Journal of Physical Chemistry p. 3130 - 3136 (1981)
Update date:2022-08-04
Topics:
Nguyen, Tam T.
King, Keith D.
The thermal unimolecular reactions of 3-methylbut-1-yne (MBT) and 3-methylbuta-1,2-diene (MBTD) have been studied over the temperature range 940-1222 K by using the technique of very low-pressure pyrolysis (VLPP).Both compounds decompose via C3-C4 bond fission producing the resonance-stabilized radicals, 1-methylpropargyl from MBT and 1-methylallenyl from MBTD.In addition, interconversion between the two reactants takes place via structural isomerization.RRKM calculations, incorporating competing pathways and a temperature-dependent gas/wall collision efficiency, show that the experimental rate constants are consistent with the following high-pressure specific rate expressions at 1100K : log(k1/s-1) = (16.3 +/- 0.3) - (71.6 +/- 1.0)/Τ for bond fission and log(k2/s-1) = (13.2 +/- 0.6) - (60.5 +/- 1.0)/Τ for isomerization for MBT, log(k3/s-1) = (16.3 +/- 0.3) - (75.3 +/- 1.0)/Τ for bond fission and log(k4/s-1) = (13.2 +/- 0.6) - (63.8 +/- 1.0)/Τ for isomerization for MBTD, where Τ = 2.303RT kcal/mol.The A factor for bond fission was assigned from the results of recent shock-stube studies of related alkynes, and the A factor for isomerization was adopted from that previously reported for the analogous allene <-> propyne interconversion.The results lead to ΔH0f300
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