Chemiluminescent reactions of fluorine and chlorine atoms with bromine azide

Chemiluminescence from the reactions of fluorine and chlorine atoms with BrN3 has been observed in a discharge-flow apparatus. The F+BrN3 reaction produces electronically excited BrF(B 3Π0+) in low vibrational levels (v≤2), as well as excited NBr(b 1Σ+). The only emission observed from the Cl+BrN3 reaction is the b 1Σ+→X 3Σ− transition in NBr. The data are consistent with mechanisms involving attack of the halogen atoms on the nitrogen chain of the azide. The vibrational excitation of the emitting products suggests the heat of formation of BrN3 to be 131±2 kcal mol−1.