✦ LIBER ✦

The kinetics and thermochemistry of the gas phase reaction of cyclopentadiene and iodine. Relevance to the heat of formation of cyclopentadienyl iodide and cyclopentadienyl radical

✍ Scribed by Shozo Furuyama; David M. Golden; Sidney W. Benson

Publisher: John Wiley and Sons
Year: 1971
Tongue: English
Weight: 492 KB
Volume: 3
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550030305

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✦ Synopsis

Abstract

The rate of the reaction of cyclopentadiene with iodine has been followed spectrophotometrically over the temperature range 171.7° to 276.5°C. The reaction first proceeds almost to the point of equilibrium with cyclopentadienyl iodide and HI, although the final products are fulvalene and HI. Equilibrium constants obtained are those predicted by bond additivity. A third‐law value of δ__H__^0^~f 298~ (c‐C~5~H~5~I,g) = 49 kcal/mole is obtained. Rate studies of the reaction up to the iodide equilibrium, yield values for the rate constant magnified image. Uncertainty in the Arrhenius parameters, as well as doubts as to the applicability of the usual assumption that E~3~ = 1 ± 1 kcal/mole, make difficult an evaluation of total cyclopentadienyl stabilization energy (TSE) from these data. However, the value is probably 15 < TSE < 20.

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