LIF MEASUREMENTS AND CHEMICAL KINETIC ANALYSIS OF NITRIC OXIDE FORMATION IN HIGH-PRESSURE COUNTERFLOW PARTIALLY PREMIXED AND NONPREMIXED FLAMES

Abstract

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of nitric oxide concentration ([NO]) in laminar, methane/air counterflow partially premixed and nonpremixed flames at six pressures up to 15 atm using excitation near 226.03 nm in the γ(0,0) band of NO. For partially premixed flames, fuel-side equivalence ratios (φB) of 1.45, 1.6, and 2.0 are studied at a global strain rate of 20 s−1. For nonpremixed flames, a complete set of NO measurements at global strain rates of 20 s−1, 30 s−1, and 40 s−1 is presented to supplement previously reported data in such flames. The quantitative NO measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). The effect of radiative heat loss on NO predictions is assessed by using a modified version of the code that considers radiation in the optically thin limit. The linear LIF measurements of [NO] are corrected for variations in the electronic quenching rate coefficient by using major species and temperature profiles generated by the opposed-flow flame code plus quenching cross sections for NO available from the literature. A pathway analysis provides the relative contribution of different NO formation mechanisms to the total amount of NO produced at various pressures. Quantitative reaction path diagrams are used to investigate pictorially species interactions during NO formation. Finally, we identify key reactions controlling NO concentrations in counterflow partially premixed and nonpremixed flames by using a sensitivity analysis. For the nonpremixed flames, NO measurements at pressures of 2–5 atm disagree substantially with predictions from either GRI mechanism. On the other hand, both mechanisms predict observed NO concentrations reasonably well beyond 6 atm. In general, for our nonpremixed flames, NO formation is dominated by the prompt route at lower pressures with an increasing contribution from the N2O pathway at higher pressures. For partially premixed flames, GRI 3.0 mimics the basic quantitative trends found in our LIF measurements at 1–15 atm. The kinetic analysis indicates that the prompt mechanism dominates at lower pressures, whereas the thermal and N2O pathways become more important at higher pressures. At any given pressure, a reduction in partial premixing results in kinetic behavior approaching that of the nonpremixed flames.