Chemiluminescence from the reaction F + Na2 → NaF + Na*(i) has been measured for six electronically excited states of Na: the upper state of the D line, 32P, and the more energetic states i = 32D, 52S, 42D, 62S, and 52D. The reaction is exoergic by 49 kcal/mol for formation of sodium in the 32P state, and slightly endoergic for the three highest energy channels. Measurements were made by recording visible chemiluminescence from the crossing region of partially collimated beams of reagents. The relative rate constants to form successively higher electronic states, i, decreased exponentially. These rates could be fitted approximately by statistical models following averaging over the breadth of thermal reagent energies. © 1989 American Chemical Society.