Combustion kinetic mechanism development using multispecies time histories in shock-tube pyrolysis of 3-pentanone

摘要

Laser-based CO and H_2O time histories during 3-pentanone oxidation were measured behind reflected shock waves over the temperature range of 1277-1678 K at pressures around 1.6 atm, complementing recent work also conducted in this laboratory (Lam et al., Combust. Flame 2012). This previous work highlighted deficiencies in the first available 3-pentanone detailed kinetic mechanism (Serinyel et al. J. Phys. Chem. A 2010), and introduced a missing decomposition pathway for the methylketene intermediate. However, the modified mechanism still does not satisfactorily reproduce all of the data obtained in this laboratory. Given the unprecedented amount of species time history data available for the high temperature pyrolysis and oxidation of 3-pentanone, further mechanism improvements can be addressed through methods of uncertainty analysis and optimization. The combination of accurate species time histories behind reflected shock waves and these methods of uncertainty analysis are shown to affirm a newly assembled detailed chemical mechanism containing high kinetic uncertainties when compared to experimental pyrolysis data. However, satisfactory agreement could not be achieved with experimental oxidation data. Thus, this work serves to identify areas where improvements in elementary reaction kinetics are necessary.