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The bulk extraction of Nd(III) from 4 M nitric acid medium was studied in a solution of N,N-di-octyl-2-hydroxyacetamide (DOHyA) in n-dodecane as a function of γ absorbed dose up to 750 kGy. The average size of reverse micellar aggregates in the irradiated and un-irradiated DOHyA samples after the extraction of Nd(III) was measured by dynamic light scattering (DLS) spectroscopy. The effect of absorbed dose of γ radiation and concentration of Nd(III) in the organic phase on the aggregation behavior of DOHyA was investigated by DLS measurements and ATR-FTIR spectroscopy. The data on irradiated and un-irradiated samples were compared. FT-IR analysis of the irradiated samples of DOHyA showed the formation of degradation products which were mainly identified as hydroxyacetic acid and primary or secondary amines. [ABSTRACT FROM AUTHOR]

A new ammonium-based task-specific ionic liquid, N,N-dioctyl-(4-trihexylammonium)butyramide bis(trifluoromethanesulfonyl)imide ([AmDOA][NTf2]), was synthesized and characterized by elemental analysis, and Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FTIR) spectroscopies. The extraction behavior of Pu(IV), U(VI), and Am(III) from nitric acid medium was studied in a solution of [AmDOA][NTf2] in an ionic liquid diluent, methyltributylammonium bis(trifluoromethanesulfonyl)imide ([N1444][NTf2]). The distribution ratio of actinides obtained in [AmDOA][NTf2]/[N1444][NTf2] was compared with other task-specific ionic liquids. The extraction stoichiometry of Pu(IV) in ionic liquid phase was determined, and the conditions needed for the efficient recovery of Pu(IV) from the loaded organic phase were evaluated. The results of these studies are reported in this article. [ABSTRACT FROM AUTHOR]

Piperidinium nitrate (Pip − NO3) and pyrrolidinium nitrate (Pyr − NO3) functional groups were anchored on a poly(styrene-divinylbenzene) matrix and evaluated the resultant anion exchange resin for the extraction of plutonium from nitric acid medium. The distribution coefficient ( Kd, mL/g) of Pu(IV) in these resins increased with the concentration of nitric acid, reaching a maximum Kd at 7 M nitric acid, followed by decrease. The extraction of Pu(IV) increased with the duration of equilibration followed by the establishment of equilibrium, occurred within four hours of equilibration. The kinetic data were fitted with pseudo-first order and pseudo-second order rate equations. The apparent plutonium exchange capacity was determined to be ∼256 mg/g for Pip − NO3 resin and 285 mg/g for Pyr − NO3 resin at 7 M nitric acid. The radiolytic degradation of Pip − NO3 and Pyr − NO3 in presence of nitric acid (7 M) was studied upto a dose of 200 KGy and the results are reported in this paper. [ABSTRACT FROM AUTHOR]

Liquid-liquid extraction of U(VI) from nitric acid medium was carried out using three different class of CHON based molecular extractants namely monoamide, malonamide, and diglycolamide present in 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide ([C4mpip][NTf2]) ionic liquid. The extractants investigated were di-n-hexyloctanamide (DHOA),N,N-dimethyl-N,N-di-octyl-2-(2-hexyloxylethyl)malonamide (DMDOHEMA) andN,N,N’,N’-tetra(ethylhexyl)diglycolamides (T2EHDGA). The extraction behavior of uranium(VI) in ionic liquid medium was investigated as a function of various parameters, such as the duration and temperature of equilibration, aqueous phase concentrations of feed acid, extractant, NaNO3, and ionic liquid cation, etc. The extraction of U(VI) observed in these systems were compared with each other and the distribution ratios of U(VI) decreased in the order T2EHDGA > DMDOHEMA > DHOA. The slope analysis of the extraction data was carried out to understand the mechanistic aspects of extraction. The extraction of U(VI) observed in [C4mpip][NTf2] ionic liquid was also compared with pyrrolidinium ([C4mpyr][NTf2]) and imidazolium ([C4mim][NTf2]) based ionic liquids under identical experimental condition. [ABSTRACT FROM PUBLISHER]

