NH3/C2H6 and NH3/C2H5OH oxidation in a shock tube: Multi-speciation measurement, uncertainty analysis, and kinetic modeling

Abstract

This study examines NH3, NO, and CO profiles during NH3/C2H6 and NH3/C2H5OH oxidation in a shock tube using laser absorption spectroscopy at 1317–1957 K and ∼2.8 bar, with 5–20% C2H6 or C2H5OH, equivalence ratios of 0.5/1.0/1.5, and a 0.9 argon dilution ratio. Metrological uncertainty analysis on mole fractions have been performed. A novel dynamic uncertainty methodology is proposed to time-resolved speciation profiles. From the experimental measurements, the promotional effect on ammonia ignition by C2H6 or C2H5OH is identical under investigated conditions. The multi-speciation profiles demonstrate reasonable relations among the consumption of NH3 and the formation of NO and CO, which show strong temperature and equivalence ratio dependence. An updated PTB-NH3/C2 1.1 mechanism accurately predicts ignition delay times and speciation profiles. Sensitivity analysis reveals NH3 chemistry’s significant control, with NH3+O2/H/OH and N2H2+M reactions being critical at >1300 K, and HO2 interactions being pivotal at 800–1200 K. The reactions related to N2H2 and N-C chemistries dominate for fuel-rich mixtures at high temperatures, resulting in a reverse equivalence ratio dependence on IDTs, namely fuel-rich mixtures exhibit the lowest reactivity. The N-C chemistries, particularly the pronounced reaction pathway of HCN→CN→NCO→HNCO→CO play a crucial role in maintaining the CO level constant after reaching its peak position under fuel-rich conditions·NH3 consumption pathways shift from NH2→H2NO→HNO→NO→NO2→N2O→N2 at intermediate temperatures to NH3→NH2→NH→N(HNO)→NO→(N2O)N2 at high temperatures. The C2-additives participate in the oxidation process by introducing additional OH/H/CH3 radicals, thereby facilitating the reactive radical pool and developing the N-C intersystem-crossing pathways. In summary, the extensive multi-speciation data, metrological uncertainty analysis, mechanism validation and development, together with comprehensive kinetic modelling can be valuable resources for further studies of ammonia combustion.