A detailed chemical kinetic mechanism was used to simulate the oxidation of n-butane/air mixtures in a motored engine. The modeling results were compared to species measurements obtained from the exhaust of a CFR engine and to measured critical compression ratios. Pressures, temperatures and residence times were considered that are in the range relevant to automotive engine knock. The compression ratio was varied from 6.6 to 15.5 to affect the recycle fraction and the maximum pressure and temperature of the fuel/air mixture. Engine speeds of 600 and 1600 rpm were examined which corresponded to different fuel/air residence times. The relative yields of intermediate species calculated by the model matched the measured yields generally to within a factor of two. The residual fraction derived from the previous engine cycle had a significant impact on the overall reaction rate in the current cycle. The influence of different components in the residual fraction, such as the peroxides, on fuel oxidation chemistry during the engine cycle was investigated.