NCN profiles were measured for five rich and lean premixed, low-pressure methane flames using laser-induced fluorescence (LIF). A semi quantitative determination of the NCN mole fractions as a function of spatial height above the burner is made by calibrating the NCN LIF signals using highly accurate OH LIF measurements in an adjacent spectral region. The resulting calibration yields an uncertainty estimate of a factor of 3 for the absolute values, but only 125% for the relative NCN profiles. For all flame conditions, the NCN profiles occur immediately downstream of previously measured CH profiles. In addition, high correlations are found between the peak CH and peak NCN concentrations and the peak NCN and postflame NO concentrations over all equivalence ratios. These observations are consistent with NCN being the primary product channel from the CH + N-2 reaction and the initial intermediate in the prompt NO formation. This is the first mechanistic study in hydrocarbon flames that provides such experimental evidence. The experimental profiles are compared to numerical calculations using modified versions of two well-established hydrocarbon kinetic mechanisms. Reasonable agreement between the calculations and experiment is found for NCN profile shape, location of peak NCN concentrations, and absolute mole fractions. However, the dependence on stoichiometry of the peak NCN concentration is overestimated. Further work is required on NCN kinetics for modeling prompt NO in laminar premixed flames. (c) 2007 The Combustion Institute. Published by Elsevier Inc. All rights reserved.