Measurements and modeling of the formation of superequilibrium radicals and nitric oxide in atmospheric pressure turbulent jet diffusion flames are presented which quantify the influence of superequilibrium on thermal NO x formation. Variation of fuel gas compositions (CO/H 2/N 2, CO/H 2/CO 2, and CO/H 2/Ar) permits partial separation of chemical and fluid mechanical effects. Superequilibrium OH radical concentrations are measured by single-pulse laser saturated fluorescence and NO and NO 2 concentrations by probe sampling and chemiluminescent detection. Four different types of probes were used to quantify probe sampling effects. In turbulent reaction zones, virtually all of the NO x in the flame occurred in the form of NO but far downstream of the flame nearly half of the NO x occurred as NO 2. Thermal NO x maximized near stoichiometric flame zones; the rich shift observed by others may be a probe sampling artifact. In turbulent CO/H 2/N 2 jet diffusion flames, both measurements and a nonequilibrium turbulent combustion model show that superequilibrium decreases average temperatures by 250K, increases average OH concentrations by a factor of 4–6, and increases thermal NO x formation principally by broadening the range of mixture fraction (both rich and lean) where thermal NO x is formed. Calculated increases in thermal NO x due to superequilibrium in turbulent CO/H 2/N 2 jet diffusion flames are factors of 2.5 at 1 atm and 1.4 at 10 atm. The two-scalar pdf model predicts that thermal NO x yield is independent of Reynolds number in disagreement with previous experimental reports.
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