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The autoignition characteristics of methanol, ethanol and MTBE (methyl tert-butyl ether) have been investigated in a rapid compression machine at pressures in the range 20-40 atm and temperatures within 750-1000 K. All three oxygenated fuels tested show higher autoignition temperatures than paraffins, a trend consistent with the high octane number of these fuels. The autoignition delay time for methanol was slightly lower than predicted values using reported reaction mechanisms. However, the experimental and measured values for the activation energy are in very good agreement around 44 kcal/mol. The measured activation energy for ethanol autoignition is in good agreement with previous shock tube results (31 kcal/mol), although ignition times predicted by the shock tube correlation are a factor of three lower than the measured values. The measured activation energy for MTBE, 41.4 kcal/mol, was significantly higher than the value previously observed in shock tubes (28.1 kcal/mol).

This paper provides an overview of spark-ignition engine unburned hydrocarbon emissions mechanisms, and then uses this framework to relate measured engine-out hydrocarbon emission levels to the processes within the engine from which they result. Typically, spark-ignition engine-out HC levels are 1.5 to 2 percent of the gasoline fuel flow into the engine; about half this amount is unburned fuel and half is partially reacted fuel components. The different mechanisms by which hydrocarbons in the gasoline escape burning during the normal engine combustion process are described and approximately quantified. The in-cylinder oxidation of these HC during the expansion and exhaust processes, the fraction which exit the cylinder, and the fraction oxidized in the exhaust port and manifold are also estimated.