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Low temperature heat release (LTHR) in HCCI combustion changes according to fuel chemical composition and engine test conditions. In this study 11 pure hydrocarbon components were blended into 12 different model fuels to evaluate the effects of fuel composition on LTHR heating value, LTHR CA50 (crank angle at 50% completion of LTHR), high temperature heat release (HTHR), and engine performance. From the heat release analysis of the test data from a supercharged 4-cylinder engine, it was determined that the HTHR CA50 (crank angle at 50% completion of HTHR) was strongly indicative of combustion stability and maximum rate of pressure rise. Moreover, the functional dependence of HTHR CA50 on LTHR heating value and LTHR CA50 was quantified. Test fuels denoted MD05, Base, MC05 and MX05 were prepared by adding 5.2vol%, 9.3vol%, 15.0vol%, and 18.2vol% of n-hexane, respectively, to a blend of 10 pure hydrocarbons.