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The oxidation mechanism of DTBP (Di-tertiary-butyl peroxide) and its role in butane oxidation have been investigated, as it pertains to the development of an LPG DI diesel engine. Ignition delay contours were analyzed to investigate the role of DTBP (ϕ≈0.2 to the total oxygen) in butane oxidation. At higher pressure and lower temperature regions, it was apparent that the addition of DTBP significantly enhances the ignition delay of butane, whereas at lower pressures and higher temperatures, this effect diminishes. Results of this study showed that the role of DTBP to enhance the ignition delay of the base fuel is through rapid heat release, rather than by radicals produced by decomposition during the base fuel ignition delay. Formaldehyde is a principal species involved in reactions for heat release in the higher pressure lower temperature region, comparable to diesel engine operating conditions.