THE EFFECTS OF COMPLEX FORMATION ON THE DEACTIVATION OF ELECTRONICALLY EXCITED URANYL IONS

The dependence of the luminescence decay of electronically excited uranyl ions on the concentrations of uranium and sulphate in aqueous solution has been investigated with a pulsed nitrogen laser as a light source and a programmable transient recorder for lifetime measurements. Single exponential decay of the Luminescence is observed. The deactivation process of the excited uranyl ions should include radiative, nonradiative, water quenching and uranium self quenching and the measured luminescenec lifetime indicates the result of all these processes. The Luminescence lifetime of uranyl ions increases with increasing concentration of sulphate and becomes constant when the equilibrium concentration of sulphate reaches 3.0 mol.L-1. The dependence of the Luminesence lifetime is similar to that of the UO2(SO4)(3)(4-) formation. This phenomenon can be interpreted in terms of the fact that in aqueous solution uranyl ions exist as aquo-uranyl ions. As the concentration of sulpahte increaes the water molecule of hydrated uranyl ions will be replaced by sulphate ions via complex formation, and the quenching of excited uranyl ions by water is reduced. The self quenccing and the water quenching rate constants of UO2(H2O)(6)(2+) and UO2(SO4)(3)(4-) are estimated. Based on the experimental results a model for the deactivation mechanism of excited uranyl ions in sulphate solution is proposed.