D(C6Fs-I) = 53.5 kcal/mol

This result disagrees with values of D(C6Fs-I) obtained in other ways and we conclude that reaction (3) probably does not involve initiation by reaction (6). Instead, initiation may involve an addition of Br to the ring in C6FsI followed by decomposition of the adduct to give CsFsBr. If correct, this implies that the Arrhenius parameters above refer to the addition reaction rather than to reaction (6).

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