The effect of ionic activity on the quenching of the quinine dication fluor
escence by chloride and bromide ions is examined in solutions of sufficient
ly low ionic strength to enable ionic activities to be taken into account b
y means of the Debye-Huckel equation. An equation for the dependence of the
Stern-Volmer constant on the ionic strength is derived in a novel way and
an iterative, linear least-squares computer program is described from which
the optimized values of the ionic size parameter for chloride (a(Cl-) = 4.
56 +/- 0.07 Angstrom) and bromide (a(Br-) = 4.98 + 0.23 Angstrom) quenching
were obtained. The ratio of these parameters (a(Br-)/a(Cl-) = 1.09 +/- 0.0
7) is found to be similar to the ratio of the ionic radii of the two specie
s, r(Br-)/r(Cl-) = 1.08. The experimental results suggest that the quenchin
g of quinine fluorescence by bromide ions is about 28% faster than that obs
erved for chloride ions. The results are consistent with the notion that th
e quenching process is dynamic one involving the formation of an activated
complex whose rate of deactivation is dependent on the ionic strength of th
e medium. (C) 2000 John Wiley & Sons, Inc.