Extraction of Am(III) from nitric acid medium was carried out in a solution of benzoylpyrazolone (HPMBP) dissolved in 1-butyl-1-methylpyrrolidinium bis(trifluoro-methanesulfonyl)imide ([C4mpyr][NTf2]) ionic liquid. The extraction behavior of Am(III) in ionic liquid phase was investigated as a function of various parameters, such as pH of aqueous phase, duration of equilibration, and concentration of ionic liquid and nitrate in aqueous phase. Appreciable extraction was obtained at low pH medium (< pH 2) unlike other diketone based extractant. Extraction of Am(III) in ionic liquid was compared with that observed in a molecular diluent,n-dodecane (n-DD) under similar experimental condition. Remarkably high distribution ratio was observed in IL medium as compared ton-DD medium. The slope analysis of the extraction data was carried out to evaluate the mechanistic aspects of extraction. Extraction mechanism was different from conventional molecular diluent. Recovery of americium from the loaded ionic liquid phase was also studied using nitric acid. [ABSTRACT FROM AUTHOR]

Iron oxide (Fe3O4) particles functionalized with diglycolamic acid (Fe-DGAH) were synthesized and characterized by TG-DTA, X-Ray diffraction,1H NMR, and scanning electron microscopy (SEM). The extraction behavior of Am(III) and Eu(III) in Fe-DGAH was studied from dilute nitric acid medium to examine the feasibility for the mutual separation of trivalent actinides and lanthanides using Fe-DGAH. For this purpose, the effect of various parameters such as the duration of equilibration and concentrations of europium, nitric acid, and diethylenetriaminepentaacetic acid (DTPA) in the aqueous phase on the distribution ratio (Kd) of Am(III) and Eu(III) was studied. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized using DTPA. The distribution ratio of ˜104mL/g was obtained for both Am(III) and Eu(III) at pH 3, and it decreased with an increase in the concentration of nitric acid. However, a separation factor of Eu(III) over Am(III) of ˜150 was achieved in the presence of DTPA. Rapid sorption of metal ions in the initial stages of equilibration followed by the establishment of equilibrium occurred within 2 h. The sorption data were fitted to the Langmuir adsorption model, and the apparent europium sorption capacity was determined to be ˜50 mg/g. The study indicated the feasibility of using Fe-DGAH particles for magnetic separation of Eu(III) from Am(III) with high separation factors. [ABSTRACT FROM AUTHOR]

Partitioning of trivalent americium from fast-reactor (FR) simulated high-level liquid waste (SHLLW) has been demonstrated, for the first time, using a modifier-free organic phase containing an unsymmetrical diglycolamide, N, N,-didodecyl- N′, N′-dioctyl-3-oxapentane-1,5-diamide (D3DODGA), in n-dodecane ( n-DD). The extraction behavior of various metal ions present in the FR-SHLLW that contained about 3.2 g/L of trivalent metal ions (Am(III) and Ln(III)) was studied using a solution of 0.1 M D3DODGA/ n-DD, by batch equilibration mode. The extraction of Am(III) was accompanied by the co-extraction of all lanthanides and unwanted metal ions such as Zr(IV), Y(III), and Pd(II) from FR-SHLLW. The co-extraction of unwanted metal ions was minimized by adding a suitable aqueous soluble complexing agents to FR-SHLLW, prior to extraction. As a result, trans-1,2-diaminocyclohexane- N,N,N′N′-tetraacetic acid (CyDTA) was identified as an appropriate reagent for preventing the extraction of zirconium and palladium, that posed problems during recovery of trivalent metal ions from the loaded organic phase. The stripping of behavior of Am(III) and Ln(III) from the loaded organic phase was studied using dilute nitric acid in batch equilibration mode. Based on those results, a counter-current mixer-settler run was performed in a 20-stage mixer-settler. About 99.9% of Am(III), Ln(III) and Y(III) from FR-SHLLW in 0.1 M D3DODGA/ n-DD was achieved in 20 contacts and the recovery of Am(III) and other trivalents from the loaded organic phase was achieved in 5 contacts using 0.01 M nitric acid. The study demonstrated the possibility of using the modifier-free reagent, D3DODGA, for the separation of trivalent actinides from FR-SHLLW. [ABSTRACT FROM AUTHOR]

