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- Methylcyclohexan (1) (remove)
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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.