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Numerical investigations are reported on the location of sites at which autoignition first develops in the end-gas ahead of a spark-ignited flame in a combustion chamber following rapid compression of an alkane + air mixture to high pressures and temperatures. Attention is drawn to the part played by the reactions that give rise to a negative temperature coefficient of reaction rate in an inhomogeneous temperature field. A ‘reduced’ kinetic mechanism was employed to model the spontaneous oxidation of n-alkanes. Flame propagation was described in terms of the ‘eddy dissipation concept’ and coupled to the more detailed mechanism by means of a switching algorithm. The CFD calculations were performed by use of KIVA II.