The extraction and stripping behavior of various metal ions present in the fast reactor simulated high-level liquid waste (FR-SHLLW) was studied using a solvent phase composed of a neutral extractant, N, N,-didodecyl- N′, N′-dioctyl-3-oxapentane-1,5-diamide (D3DODGA) and an acidic extractant, di-2-ethylhexyl diglycolamic acid (HDEHDGA) in n-dodecane ( n-DD). The third phase formation behavior of the solvent formulation D3DODGA + HDEHDGA/ n-DD, was studied when it was contacted with FR-SHLLW, and the concentration of neutral and acidic extractant needed to avoid the third phase formation was optimized. The distribution ratio of various metal ions present in FR-SHLLW was measured in a solution of 0.1 M D3DODGA + 0.2 M HDEHDGA/ n-DD. The extraction of Am(III) was accompanied by the co-extraction of lanthanides and unwanted metal ions such as Zr(IV), Y(III), and Pd(II). A procedure was developed to minimize the extraction of unwanted metal ions by using aqueous soluble complexing agents in FR-SHLLW. Based on those results, the counter-current mixer-settler run was performed in a 20-stage mixer-settler. Quantitative extraction of Am(III), Ln(III), Y(III), and Sr(II) in 0.1 M D3DODGA + 0.2 M HDEHDGA/ n-DD was observed. The recovery of Am(III) from the loaded organic phase was carried out by the optimized aqueous formulation composed of 0.01 M diethylenetriaminepentaacetic acid (DTPA) + 0.5 M citric acid (CA) at pH 1.5. The stripping of Am(III) was accompanied by co-stripping of some early lanthanides. However the later lanthanides (Eu(III) and beyond) were not back extracted to Am(III) product. Therefore, the studies foresee the possibility of intra-lanthanides as well as lanthanide-actinide separation in a single-processing cycle. [ABSTRACT FROM AUTHOR]

The organic solvent phase composed ofN,N,N’,N’-tetra-2-ethylhexyl diglycolamide (TEHDGA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) inn-dodecane (n-DD) is regarded as a promising candidate for single-cycle separation of americium (III) from high-level liquid waste. The radiochemical degradation of a solution of TEHDGA + HDEHP/n-DD was investigated by irradiating the solvent to various absorbed dose levels ofγ-radiation. The neat extractants or a solution of extractants inn-dodecane were irradiated in the presence and absence of nitric acid. The degree of degradation was assessed by measuring the variation in the extraction behavior of Am(III), Eu(III) and other metal ions in irradiated solvent systems. The distribution ratio of americium and europium decreased with increase of absorbed dose. The presence ofn-dodecane enhanced the radiolytic degradation of the solvent; however, the role of nitric acid during degradation was insignificant. The recovery of Am(III) and Eu(III) from the irradiated solvent system was studied. The recovery of Am(III) was quantitative in 3 contacts; however, the separation factor of Eu(III) over Am(III) during stripping decreased marginally with increase of absorbed dose. [ABSTRACT FROM PUBLISHER]

