Mj. Bramwell et Jc. Whitehead, Chemiluminescence from the reactions of atomic and molecular fluorine withphosphorous trichloride and tribromide, PCCP PHYS C, 2(4), 2000, pp. 737-740
Visible emission (500-850 nm) from electronically-excited ClF(B) and BrF(B)
can be generated chemically in the gas-phase reactions of atomic and molec
ular fluorine with PCl3 and PBr3, respectively, at pressures < 5 mbar. The
vibrational distributions of the excited products are effectively relaxed a
t these pressures. It is concluded that the excited states are produced by
three-body recombination of the appropriate halogen atoms in the case of th
e atomic fluorine reactions whilst a direct reaction may produce the chemil
uminescent products for the molecular fluorine reactions. Ultraviolet emiss
ion (270-400 nm) from the ion-pair states of molecular bromine is observed
from the reaction of atomic fluorine with PBr3 but there is no analogous ch
lorine emission in the case of the F + PCl3 reaction.