Investigation of NCN and prompt-NO formation in low-pressure C1–C4 alkane flames

Temperature, CH, NCN, and NO profiles were measured for eight low-pressure hydrocarbon flames fueled by methane, ethane, propane, and butane using laser-induced fluorescence (LIF) diagnostics. These measurements were used (1) to assess NCN and prompt-NO formation chemistry across a series of fuels of increasing number of carbons at different equivalence ratios (ϕ = 1.07 and 1.28); (2) to examine the predictive capabilities of current C1–C4 hydrocarbon and NCN formation/consumption combustion mechanisms on properly capturing prompt-NO formation and (3) to examine the postulation that additional prompt-NO precursors (other than CH) exist for fuels larger than methane. For a given equivalence ratio, the measured peak CH concentration is fairly constant across all four fuels, while both the peak NCN and post-flame NO concentrations steadily increase. Furthermore, it is found that as the fuels increase in number of carbons, i.e., methane to butane, the correlation between the peak NCN and post-flame NO remains high, while the correlation between peak CH and peak NCN and peak CH and post-flame NO becomes increasingly lower. This is especially evident for rich flame cases. The experimental profiles are compared to numerical calculations using two comprehensive kinetic mechanisms suitable for C4 chemistry, where the CH + N2 → NCN + H reaction is assumed as the only prompt-NO initiation reaction. For the ϕ = 1.28 flame cases, CH is over-predicted using both mechanisms for all four fuels and by as much as 60%, while for the ϕ = 1.07 cases, CH is predicted to within 15% of the experimentally-derived results, although there is some discrepancy concerning the spatial locations of the CH profiles. For both NCN and NO, there is an increasing under-prediction for the ϕ = 1.28 cases as the fuel increases in number of carbons, while for the ϕ = 1.07 cases there is a systematic under-prediction of NCN and NO with a weaker (although evident) fuel dependence. From the experimental results and the comparison to modeling predictions, it is apparent that additional work concerning CH formation and consumption kinetics is necessary to accurately capture the CH concentration profiles across a broad range of conditions. Furthermore the comparisons to the modeling predictions using only a single prompt-NO precursor, CH, indicate a reasonable plausibility that (an) additional prompt-NO precursor (s) exist and become important when considering fuels larger than methane, especially under rich flame conditions. Possible precursors in addition to CH are discussed.