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This article investigates the effects of various primary reference fuel (PRF) blends, compression ratios, and intake temperatures on the thermodynamics and performance of homogeneous charge compression ignition (HCCI) combustion in a Cooperative Fuels Research (CFR) engine. Combustion phasing was kept constant at a CA50 phasing of 5° after top dead center (aTDC) and the equivalence ratio was kept constant at 0.3. Meanwhile, the compression ratio varied from 8:1 to 15:1 as the PRF blends ranged from pure n-heptane to nearly pure isooctane. The intake temperature was used to match CA50 phasing. In addition to the experimental results, a GT-Power model was constructed to simulate the experimental engine and the model was validated against the experimental data. The GT-Power model and simulation results were used to help analyze the energy flows and thermodynamic conditions tested in the experiment.