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Pyrolysis of 2,4‐dimethylhexene‐l and the stability of isobutenyl radicals

1973; Wiley; Volume: 5; Issue: 6 Linguagem: Inglês

10.1002/kin.550050604

1097-4601

Wing Tsang,

Combustion and Detonation Processes

Abstract 2,4‐Dimethylhexene‐l has been decomposed in single‐pulse shock tube experiments. Rate expressions for the initial reactions are and sec −1 at 1.5–5 atm and 1050°K. This leads to Δ H ° f300 (CH 2 = C(CH 3 )CH 2 ) = 124 kJ/mol, or an allylic resonance energy of 50 kJ/mol. Rate expressions for the decomposition of the appropriate olefins which yield isobutenyl radicals and methyl, ethyl, isopropyl, n ‐propyl, t ‐butyl, and t ‐amyl radicals, respectively, are presented. The rate expression for the decomposition of isobutenyl radical is (at the beginning of the fall‐off region). For the combination of isobutenyl and methyl radicals, the rate constant at 1020°K is Combination of this number and the calculated rate expression for 2‐methylbutene‐1 decomposition gives S . (1100) = 470 J/mol °K. This yields It is demonstrated that an upper limit for the rate of hydrogen abstraction by isobutenyl from toluene is