We report on new and much more precise cation-exchange data of element 104, rutherfordium (Rf), in the fluoride ion concentration [F−] range of 5.29×10−5−1.04×10−3 M. The result based on one-atom-at-a-time chemistry clearly demonstrates that the distribution coefficients (Kd) decrease with increasing [F−], suggesting successive fluoride complexation of Rf. The complexation of Rf is briefly discussed in terms of fully relativistic density functional calculation theory.
We have investigated the cation-exchange behavior of element 104, rutherfordium (Rf), together with its lighter group-4 homologs Zr and Hf, and the tetravalent pseudo-homolog Th in HF/HNO3 mixed solution. The results, obtained on a one-atom-at-a-time scale, demonstrate that distribution coefficients (Kd) of Rf in HF/0.10 M HNO3 decrease with increasing concentration of the fluoride ion [F−]. This resembles the behavior of the homologs, indicating the consecutive formation of fluorido complexes of Rf. We also measured the Kd values of Rf and the homologs as a function of the hydrogen ion concentration [H+] in the range of [F−] = 5.29 × 10−7–3.17 × 10−6 M. The log Kd values decrease linearly with an increase of log[H+] with slopes between −2.1 and −2.5. This indicates that these elements are likely to form the same chemical compounds: mixture of [MF]3+ and [MF2]2+ (M = Rf, Zr, Hf, and Th) in the studied solution. It is also ascertained that the fluorido complex formation of Rf is significantly weaker than that of Zr and Hf, but it is stronger than that of Th.
Eu(III) / Cm(III) / LiCl-(H 2 O + CH 3 OH) solution / Inner-sphere chloro complex / Anion exchange resin / Time-resolved laser-induced fluorescence spectroscopySummary. In anion exchange resin systems with LiClaqueous 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 H 2 O ), i.e., the number of water molecules in the first coordination sphere of M(III) and from peak area ratio (in emission spectrum of Eu(III), which reflects the ligand environment both in the inner-and outer-spheres of Eu(III). The N H 2 O 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 H 2 O 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 H 2 O . The sorption equilibrium of M(III) was discussed by comparing the extent of the chloro complexation with the distribution coefficient.
The backward solvent extraction with dithizone-carbon tetrachloride solutions was used to examine the chemical species of Bi(III). A tracer concentration of Bi(III) (<10−7 mol dm−3) was found to exist in the form of Bi3+, Bi(OH)2+, Bi(OH)2+, and Bi(OH)3 in 1.0 mol dm−3 (H,Na)ClO4, and Bi(NO3)n3−n, Bi(OH)(NO3)n2−n, Bi(OH)2(NO3)n1−n, and Bi(OH)3(NO3)nn− in 1.0 mol dm−3 (H,Na)NO3 solutions depending on the acidity of the solutions. The constants of successive hydrolysis, β1, β2, and β3, were calculated by using the distribution data. The resulting logβ1, logβ2, and logβ3 values were 12.0, 22.9, and 33.9 for 1.0 mol dm−3 (H,Na)ClO4 solution, and 11.9, 22.7, and 33.2 for 1.0 mol dm−3 (H,Na)NO3 solution, respectively. The chemical composition of the extracted species was most probably Bi(HDz)3.
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