A novel 2-oxy-N,N-dioctylacetamide anchored on Merrifield resin was synthesized and characterized by elemental analysis, TG-DTA and IR spectroscopy, for the first time. The extraction behavior of Am(III) and Eu(III) from nitric acid medium in the dioctylacetamide anchored resin (R-DOA) was studied as a function of various parameters such as duration of equilibration, concentration of nitric acid and sodium nitrate etc. The distribution coefficient ( Kd) of Am(III) and Eu(III) in R-DOA increased with increase in concentration of nitric acid. The Kd values reached a maximum at 3-4 M nitric acid concentration in both cases, followed by decrease in Kd values. Rapid extraction of Am(III) and Eu(III) from nitric acid medium was observed in the initial stages of equilibration followed by the establishment of equilibrium occurred within 60 min. The extraction data was fitted in to the first order rate equation. The recovery of Am(III) and Eu(III) from the loaded organic phase was studied using dilute nitric acid. The results revealed that 2-oxyacetamide functionalized resin is the promising candidate for the separation of trivalent actinides and lanthanides from nitric acid medium. [ABSTRACT FROM AUTHOR]

The extraction behavior of palladium in a solution of tri-n-octylmethylammonium nitrate (TOMAN) and 1,3-diisopropyl benzene (DIPB) in presence of tri-n-butyl phosphate as phase modifier was studied. The distribution ratio of palladium (D) increased with increase in the concentration of nitric acid, reached a maximum at 1 M in nitric acid, followed by decrease in D values. The cyclic voltammogram of the palladium in extracted organic phase (0.5 M TOMAN + 0.1 M TBP/DIPB) showed a surge in cathode current at −0.5 V was due to the palladium deposition. The results confirmed the feasibility of using the organic phase for electrodeposition of palladium directly from extracted phase. [ABSTRACT FROM AUTHOR]

The extraction behavior of Am(III) in a solution of tetra-(2-ethylhexyl)diglycolamide (TEHDGA) inn−dodecane (n−DD) or toluene was studied as a function of nitric acid concentration. The distribution ratio of Am(III) in 0.1 M TEHDGA/molecular diluent increased with increase in the concentration of nitric acid. Since the Aliquat-336 based ionic liquid namely, tri-n-octylmethylammonium di-(2-ethylhexyl)phosphate ([A336]+[DEHP]−) was miscible in molecular diluents such asn-DD and toluene, the extraction behavior of Am(III) in TEHDGA/molecular diluent was investigated in the presence of small concentrations of ionic liquid to understand the role of ionic liquid in extraction. The distribution ratio of Am(III) in 0.2 M [A336]+[DEHP]−/molecular diluent was negligible. Significant increase in distribution ratio of Am(III) was observed when [A336]+[DEHP]−was added to 0.1 M TEHDGA/molecular diluent. Since [A336]+[DEHP]−was converted into its components, namely tri-n-octylmethylammonium nitrate ([A336]+[NO3]−) and di-(2-ethylhexyl)phosphoric acid (HDEHP) when contacted with nitric acid, the extraction behavior of Am(III) in 0.1 M TEHDGA/molecular diluents was also studied in the presence of [A336]+[NO3]−and HDEHP to elucidate the mechanism of extraction. The study confirmed that the extraction of Am(III) in ionic liquid medium was controlled by constituents of ionic liquid and the distribution ratio of Am(III) obtained in organic phase was due to the resultant of contributions of ionic liquid constituents. [ABSTRACT FROM PUBLISHER]

The unsymmetrical diglycolamide, di-dodecyl-di-octyl diglycolamide (D3DODGA) is a modifier-free extractant proposed for partitioning of trivalent actinides from nitric acid medium. D3DODGA has been evaluated for the feasibility of using it in the absence of a phase modifier, for the partitioning of minor actinides from fast reactor high-level liquid waste (FR-HLLW). The extraction behavior of various metal ions present in the simulated FR-HLLW was studied in a solution of 0.1 M D3DODGA/n-dodecane from nitric acid medium. The distribution ratio of about 20 metal ions was measured as a function of concentration of nitric acid and other interfering ion. The extraction was found to be strongly dependent on the oxidation state of the metal ion. The extraction of Am(III) from 3–4 M nitric acid medium was quantitative in a single contact. However, it was accompanied by the quantitative extraction of fission products such as trivalent lanthanides (Ln(III)), Y(III), and Zr(IV). The extraction of Sr(II), Pd(II), and Ru(III) in 0.1 M D3DODGA/n-dodecane was not insignificant, but quite low. The extraction of Ba(II), Ni(II), Mo(VI), and Fe(III) was marginal and the extraction of Co(II), Sb(III), Mn(II), and Cs(I) in 0.1 M D3DODGA/n-dodecane was negligible. Our results indicated that 0.1 M D3DODGA/n-dodecane is a promising candidate for the separation of trivalent actinides from fast reactor high-level liquid waste containing significant quantities of trivalent lanthanides and actinides. [ABSTRACT FROM PUBLISHER]

