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We have studied the chemical aspects of the compression ignition of n-butane experimentally in a spark ignition engine and theoretically using computer simulations with a detailed chemical kinetic mechanism. The results of these studies demonstrate the effect of initial charge composition on autoignition. Experimentally, when the initial charge consisted of 80% fresh charge and 20% recycled products of combustion, we observed that autoignition was inhibited. On the other hand, charging with 80% fresh charge and 20% partial oxidation products from the previous motored cycle resulted in enhanced low-temperature chemistry (with the associated heat release and temperature increase) and autoignition. We assessed how well the detailed kinetic model could predict the autoignition and modified the model to better simulate the experimental observations. We also assessed how chemical preconditioning of the fuel-air charge affected the autoignition process.