This study examined the impact and fate of sodium (fed as an aqueous nitrate solution) in fuel-rich methane/air and methane/methyl chloride/air flames as a function of equivalence ratios that experienced diffusion of air from the surroundings. The flames were stabilized on a slotted, uncooled burner. The data set was divided into profiles of relative sodium atom concentrations, temperatures, and selected stable species concentrations. The flames were simulated using a modified version of the Sandia FORTRAN program for modeling steady laminar one-dimensional premixed flames complete with detailed mechanisms. The results showed that maximum sodium atom concentration in the flame is decreased by an increase in equivalence ratio as well as an increase in chlorine loading. In addition, the location of maximum sodium atom concentration is shifted to a higher height above burner as the equivalence ratio is increased.