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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.

The effect of engine operating parameters (speed, spark timing, and fuel-air equivalence ratio [Φ]) on hydrocarbon (HC) oxidation within the cylinder and exhaust system is examined using propane or isooctane fuel. Quench gas (CO2) is introduced at two locations in the exhaust system (exhaust valve or port exit) to stop the oxidation process. Increasing the speed from 1500 to 2500 RPM at MBT spark timing decreases the total, cylinder-exit HC emissions by ∼50% while oxidation in the exhaust system remains at 40% for both fuels. For propane fuel at 1500 rpm, increasing Φ from 0.9 (fuel lean) to 1.1 (fuel rich) reduces oxidation in the exhaust system from 42% to 26%; at 2500 RPM, exhaust system oxidation decreases from 40% to approximately 0% for Φ = 0.9 and 1.1, respectively. Retarded spark increases oxidation in the cylinder and exhaust system for both fuels. Decreases in total HC emissions are accompanied by increased olefinic content and atmospheric reactivity.

An experimental study was performed to develop a more fundamental understanding of the effects of secondary air injection (SAI) on exhaust gas emissions and catalyst light-off characteristics during cold start of a modern SI engine. The effects of engine operating parameters and various secondary air injection strategies such as spark retardation, fuel enrichment, secondary air injection location and air flow rate were investigated to understand the mixing, heat loss, and thermal and catalytic oxidation processes associated with SAI. Time-resolved HC, CO and CO₂ concentrations were tracked from the cylinder exit to the catalytic converter outlet and converted to time-resolved mass emissions by applying an instantaneous exhaust mass flow rate model. A phenomenological model of exhaust heat transfer combined with the gas composition analysis was also developed to define the thermal and chemical energy state of the exhaust gas with SAI.

The effects of secondary air on the exhaust oxidation of particulate matters (PM) have been assessed in a direct-injection-spark-ignition engine under fuel rich fast idle condition (1200 rpm; 2 bar NIMEP). Substantial oxidation of the unburned feed gas species (CO and HC) and significant reduction of both the particulate number (up to ∼80%) and volume (up to ∼90%) have been observed. The PM oxidation is attributed to the reactions between the PM and the radicals generated in the oxidation of the feed gas unburned species. This hypothesis is supported by the observation that the reduction in PM volume is proportional to the amount of heat release in the secondary oxidation.

Experiments were conducted to determine the effects of substantial spark retard on combustion, hydrocarbon (HC) emissions, and exhaust temperature, under cold engine conditions. A single-cylinder research engine was operated at 20° C fluid temperatures for various spark timings and relative air/fuel ratios. Combustion stability was observed to decrease as the phasing of the 50% mass fraction burned (MFB) occurred later in the expansion stroke. A thermodynamic burn rate analysis indicated combustion was complete at exhaust valve opening with -20° before top dead center (BTDC) spark timings. Chemical and thermal energy of the exhaust gas was tracked from cylinder-exit to the exhaust runner. Time-resolved HC concentrations measured in the port and runner were mass weighted to obtain an exhaust HC mass flow rate. Results were compared to time averaged well downstream HC levels.

The fate of hydrocarbon species in the exhaust systems of spark-ignition engines is an important part of the overall hydrocarbon emissions problem. In this investigation models were developed for the instantaneous heat transfer, fluid mixing, and hydrocarbon oxidation in an engine exhaust port. Experimental measurements were obtained for the instantaneous cylinder pressure and instantaneous gas temperature at the exhaust port exit for a range of engine operating conditions. These measurements were used to validate the heat transfer model and to provide data on the instantaneous cylinder gas state for a series of illustrative exhaust port hydrocarbon oxidation computations as a function of engine operating and design variables. During much of the exhaust process, the exhaust port heat transfer was dominated by large-scale fluid motion generated by the jet-like flow at the exhaust valve.