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Kinetics of competitive pathways in the thermal unimolecular decomposition of hex-1-yne

✍ Scribed by Keith D. King

Publisher
John Wiley and Sons
Year
1981
Tongue
English
Weight
507 KB
Volume
13
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The thermal unimolecular decomposition of hex‐1‐yne has been investigated over the temperature range of 903–1153 K using the technique of very low‐pressure pyrolysis (VLPP). The reaction proceeds via the competitive pathways of C~3~C~4~ fission and molecular retro‐ene decomposition, with the latter being the major pathway under the experimental conditions. RRKM calculations, generalized to take into account two competing pathways, show that the experimental unimolecular rate constants are consistent with the high‐pressure Arrhenius parameters at 1100 K given by
and
where θ = 2.303 RT kcal/mol and the A factors were assigned from the results of recent shock‐tube studies of hex‐1‐yne and related alkynes. The results for CC fission are consistent with previous VLPP and shock‐tube determinations of the propargyl resonance energy, and the parameters for the molecular pathway are consistent with systematic trends for the retro–ene decomposition of unsaturated hydrocarbons.

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