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Addition of nitroalkanes to gasoline is shown to reduce the octane quality. The reduction in the Motor Octane Number (MON) is greater than the reduction in the Research Octane Number (RON). In other words addition of nitroalkanes causes an increase in octane sensitivity. The temperature of the compressed air/fuel mixture in the MON test is higher then in the RON test. Through chemical kinetic modelling, we are able to show how the temperature dependence of the reactions responsible for break-up of the nitroalkane molecule can lead to an increase in octane sensitivity. Results are presented from an Homogenous Charge Compression Ignition (HCCI) engine with a homogeneous charge in which the air intake temperature was varied. When the engine was operated on gasoline-like fuels containing nitroalkanes, it was observed that the combustion phasing was much more sensitive to the air intake temperature. This suggests a possible means of controlling combustion phasing for HCCI.