A new approach, namely 'Single-cycle method for partitioning of Minor Actinides using completely incinerable ReagenTs' (SMART), has been explored for the separation of Am(III) from Eu(III) present in nitric acid medium. The extraction behavior of Am(III) and Eu(III) in a solution of an unsymmetrical diglycolamide, N, N,-didodecyl- N′, N′-dioctyl-3-oxapentane-1,5-diamide (D3DODGA), and an acidic extractant, N, N-di-2-ethylhexyl diglycolamic acid (HDEHDGA), in n-dodecane was studied. The distribution ratio of both these metal ions in D3DODGA-HDEHDGA/ n-dodecane initially decreased with increase in the concentration of nitric acid reached a minimum at 0.1 M nitric acid followed by increase. Synergic extraction of Am(III) and Eu(III) was observed at nitric acid concentrations above 0.1 M and antagonism at lower acidities. Contrasting behavior observed at different acidities was probed by the slope analysis of the extraction data. The study revealed the involvement of both D3DODGA and HDEHDGA during synergism and increased participation of HDEHDGA during antagonism. The stripping behavior of Am(III) and Eu(III) from the loaded organic phase was studied as a function of nitric acid, DTPA, and citric acid concentrations. The conditions needed for the mutual separation of Am(III) and Eu(III) from the loaded organic phase were optimized. Our studies revealed the possibility of separating trivalent actinides from HLLW using these completely incinerable reagents. [ABSTRACT FROM AUTHOR]

The radiolytic degradation of N, N-di-dodecyl- N′, N′-di-2-ethylhexyl-3-oxapentane-1,5-diamide (DDEHDGA) was studied at various absorbed doses of γ-radiation. The degradation was assessed by measuring the variation in the extraction behavior of Am(III) in irradiated solvent systems composed of neat DDEHDGA or 0.1 M DDEHDGA/ n-dodecane in the presence and absence of nitric acid. The distribution ratio of americium ( D) decreased with increase of absorbed dose. The presence of n-dodecane and nitric acid enhanced the radiolytic degradation of the solvent. The third phase formation behavior of Nd(III) decreased with increase of absorbed dose and the third phase was not observed at absorbed doses above 100 kGy. The recovery of Am(III) from the irradiated system was near quantitative in five contacts. The study revealed that the extraction and stripping behavior of the irradiated solvent was quite satisfactory for partitioning of minor actinides from real wastes. [ABSTRACT FROM AUTHOR]

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-octyldiglycolamide (TODGA), bis(2-ethylhexyl)phosphoric acid (HDEHP), andn-dodecane (n-DD) was studied to understand the role of TODGA and HDEHP in the combined solvent system. The extraction behavior of these metal ions was compared with those observed in TODGA/n-DD and HDEHP/n-DD. The effect of various parameters such as concentrations of HNO3, TODGA, and HDEHP on the distribution ratio of Am(III) and Eu(III) was studied. Synergistic extraction of both the metal ions observed at lower acidities (<2.0 M) was attributed to the involvement of TODGA and HDEHP for extraction. However, the extraction of Am(III) and Eu(III) in the combined solvent was comparable with that observed in TODGA at higher acidities. The slope analysis of the extraction data confirmed the involvement of both the extractants at all acidities investigated in the present study. [ABSTRACT FROM AUTHOR]

