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The prediction of knock onset in spark-ignition engines requires a chemical model for the autoignition of the hydrocarbon fuel-air mixture, and a description of the unburned end-gas thermal state. Previous studies have shown that a reduced chemistry model developed by Keck et al. adequately predicts the initiation of autoignition. However, the combined effects of heat transfer and compression on the state of the end gas have not been thoroughly investigated. The importance of end-gas heat transfer was studied with the objective of improving the ability of our knock model to predict knock onset over a wide range of engine conditions. This was achieved through changing the thermal environment of the end gas by either varying the inlet air temperature or the coolant temperature. Results show that there is significant heating of the in-cylinder charge during intake and a substantial part of the compression process.

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).

Measurements were made of exhaust histories of the following species: unburned hydrocarbons (HC), carbon monoxide, carbon dioxide, oxygen, and nitric oxide (NO). The measurements show that the exhaust flow can be divided into two distinct phases: a leading gas low in HC and high in NO followed by a trailing gas high in HC and low in NO. Calculations of time resolved equivalence ratio throughout the exhaust process show no evidence of a stratified combustion. The exhaust mass flow rate is time resolved by forcing the flow to be locally quasi-steady at an orifice placed in the exhaust pipe. The results with the quasi-steady assumption are shown to be consistent with the measurements. Predictions are made of time resolved mass flow rate which compare favorably to the experimental data base. The composition and flow histories provide sufficient information to calculate the time resolved flow rates of the individual species measured.