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The chemical kinetic mechanism determines the ignition timing of homogeneous charge compression ignition (HCCI) engines. The correlation of the ignition delay in shock tubes and HCCI engines under different operating conditions was studied with a reduced mechanism of the primary reference fuel (PRF) composing of n-heptane and iso-octane. According to the similarity analysis of the sensitivity coefficient, the operating conditions which affect the similarity factor are recognized. The results indicate that, under the negative temperature coefficient (NTC) region of the ignition delay in shock tubes, the weight of each reaction on the ignition delay in shock tubes is similar to that in HCCI engines. The ignition delay time in HCCI engines is defined as the period from the time of start of heat release (SHR) with the HRR greater than zero to CA10. At the high equivalence ratios in shock tubes, the similarity factor at the low ambient temperatures is small.