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The oxidation chemistry of paraffins, aromatics, olefins and MTBE were examined. Detailed chemical kinetics calculations were carried out for oxidation of these compounds in the engine cycle. The oxidation rates are very sensitive to temperature. At temperatures of over 1400 K (depending on the fuel), all the hydrocarbons are essentially oxidized for typical residence time in the engine. Based on the kinetics calculations, a threshold temperature is defined for the conversion of the fuel species to CO, CO2, H2O and partially oxidized products. The difference in the survival fraction between aromatics and non-aromatics is attributed to the higher threshold temperature of the aromatics.

A technique has been developed to measure the desorption and subsequent oxidation of fuel in the oil layer by spiking the oil with liquid fuel and firing the engine on gaseous fuel or motoring with air. Experiments suggest that fuel desorption is not diffusion limited above 50 °C and indicated that approximately two to four percent of the cylinder oil layer is fresh oil from the sump. The increase in hydrocarbon emissions is of the order of 100 ppmC1 per 1% liquid fuel introduced into the fresh oil in a methane fired engine at mid-speed and light load conditions. Calculations indicate that fuel desorbing from oil is much more likely to produce hydrocarbon emissions than fuel emerging from crevices.

The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke.