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A recently developed Laser Raman Scattering system was applied to measure the in-cylinder air-fuel ratio and the residual gas content (via the water content) of the charge simultaneously in a firing spark-ignition engine during cold start and warm-up. It is the main objective of this work to elucidate the origin of misfires and the necessity to over-fuel at cool ambient temperatures. It turns out that the overall air-fuel ratio and residual gas content (in particular the residual water content) of the charge appear to be the most important parameters for the occurrence of misfires (without appropriate fuel enrichment), i.e., the engine behaviour from cycle to cycle becomes rather predictable on the basis of these data. An alternative explanation for the necessity to over-fuel is given.