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A theoretical model for predicting cetane number of primary reference fuels from parameters measurable by proton nuclear magnetic resonance is presented. This modeling technique is expanded to include secondary reference fuels, pure hydrocarbons, and commercial-type fuels. An evaluation of the ignition process indicated that not only hydrogen type distribution measurable by proton NMR, but also relative hydrogen population is important in predicting cetane number. Two mathematical models are developed. One predicts cetane number of saturate fuels and the second predicts cetane number of fuels containing aromatic components. The aromatic fuel model is tested using the ASTM Diesel Check Fuels and shown to predict within the standard error of the model.