RESUMO
Separation of Am3+ and Cm3+ is one of the most challenging yet unavoidable steps in the back end of the nuclear cycle. Various ligands evaluated for Am/Cm separation have their own merits and demerits, and not a single ligand has been uniquely proposed for this purpose. In the present work, we evaluated N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) vis-à-vis N,N,N',N'-tetra-2-ethylhexyldiglycolamide (T2EHDGA) in combination with a hydrophilic 2,6-bis(1,2,4-triazinyl)pyridine (SO3PhBTP) derivative in the aqueous phase for the separation of Am3+ and Cm3+ from nitric acid medium. The results showed that marginal selectivity for Am3+ over Cm3+ was observed with T2EHDGA in the presence of SO3PhBTP, which was attributed to the difference in the entropy change for their extraction from both the temperature-dependent liquid-liquid extraction and computational studies.
RESUMO
Crown ethers dissolved in suitable medium are well known to promote the extraction of alkali (M(+)) and alkaline-earth (M(2+)) cations from aqueous to organic phases. Di-tert-butyl-cyclohexano18crown6 (DTBDCH18C6) has been identified as an effective and selective extractant for Sr(II) from nitric acid medium. An attempt was made to evaluate the feasibility of (85,89)Sr recovery from synthetic soil samples (0.5 g; particle size: <100 µm) by SFE route (pressure: 200 kg/cm(2); T: 40 °C) employing DTBDCH18C6 dissolved in methanol/nitric acid medium as phase modifier. The effect of various experimental parameters such as (i) dynamic/static mode of extraction, (ii) time of equilibration (15-150 min during static mode of extraction using 3 mL of modifier), (iii) nitric acid concentration (1-6M), (iv) picrate as counter-anion, and (v) crown ether concentration in the modifier phase (2×10(-4)-2×10(-3) M) on Sr(II) extraction was studied. Based on these studies, 2×10(-4) M DTBDCH18C6 dissolved in methanol/4M HNO(3) was chosen as modifier and 30 min as equilibration time for batch mode employing 3 mL modifier solution in the static mode. Three successive batches employing 3 mL modifier solution (after each extraction stage) showed near quantitative recovery (>95%) of (85,89)Sr from soil samples. Dynamic mode extraction using 2×10(-4) M DTBDCH18C6 dissolved in methanol/4M HNO(3) as modifier suggested that near quantitative recovery (>95%) of (85,89)Sr could be achieved within 1h. By contrast, ~10% (137)Cs extraction was observed from soil samples under identical experimental conditions. These studies demonstrate the potential of the SFE technique for the analysis of (90)Sr in different environmental samples.