Thermal stability of neat octyl(phenyl)- N, N-diisobutylcarbamoylmethylphosphine oxide (OΦD[IB]CMPO) and TRUEX solvent composition (0.2M OΦD[IB]CMPO-1.2M tri n-butyl phosphate-in n-dodecane) in the presence and absence of nitric acid has been studied in ambient air in a closed vessel, employing an adiabatic calorimeter. Enthalpies and kinetic parameters for the decomposition reaction were derived wherever possible and are reported for the first time. Neat OΦD[IB]CMPO was found to be thermally stable up to 633 K and exhibited an exothermic decomposition later. It decomposed at lower temperatures (376-386 K) depending on the nitric acid concentration. The exothermic rise in temperature and pressure increased exponentially, while activation energies exhibited exponential decrease for the decomposition reactions with increase in nitric acid content. TRUEX solvent was found to be stable up to 661 K in the absence of nitric acid while in the presence of 8 and 4M HNO, it decomposed between 387 and 413 K. All these samples on decomposition formed incompressible gases and viscous black liquids. The results also indicate that the neat OΦD[IB]CMPO and the TRUEX solvent are thermally more stable than neat tri n-butyl phosphate (TBP), PUREX solvent (1.1M TBP/ n-DD), neat diamyl amyl phosphonate (DAAP) and 1.1M DAAP/ n-DD, triisoamyl phosphate (TiAP) and 1.1M TiAP/ n-DD. [ABSTRACT FROM AUTHOR]

The extraction behavior of Eu(III) and Am(III) in a solution of bis(2-ethylhexyl)diglycolamic acid (HDEHDGA) in n-dodecane (n-DD) from citric acid (CA) medium was studied as a function of various parameters. The extraction increased with increase of pH, reached a maximum at pH 2 followed by decrease. The stripping behavior of Eu(III) and Am(III) from the loaded organic phase was studied by using a solution of diethylenetriaminepentaacetic acid (DTPA) and CA. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized. Based on the optimized conditions, the feasibility of separating Am(III) from Eu(III) present in CA feed solution was investigated in a 20- stage mixer-settler. Quantitative extraction of Eu(III) and Am(III) in 0.1 M HDEHDGA/n-DD was achieved in 3–4 stages, whereas the selective back extraction of Am(III) was achieved in ∼20 stages upon contacting the loaded organic phase with a stripping formulation composed of DTPA-CA at pH 1.5. The results confirmed the possibility of using diglycolamic acid for the separation of trivalent actinides from the chemically similar lanthanides, which is indeed necessary for transmutation of minor actinides present in high-level liquid waste (HLLW). [ABSTRACT FROM AUTHOR]

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-bis(2-ethylhexyl)diglycolamide (TEHDGA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) in n-dodecane (n-DD) was studied from nitric acid medium. The distribution ratio of Am(III) and Eu(III) in TEHDGA-HDEHP/n-DD was measured as a function of various parameters such as concentrations of nitric acid, TEHDGA, HDEHP, and nitrate ion. The data were compared with those obtained in individual solvents namely 0.1 M TEHDGA/n-DD and 0.25 M HDEHP/n-DD. The synergistic extraction of Am(III) and Eu(III) observed in a solution of 0.1 M TEHDGA – 0.25 M HDEHP/n-DD was attributed to the involvement of both TEHDGA and HDEHP for extraction. Slope analysis of the extraction data indicated the predominant participation of HDEHP for extraction at low acidities and TEHDGA and nitrate ion at higher acidity. The stripping behavior of Am(III) and Eu(III) from the extracted organic phase was investigated using citric acid (CA) and diethylenetriaminepentaacetic acid (DTPA). A suitable aqueous formulation was developed to separate Am(III) alone from chemically similar Eu(III) present in loaded organic phase, to facilitate a single-step separation of trivalent actinides from the high-level liquid waste (HLLW). [ABSTRACT FROM AUTHOR]

