The equilibrium extraction behavior of Sm(III), Eu(III) and Dy(III) from aqueous NaClO4 solutions in the pH range of 4–9 at 0.1 M ionic strength into organic solutions of 1-nitroso-2-naphthol (HA) and 1,10-phenanthroline (Phen) has been studied. The equilibrium concentrations of Eu were assayed through the 344 keV photopeak of the152Eu radiotracer used. The concentrations of Sm and Dy were measured by irradiating one mL portions of the organic extract and analyzing the 104 and 108 keV photopeaks of the short-lived neutron activation products,155Sm and165mDy, respectively. Quantitative extraction of Eu with 5×10–2 M HA alone was obtained in the pH range of 6.7–7.8 with n-butanol, 7.4–8.5 with chloroform, 8.0–8.7 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.1–8.0 with methyl isobutyl ketone (MIBK). But, Eu was extracted only to a maximum of 78% and 83% in the pH range of 8.3–8.9 and 7.4–8.1 with carbon tetrachloride and xylene, respectively. The extraction of Sm and Dy were found quantitative in the pH range of 6.3–7.0 and 6.6–7.1, respectively, with 5×10–2 M HA alone in MIBK solutions. The synergistic extraction of Eu was quantitative in the pH range of 6.6–9.8 with chloroform, 7.8–8.9 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.0–9.6 with MIBK when 1×10–2 M each of HA and Phen were employed. Sm and Dy were quantitatively extracted into MIBK solutions containing 5×10–2 M each of HA and Phen in the pH range 6.0–7.5 and 6.1–7.5, respectively. The distribution ratios of these lanthanides (Ln) were determined as a function of pH, and HA and Phen concentrations. The analysis of the data suggests that these Ln are extracted as LnA3 chelates when HA alone is used. In the presence of HA and Phen, both LnA3(Phen) and LnA3(Phen)2 adducts are formed only in the MIBK system while LnA3(Phen) complexes are the predominant ones in all other solvent systems studied. The extraction constants and the adduct formation constants of these complexes have been calculated.
Solid-state Ln–C8H7O3 compounds, where Ln stands for Eu(III) and Gd(III) and C8H7O3 is 3-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential
scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, elemental analysis and complexometry were
used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition,
dehydration, thermal stability and decomposition of the isolated compounds.
Organic substances present in radioactive waste lower the sorption of metal ions at the high pH in cement matrices and, hence,
enhance their possible migration. The aim of this study was to develop a method to compare organic substances or their degradation
products with respect to what extent they affect metal sorption. Batch sorption studies were performed with cement or TiO2 as solid phase and Eu(III) as a model element for trivalent lanthanides and actinides at pH 12.5 (representative of a cement
waste matrix during the first approximately 100,000 years). Different kinds of ligands were studied in a broad concentration
range, e.g., organic acids, cement additives, cleaning agents and degradation products from ion-exchange resin.
Authors:T. Nishida, Z. Klencsár, E. Kuzmann, A. Vértes, and T. Tamaki
151Eu Mössbauer spectrum of IR-transmitting calcium aluminate glass, 60CaO·32Al2O3·5Fe2O3·3Eu2O3, consists of a broad peak due to distorted Eu(III) with and values of 0.91 and –2.02 mm·s–1, respectively. Debye temperatures (
D) of 360 and 320 K were obtained from the temperature dependence of absorption area (A) and that of , respectively. These
D values indicate that Eu(III) atoms occupy substitutional sites of distorted Al(III)O4 tetrahedra in calcium aluminate glass. The value of 0.62 mm/s obtained from the heat-treated sample (glass ceramic) indicates that Eu(III)-O bonds became less covalent. A smaller value of –1.20 mm·s–1 was obtained for Eu(III) in the glass ceramic, indicating less distorted Eu(III)O4 tetrahedra.
Temperature effect on the synergic extraction of Eu(III) by thenoyltrifluoroacetone (HTTA) in the presence of 2,2-bipyridyl(bipyr)
and 1,10-phenanthroline (phen) from sodium acetate buffer solution at pH 4.20 has been investigated. Extractions were carried
out at 15, 25, and 35°C. It was observed that the increasing temperature favours the extraction of Eu(III) by HTTA alone while
the reverse is true for synergic extractions. The extraction data indicate the formation of synergic adducts containing only
one molecule of the bidentate amine i.e. Eu(TTA)3. B where B=bipyr or phen. The synergic reaction is favoured by the enthalpy changes alone. Thermodynamic parameters suggest
a mechanism for the synergic extraction which involves complex formation with an increase or expansion of the coordination
number of the central metal atom. Larger synergic and enthalpy changes observed for phen as compared to bipyr are probably
due to the cis position of its N-atoms readily available for chelate ring formation.
