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This thesis is a combined work of understanding the high temperature oxidation chemistry of cycloalkanes viz. methylcyclohexane based on previously developed cyclohexane and extending it to generate the larger n-propylcyclohexane chemical kinetic mechanism. The detailed kinetic reaction mechanism model for the oxidation of 1-hexene previously developed has been added to account for the ring opening of cyclohexane forming 1-hexene. As an update to the publication, preference of allylic H-abstractions from 1-hexene has been taken into account and retro-ene reaction producing propene has been added. The complete model is composed of 329 species and 2065 reactions with 3796 reversible elementary reactions. Further, these models have been validated against different experiments such as shock tubes, jet stirred reactors and laminar flames to cover full range of temperatures, pressures and equivalence ratios making the models comprehensive and was found to be adequate to satisfactorily reproduce the experimental data. The allylic radicals (C₆H₁₁-D1R3) preferred abstractions from 1-hexene improves the C₆H₁₁ profiles in the 1-hexene model. But it also influences the otherwise isomerization path of C₆H1₁₁-D1R6 to CYC₆H₁₁ (Cyclohexyl radical) which would further form cyclohexene (CYC₆H₁₀). It is observed that CYC₆H₁₀ profiles in 1-hexene flames and cyclohexane speciation are over-predicted. The major decomposition pathway of the cycloalkanes is through H-abstractions on the ring. The path which leads towards ring opening to form olefin is observed for cyclohexane and methylcyclohexane but is very low. The fulvene pathway influence on benzene profiles of 1-hexene is obvious but do not seem to affect the cycloalkanes. This infers there are other benzene formation pathways in cycloalkanes. Some possible pathways would be the dehydrogenation of dienes and dehydrogenation of cyclo-olefins.
In recent years, biodiesel is an alternative fuel to petroleum diesel that is renewable and creates less harmful emissions than conventional diesel. Biodiesel blends – usually B20 or below, have been the most commonly used biodiesel blends. In current study, the kinetic mechanism of n-decane/α-methylnaphthalene (AMN)/methyl-decanoate (MD) blend is developed and validated as the surrogate for biodiesel/diesel blends. The IDEA reference fuel (70% n-decane/30% AMN by liquid volume) was formulated in the past as a two-component diesel surrogate fuel. A comprehensive and compact oxidation model for the IDEA reference fuel is developed. One important fuel-fuel interaction pathway via reaction pathway of A2CH2 + HO2 is observed and detailed discussed. The IDEA blends are validated by comprehensive target experiments for n-decane, AMN, and the AMN/n-decane blends. Ignition delay times, flame speeds, and species composition in jet stirred reactor and counter flow flames are successfully simulated for a broad range of temperatures (500-2000 K) and pressures (1-50 bar). The simulations of the IDEA blend with current mod-el show acceptable agreement when compared with different experiments of ignition delay times for diesel fuels as well as flame speed experiments. With a chain of ten carbon atoms and a methyl-ester group attached, MD is considered as a one-component surrogate fuel for biodiesel. A comprehensive and compact kinetic model for MD is developed. The mechanism is critically tested by comparison of model predictions with experimental data over a wide temperature (500 to 1500 K) and pressure (1 to 20 bar) range and for different fuel/oxidizer ratios. The good maintenance of chemical information during the reduction has been confirmed by simulation results, as well as the sensitivity and flow analyses performed using the detailed and the skeletal model. The MD model is compared with available experimental ignition delay times of biodiesel fuels. The good agreement between the simulations and the experiments proves that this model is a reliable kinetic model for simulations, either used by itself or in combination with IDEA blend. To improve the mechanism analysis, this thesis introduces a new three-stage reactive flow analysis. The final skeletal n-decane/AMN/MD blend with skeletal base mechanism includes 295 species and 3500 reactions by using the CGR approach. Based on the above validations and comparisons, current blend is considered as one surrogate for biodiesel/diesel blends that is suitable for improving kinetic understanding and for application in engine simulations.