Extraction of europium(III) from nitric acid medium by a solution of tri- n-butylphosphate (TBP) and n-octyl(phenyl)- N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in the room temperature ionic liquid, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (amimNTf where a = butyl or hexyl or octyl), was studied. The distribution ratio of Eu(III) in TBP-CMPO/bmimNTf was measured as a function of various parameters such as the concentrations of nitric acid, CMPO and NaNO. Remarkably large distribution ratios were observed for the extraction of europium(III) when bmimNTf acted as diluent. The stoichiometry of metal-solvate in organic phase was determined by the slope analysis of extraction data. [ABSTRACT FROM AUTHOR]

Room temperature ionic liquids (RTILs) containing β-diketonate anions have been prepared and studied for the extraction of 239Pu(IV), 233U(VI), and 241Am(III) from nitric acid medium. The ionic liquids such as alkylquaternaryammonium thenoyltrifluoroacetonate (R4NTTA), and 1-alkyl-3-methylimidazolium thenoyltrifluoroacetonate (amimTTA), with methyl, butyl, hexyl, heptyl, and octyl moieties have been prepared and characterized by 1H and 13C nmr and IR spectroscopy. The distribution ratio of plutonium(IV) (DPu(IV)) in a solution of tri-n-octylmethylammonium thenoyltrifluoroacetonate (TOMATTA) present in tri-n-octylmethylammonium bis(trifluoromethylsulfonyl)imide (TOMANTf2) and amimTTA in amimNTf2 was studied as a function of various parameters. The unique property of β-diketonate ionic liquids, namely, the miscibility in molecular diluents, was exploited to elucidate the mechanism of Pu(IV) extraction in these ionic liquids. [ABSTRACT FROM AUTHOR]

A new unsymmetrical diglycolamide, N,N-di-2-ethylhexyl-N',N'-di-octyl-3-oxapentane-1,5-diamide, trivially known as di-ethylhexyl-di-octyl-diglycolamide (DEHDODGA) has been synthesized, and characterized by 1H, and 13C nmr, mass, and IR spectroscopy. Extraction behavior of 241Am(III), (152+154)Eu(III), 239Pu(III), 239Pu(IV), 233U(VI), 137Cs(I), and (85+89)Sr(II) from nitric acid medium by a solution of DEHDODGA in n-dodecane was studied, at 298-333 K. The effect of concentrations of HNO3 and DEHDODGA and of temperature on the distribution ratio (DM) was studied. Extraction of Eu(III), Am(III), Pu(III), and Pu(IV) increased with increase in nitric acid concentration, and the distribution ratio of Cs(I) was insignificant. However, the distribution ratios of U(VI) and Sr(II), though not insignificant, but was quite less compared to trivalents, and Pu(IV). The DSr(II) increased with increase in the concentration of nitric acid, reaching a maximum at 4 M followed by decrease. The stoichiometry of Am(III) - DEHDODGA was determined by slope analysis of extraction data, and the enthalpy change accompanied by the extraction of Eu(III), Pu(III), and Am(III) was determined and reported in this article. [ABSTRACT FROM AUTHOR]

Extraction–electrodeposition (EX–EL) process has been developed for the quantitative recovery of palladium from nitric acid medium and fast reactor-simulated high-level liquid waste (FR-S-HLLW). The process exploits some characteristic properties of room temperature ionic liquid, tri- n-octylmethylammonium nitrate (TOMAN), for quantitative and favorable recovery of palladium. Extraction of palladium (II) from FR-S-HLLW and nitric acid medium by a solution of 0.5 M TOMAN in chloroform has been studied in detail. More than 60% of palladium was extracted in a single contact of equal volumes of organic and aqueous phases and nearly five contacts were required for quantitative extraction. The electrochemical behavior of palladium (II) present in the organic phase was investigated at stainless steel electrode by cyclic voltammetry. A surge in cathodic current occurring at a potential of –0.5 V (vs. Pd) was due to the reduction of palladium (II) to palladium (0). The kinetics of electrodeposition was followed by the UV–VIS absorption spectrum of palladium present in organic phase and under the given conditions nearly 20 and 35 h were required for the quantitative deposition of palladium from organic phase, which was obtained after extraction of palladium from 4 M nitric acid and FR-S-HLLW, respectively. Decontamination of palladium from other fission products during extraction and electrodeposition was studied and the results are reported in this article. [ABSTRACT FROM AUTHOR]

