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) E 298 = Δ E 298 ; (2) E 1100 = Δ E 1100 ; (3) log A 1100 = 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.