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Hydrocarbon thermal ignition in internal combustion engines is controlled by the balance of heat release rate by chemical reactions and internal energy formation or removal rate by adiabatic compression or expansion. Heat release rate can be described by a simple “Universal Rule”, that the heat release rate during the thermal ignition preparation period is determined by H2O2 loop composed of four elementary reactions. This rule was validated by sensitivity analysis and response analysis to perturbation of intermediate species concentrations. The rule was applied to clarify several subjects with experimental backgrounds, such as ignition characteristics of higher octane number fuels, an old and well-known knocking model and the influence of H2 addition.

Ignition process chemistry was analyzed using a detailed chemical kinetic model of n-heptane generated by KUCRS (Knowledge-basing Utilities for Complex Reaction Systems), wherein pressure-dependent rate constants of the O₂ addition to alkyl radicals and hydroperoxy alkyl radicals and the thermal decomposition of ketohydroperoxides have been introduced. Then, the effect of the initial pressure and the individual effects of the initial fuel, O₂ and N₂ molar concentrations on a relationship between the initial temperature and the ignition delay were discussed. When the initial temperature increases, the branch of C₇H₁₄OOH removal into the second O₂ addition and the decomposition into C₇H₁₄cyO and OH is more sensitive to the pressure and the O₂ concentration, and thus, the LTO preparation phase is more affected by the pressure and the O₂ concentration. The LTO phase terminates mainly by the OH removal by intermediate species.

A systematic chemical lumping method has been proposed, based on the detailed kinetic analysis of hydrocarbon fuel ignitions. The model constructed by using this method contains two reaction sets, RO2 and fragment reaction package. The ignition characteristics of each fuel can be reflected by only adjusting several rate parameters in RO2 reaction package. From the comparison with detailed model, it was confirmed that this simplified model well reproduces the results of detailed one without missing the kinetics of hydrocarbon ignitions. We concluded that this new lumping approach has the possibility to be applicable to every hydrocarbon fuels.