The extraction of U(VI), Eu and Am by the aromatic main component (HA) of LIX 64N dissolved in toluene was studied at pH 3–9. The values of pH1/2 for the extraction with 0.146 M HA are 4.0, 5.5 and 5.2, and the pH's of maximum extraction are 6.0, 6.8, and 7.0 for U(VI), Eu and Am, respectively. The stoichiometry of the extracted chelates determined by the slope analysis is UO2A2 and MA3–nYn (n=1,2) for Eu and Am, the ligand Y being probably the nitrate anion. The addition of tri-n-octylphosphine oxide (TOPO) enhances the extraction of U(VI) and especially of Eu at pH<6. An Eu chelate species solvated by 2 TOPO molecules is extracted at pH 4 by the mixture of HA+TOPO, whereas the species extracted at pH 6.5 is not solvated by TOPO.
The extraction behavior of Sm(III), Eu(III) and Dy(III) with 1-nitroso-2-naphthol (HA) and trioctylphosphine oxide (TOPO) in methyl isobutyl ketone (MIBK) from aqueous NaClO4 solutions in the pH range 4–9 at 0.1M ionic strength has been studied. The equilibrium concentrations of Sm and Dy were measured using their short-lived neutron activation products,155Sm and165mDy, respectively. In the case of Eu, the concentrations were assayed through the152,154Eu radiotracer. The distribution ratios of these elements were determined as a function of pH, 1-nitroso-2-naphthol and TOPO concentrations. The extractions of Sm, Eu and Dy were found to be quantitative with MIBK solutions in the pH range 5.9–7.5, 5.6–7.5 and 5.8–7.5, respectively. Quantitative extraction of Eu was also obtained between pH 5.8 and 8.8 with chloroform solutions. The results show that these lanthanides (Ln) are extracted as LnA3 chelates with 1-nitroso-2-naphthol alone, and in the presence of TOPO as LnA3(TOPO) and LnA3(TOPO)2 adducts. The extraction constants and the adduct formation constants of these complexes have been calculated.
The following extraction systems have been studied: (Ce3++Eu3+) (NO3)-(EDTA, DCTA, DTPA)/TBP in n-alkane and (Ce3++Eu3+)(NO3)/DEHPA in n-alkane at concentration ratios as follows: [Ce3+]=trace –1 mol·dm–3, [Eu3+]=trace –0.1 mol·dm–3. [TBP]=(0.183–1.83) mol·dm–3, [DEHPA]=(5·10–3–0.1) mol·dm–3, [(H, Na)NO3]=(0.1–6) mol·dm–3, [Eu3+]: [EDTA, DCTA, DTPA]=11–110. The initial concentration of Eu3+ in aqueous phase in the extraction system containing a mixture of Ce3+ and Eu3+ was trace, 1% and 10% compared with the Ce3+ concentration. The distribution of the elements between the phases was observed radiometrically using141Ce,152Eu and154Eu. The results are documented by the distribution ratios DCe, DEu and separation factor =DEu/DCe as functions of variable parameters of the systems.
Authors:Emanuel Makrlík, P. Vaňura, and P. Selucký
From extraction experiments and γ-activity measurements, the extraction constants corresponding to the general equilibrium Eu3+(aq) + 3A−(aq) + L(nb) ⇔ EuL3+(nb) + 3A−(nb) taking part in the two-phase water–nitrobenzene system (A− = CF3SO3−; L = p-tert-butylcalixarene, p-tert-butylcalixarene; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Further, the stability constants of the
EuL3+ complexes in nitrobenzene saturated with water were calculated for a temperature of 25 °C as log βnb(EuL3+) = 6.4 ± 0.1 (L = p-tert-butylcalixarene) and log βnb(EuL3+) = 11.3 ± 0.1 (L = p-tert-butylcalixarene).
Synergic extraction of trivalent Eu, Gd and Am from aqueous perchlorate medium has been studied using mixtures of thenoyltrifluoroacetone (HTTA) and 15-crown-5 or 18-crown-6 (CE) in chloroform at (25±1) °C. Slope analysis of the extraction results indicated a general formula of M(TTA)3·(CE)2 for the extracted species. The stability order took the sequence Eu(TTA)3·(CE)2>Am(TTA)3)·(CE)2>>Gd(TTA)3·(CE)2 with 15C5 and Am(TTA)3·(CE)2>Eu(TTA)3·(CE)2>Gd(TTA)3·(CE)2 with 18C6. The synergic factors, extracton constants and formation constants of the extracted species were determined and discussed in terms of the correspondence between cavity size of the crown ethers and ionic crystal radii.