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In anion exchange resin systems with LiCl-aqueous and LiCl-(H 2 O + CH 3 OH) solutions, the extent of chloro complexation of M(III) (M = Eu, Cm) was estimated from inner-sphere hydration number ( N  H2O ),  i.e. , the number of water molecules in the first coordination sphere of M(III) and from peak area ratio ( A  2 / A  1 ) of  5  D  0  →  7  F  2  transition ( A  2 ) to  5  D  0  →  7  F  1  transition ( A  1 ) in emission spectrum of Eu(III), which reflects the ligand environment both in the inner- and outer-spheres of Eu(III). The  N  H2O  of M(III) both in the solution and resin phases decreased with an increase of LiCl and CH 3 OH concentrations, indicating the formation of an inner-sphere M(III)-chloro complex. From the comparison of  N  H2O  between the both phases, it was found that the extent of the inner-sphere chloro complexation of M(III) in the resin phase is higher than that in the solution phase. The  A  2 / A  1  ratio in the both phases increased with an increase of interaction of Eu(III) with Cl − , which are well correlated with the results of  N  H2O . The sorption equilibrium of M(III) was discussed by comparing the extent of the chloro complexation with the distribution coefficient.

radiochimica acta

Direct evidence for enhanced inner-sphere chloro complexation of Eu(III) and Cm(III) in anion exchange resin phase studied by time-resolved laser-induced fluorescence spectroscopy