Commercially available polystyrene-divinylbenzene (PS-DVB) resins functionalized with isothiouronium (Tulsion CH-95), phosphinic acid (Tulsion CH-96) and methylene thiol (Tulsion CH-97) moieties have been used for separating palladium from nitric acid medium. Extraction of palladium has been studied as a function of time, concentration of nitric acid and palladium. The distribution coefficients ( K d, ml/g) of palladium on sulfur based resins (Tulsion CH-95 and Tulsion CH-97) are higher (5000-104ml/g in 0.1M nitric acid) than on Tulsion CH-96 resin and decrease with increasing concentration of nitric acid. The initial rate of extraction of palladium by Tulsion CH-95 and Tulsion CH-97 resins was very rapid and the time required for the establishment of equilibrium was a function of palladium concentration in the aqueous phase. The rate data could be fitted by a second order rate equation and the magnitude of rate constant for the extraction of palladium by these resins (~102M-1. min-1) decreased in the order of: Tulsion CH-95 > Tulsion CH-97 > Tulsion CH-96. The extraction isotherms of Tulsion CH-95 were fitted by Langmuir adsorption model and the coefficients were obtained by regression. The extraction capacity of palladium on Tulsion CH-95 was found to be ~20 mg/g at 3M nitric acid. Column experiments have been conducted and the data were fitted using Thomas model. A column utilization of 75% was achieved for the extraction of palladium by Tulsion CH-95 resin. [ABSTRACT FROM AUTHOR]

A systematic study on the extraction of U(VI) from nitric acid medium by tri-n-butylphosphate (TBP) dissolved in a non-traditional diluent namely 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) ionic liquid (IL) is reported. The results are compared with those obtained using TBP/n-dodecane (DD). The distribution ratio for the extraction of U(VI) from nitric acid by 1.1M TBP/bmimPF6 increases with increasing nitric acid concentration. The U(VI) distribution ratios are comparable in the nitric acid concentration range of 0.01M to 4M, to the ratios measured using 1.1M TBP/DD. In contrast to the extraction behavior of TBP/DD, the D values continued to increase with the increase in the concentration of nitric acid above 4.0M. The stoichiometry of uranyl solvate extracted by 1.1M TBP/IL is similar to that of TBP/DD system, wherein two molecules of TBP are associated with one molecule of uranyl nitrate in the organic phase. Ionic liquid alone also extracts uranium from nitric acid, albeit to a small extent. The exothermic enthalpy accompanying the extraction of U(VI) in TBP/bmimPF6 decreases with increasing nitric acid and with TBP concentrations. [ABSTRACT FROM AUTHOR]

Organic complexing moieties such as amine, 2°-amide and benzamide functional groups were covalently linked to silica gel by performing organomodification on commercially available silica gel. The extraction of uranium as a function of pH, time, concentration of uranium and the effect of ions such as Fe2+, Co2+, Ni2+ and CO32- on the distribution coefficient of uranium by sorbent was studied. The data was fitted into Langmuir adsorption isotherm. The selectivity of the sorbents towards uranium were found to decrease in the order gel-amine >> gel-benzamide @ gel-2°-amide at all pHs. The presence of metal ions such as Fe2+, Co2+, Ni2+ and CO32- were found to decrease the distribution coefficients (Kd, ml/g) of uranium and the decrease was very high when Fe2+ was present. The performance of the sorbent, gel-amine, under a given column condition was tested by following the breakthrough curve of uranium up to C/C0 = 0.025. The sorbent was found to be good for the quantitative pre-concentration of uranium from a large amount of sodium. [ABSTRACT FROM AUTHOR]