Photoluminescence studies on the complexation of Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitrate medium

Abstract

UREX process has been proposed for selective extraction of U(VI) and Tc(VII) from nitric acid medium (∼1M HNO3) using tri-n-butyl phosphate (TBP) as extractant and retaining Pu, Np and fission products in the aqueous phase. The feasibility of the use of luminescence spectroscopy as a technique to understand the complexation of trivalent f-elements cations viz. Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitric acid medium has been examined. The luminescence lifetimes for the 1×10−3M Eu(III) and AHA complex system decreased with increased AHA concentration from 116±0.2μs (no AHA) to 1.6±0.1μs (0.1M AHA) which was attributed to dynamic quenching. The corrected fluorescence intensities were used to calculate the stability constant (log K) for the formation of 1:1 Eu3+–AHA complex as 1.42±0.64 under the conditions of this study. By contrast, the Tb(III)–AHA system at pH 3 (HNO3) did not show any significant variation in the life times of the excited state (364±9μs) suggesting the absence of dynamic quenching. The spectral changes in Tb(III)–AHA system showed the formation of 1:1 complex (log K: 1.72±0.21). These studies suggest that the extent of AHA complexation with the rare earth elements will be insignificant as compared to tetravalent metal ions Pu(IV) and Np(IV) under UREX process conditions.