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Thermal stability of intermediate sized acetylenic compounds and the heats of formation of propargyl radicals

1978; Wiley; Volume: 10; Issue: 7 Linguagem: Inglês

10.1002/kin.550100705

1097-4601

Wing Tsang,

Advanced Combustion Engine Technologies

Abstract 4‐Methylhexyne‐1, 5‐methylhexyne‐1, hexyne‐1, and 6‐methylheptyne‐2 have been decomposed in comparative‐rate single‐pulse shock‐tube experiments. Rate expressions for the initial decomposition reactions at 1100°K and from 2 to 6 atm pressure are In combination with previous results, rate expressions for propargyl CC bond cleavage are related to that for the alkanes by the expression These results yield a propargyl resonance energy of D ( n C 3 H 7 ‐H) – D (C 3 H 3 ‐H) = 36 ± 2 kJ, in excellent agreement with a previous shock‐tube study. They also lead to D (CH 3 C≡CCH 2 ‐H) – D (C 3 H 3 ‐H) = 0.6 ± 3 kJ, D ( s C 4 H 9 ‐H) – D ( i C 3 H 7 ‐H) = 0 ± 3 kJ, D ( i C 4 H 9 ‐H) – D ( n C 3 H 7 ‐H) = 2 ± 3 kJ, and D ( n C 3 H 7 ‐H) – D ( i C 3 H 7 ‐H) = 13.9 ± 3 kJ (all values are for 300°K). The systematics of the molecular decomposition process are explored.