Synergistic extraction behavior of samarium(III), europium(III) and dysprosium(III) with 1-nitroso-2-naphthol and 1,10-phenanthroline

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 and^165mDy, 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.