Very low-pressure pyrolysis (VLPP) of alkanes: n-butane, 2,3-dimethylbutane, 2,2′,3,3′ -tetramethylbutane, and isobutane

The four species in the title were decomposed under VLPP conditions at temperatures in the vicinity of 1100°K. Three model transition states were constructed that fit the low-pressure data thus obtained and that also yield (1) E298 = ΔE298; (2) E1100 = ΔE1100; (3) log A1100 = 16.4 per C–C bond broken. The predictions of these models as to values of the high-pressure rate constants for bond scission and the reverse rate constants (radical combination) are compared with existing data.

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