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Octane-on-Demand (OoD) is a promising technology for reducing greenhouse emissions from automobiles. The concept utilizes a low-octane fuel for low and mid load operating conditions, and a high-octane additive is added at high load operating conditions. Researchers have focused on the minimum ethanol content required for operating at high load conditions when the low-octane fuel becomes knock limited. However, it is also widely known that ethanol has a high tendency to pre-ignite, which has been linked with its high laminar flame speed and surface ignition tendency. Moreover, ethanol has a lower stoichiometric air-fuel ratio, requiring a larger injected fuel mass per cycle. A larger fuel mass increases the potential for oil dilution by the liquid fuel, creating precursors for pre-ignition. Hence, the limits on ethanol addition owing to pre-ignition also need consideration before the technology can be implemented.