Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 266 - 271 (1980)
Update date:2022-08-11
Topics:
Trenwith, Antony B.
Measurements of the rate at which methane is formed in the pyrolysis of 1,3-hexadiene at temperatures over the range 694-759 K and pressures between 25 and 200 Torr show that the dissociation reaction CH3CH2CH=CHCH=CH2 -> CH3.+ .CH2CH=CHCH=CH2 is a homogeneous, first-order reaction under these conditions and the rate expression is log(k1/s-1) = (15.92 +/- 0.17)-(66390 +/- 840)/θ where θ = 2.303RT/cal mol-1 (1 cal = 4.18 J).The experimental activation energy yields for the pentadienyl radical, ΔH<*> = 45.9 +/- 1.0 kcal mol-1 at 298 K and a resonance energy of 18.5 +/- 1.5 kcal mol-1, assuming a value of 98.2 kcal mol-1 for the primary C-H bond dissociation energy in alkenes.
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