Abstract
The pyrolysis of isobutane was investigated in the ranges of 770° to 855°K and 20 to 150 Torr at up to 4% decomposition. The reaction is homogeneous and strongly self‐inhibited. A simple Rice‐Herzfeld chain terminated by the recombination of methyl radicals is proposed for the initial, uninhibited reaction. Self‐inhibition is due to abstraction of hydrogen atoms from product isobutene giving resonance‐stabilized 2‐methylallyl radicals which participate in termination reactions. The reaction chains are shown to be long. It is suggested that a previously published rate constant for the initiation reaction (1)
is incorrect and the value k~1~ = 10^16.8^ exp (−81700 cal mol^−1^/RT)s^−1^ is recommended. The values of the rate constants for the reactions (4i)
(4__t__)
(8)
are estimated to be
and
From a recalculation of previously published data on the pyrolysis of isobutane at lower temperatures and higher pressures, the value k~11c~, = 10^9.6^ cm^3^ mol^−1^ s^−1^ is obtained for the rate constant of recombination of t‐butyl. A calculation which is independent of any assumed rate constants or thermochemistry shows that the predominant chain termination reaction is the recombination of two methyl radicals in the conditions of the present work and the recombination of two t‐butyl radicals in those of our previous study at lower temperatures and higher pressures.