Colloquium: REACTION KINETICS / INTERNAL COMBUSTION ENGINES Word Count (Method 1): The total word count (exclusive of title page, abstract) is: 5793 words Word Count (Performed from automatic counting function in MS Word plus References/Tables/Equations/ Figures) Abstract: 235 words, not included in word count Equations: 0 words (0 equations, single column) Figures: 1030 words (4 figures with captions) 3 single 50(+10) 132 4 double 52(+10) 273 Captions 116 Total: 6055 words Supplemental Materials: One supplemental material is available.
AbstractMulti-stage heat release is an important feature of hydrocarbon auto-ignition that influences engine operation. This work presents findings of previously unreported three-stage heat release in the autoignition of n-heptane/air mixtures at lean equivalence ratios and high pressures. Detailed homogenous gas-phase chemical kinetic simulations were utilized to identify conditions where two-stage and threestage heat release exist. Temperature and heat release profiles of lean n-heptane/air auto-ignition display three distinct stages of heat release, which is notably different than two-stage heat release typically reported for stoichiometric fuel/air mixtures. Concentration profiles of key radicals (HO2 and OH) and intermediate/product species (CO and CO2) also display unique behavior in the lean autoignition case. Rapid compression machine measurements were performed at a lean equivalence ratio to confirm the existence of three-stage heat release in experiments. Laser diagnostic measurements of CO concentrations in the RCM indicate similar concentration-time profiles as those predicted by kinetic modeling. Computational singular perturbation was then used to identify key reactions and species contributing to explosive time scales at various points of the three-stage ignition process.Comparisons with two-stage ignition at stoichiometric conditions indicate that thermal runaway at the second stage of heat release is inhibited under lean conditions. H+O2 chain branching and CO oxidation reactions drive high-temperature heat release under stoichiometric conditions, but these reactions are suppressed by H, OH, and HO2 radical termination reactions at lean conditions, leading to a distinct third stage of heat release.