SOLVENT EXTRACTION OF SOME TERVALENT LANTHAN01DS WITH 5-BR0M0-, 3,5-DIBROMO- AND 5-NITROSALICYLALDEHYDE ACETOHYDRAZONES

ABSTRACT

5-Bromo-, 3,5-dibromo- and 5-nitrosalicylaldehyde acetohydrazones (BSAH, DBSAH and NSAH, respectively, or H₂L) were synthesized. The extraction of lanthanoid ions (Ln3+) including praseodymium, europium and ytterbium ions into 1,2-dichloroethane with the synthesized hydrazones in the presence of both tri-n-butylphos-phate (TBP) and perchlorate has been investigated. The extracted species were (Ln³⁺)(HLP^?)₂(TBP)₃(CI₄ ^?) for all the hydrazones. The acid dissociation constants, Ka, and the partition coefficients, K_o, of the hydrazones and the extraction constants, K_ex, of the lanthanoid complexes were determined. The introduction of electron-withdrawing bromo or nitro groups to the 3- and/or 5-position of the benzene ring in salicylaldehyde acetohydrazone (SAH), the mother compound of the synthesized hydrazones, was very effective for increasing not only the K_ex value of SAH but also its K_D value and the K_ex values of its lanthanoid complexes. Taking into consideration the above-mentioned three constants, of the synthesized hydrazones DBSAH was the most balanced and recommend-able extractant for the lanthanoids.     

SOLVENT EXTRACTION OF SOME TERVALENT LANTHANOIDS WITH SALICYLALDEHYDE n-ALKANOHYDRAZONES

Sal icylaldehyde n-alkanohydrazones (SAAH or H₂L) having 1 to 13 carbon atoms in their alkyl chains were synthesized and used for the extraction of some lanthanoid ions (Ln³⁺) including praseodymium, europium and ytterbium ions from aqueous solutions containing both tri-n-butyIphosphate (TBP) and perchlorate into I,2-dichloroethane The extracted species were (Ln³⁺) (HL-)₂(TBP)₃(C10₁,-) for all SAAH. The partition coefficients, Kd, of SAAH increased with an increase in the carbon number of the alkyl chain, the increment of log Kb being 0.64 per a carbon atom. The acid dissociation constants of SAAH also increased slightly with an increase in the carbon number, but the extraction constants of their lanthanoid complexes were almost independent of the length of the alkyl chain.     

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln³⁺) and 5f-elements (actinides, An³⁺) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln³⁺ and An³⁺ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu³⁺/Am³⁺ model pair cations (SF_Am/Eu) in extraction experiments on a semi-quantitative level.

The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM]³⁺, (H₂O)_nM(NO₃)₃ (n = 3, 4), and LM(NO₃)₃ (M = Eu, Am).

Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln³⁺ and An³⁺ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An³⁺ and Ln³⁺ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation.

Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N′,N′-tetraalkyl diamides (“effect of anomalous aryl strengthening”). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An³⁺/Ln³separation selectivity in the series of dipicolinic acid diamides.     

Coordination chemistry of a para-tert-octylcalix[4]arene fitted with phosphinoyl pendant arms towards 4f-elements: Extraction,synergism, separation

The solvent extraction of trivalent lanthanoids (Ln³⁺) by 5,11,17,23-tetra(para-tert-octyl)-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene (S), bearing four phosphine oxide donor groups at the lower rim as synergistic agent in combination with a 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP) in CHCl₃ from chloride medium at µ = 0.1 was quantitatively described in the form of LnP₃·S complexes. The role of the synergistic agent on the extraction process was discussed. The values of the separation factors have been evaluated. On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid mixed complex of Eu(III) with HP and S were proposed.     

Effect of Coordination Modes of HL Ligand on the Molecular Architecture of Its Transition Metal Complexes (HL = 5-Methyl-2-Phenyl-4-[(2-<Emphasis Type="Italic">o</Emphasis>-Tolylamino)-Phenylmethylene]pyrazol-3(2H)-one)

Abstract  Two Ag⁺ complexes [Ag(HL)₂(PF₆)] (1) and [(AgL) _n  · n(CH₂Cl₂) · n(0.5H₂O)] (2) (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) were synthesized and structurally characterized by EA analysis, IR spectra and X-ray crystallography. The result shows that two expected coordination modes (Modes I and III in Scheme 1) of the HL ligand, can be observed in its Ag⁺ complexes, while not in other transition metal ions (Ni²⁺, Co²⁺ or Cu²⁺) complexes whether deprotonation or not for the HL ligand. Graphical Abstract  Three possible coordination modes (Modes I, II or III in Scheme 1) of the selected HL (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) ligand, can be adopted, in which Modes I and III can be observed in its two Ag⁺ complexes [Ag(HL)₂(PF₆)](1) and [(AgL) _n  · n(CH₂Cl₂) · n(0.5H₂O)] (2), while Mode II just observed in its transition metal ions (Cu²⁺, Ni²⁺, or Co²⁺) complexes, resulting from the deprotonatd form of the HL ligand and the coordination characters of transition metal ions.      

Preparation,luminescence properties,and application of temperature sensing and anti-counterfeiting of La2MgTiO6:Yb3+/Ln3+/Mn4+

The doping of transition metal ions in the up-conversion (UC) luminescent material doped with Yb³⁺/Ln³⁺ is a facile way to increase their UC luminescence intensities and alter their colors. In this study, La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ (Ln³⁺ = Er³⁺, Ho³⁺, and Tm³⁺) phosphors showing excellent luminescence properties were prepared by a solid-state method. The sensitivity of the La₂MgTiO₆:Yb³⁺/Ln³⁺/Mn⁴⁺ phosphor was double that without Mn⁴⁺, because Mn⁴⁺ affects the UC emissions of Ln³⁺ via energy transfer between these ions. Moreover, Mn⁴⁺ also acts as a down-conversion activator, which can combine with UC ions to achieve multi-mode luminescence at different wavelengths. Under 980 nm excitation, these samples emit green light (from Er³⁺ and Ho³⁺) and blue light (from Tm³⁺). In contrast, under 365 nm excitation, they emit red light (from Mn⁴⁺). Further testing revealed that the La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ phosphors have potential applications in temperature sensing and anti-counterfeiting.     

Synthesis,Characterization and Anti-Breast Cancer Activity of New 4-Aminoantipyrine-Based Heterocycles

4-Aminoantipyrine was utilized as key intermediate for the synthesis of pyrazolone derivatives bearing biologically active moieties. The newly synthesized compounds were characterized by IR, ¹H- and ¹³C-NMR spectral and microanalytical studies. The compounds were screened as anticancer agents against a human tumor breast cancer cell line MCF7, and the results showed that (Z)-4-((3-amino-5-imino-1-phenyl-1H-pyrazol-4(5H)-ylidene)methylamino)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 5, 3-(4-bromophenyl) -1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 13, 1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1-Hpyrazol- 4-yl)-3-(4-iodophenyl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 14, 3,3′-(4,4′-sulfonylbis(4,1-phenylene))bis(1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol- 4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile) 16, (Z)-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-hydrazono-4-oxo-3-phenyl-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 17, (Z)-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-oxo-3-phenyl-2-(2-phenylhydrazono)-1,2,3,4-tetrahydro pyrimidine-5-carbonitrile 18, and (Z)-4-(3-amino-6-hydrazono-7-phenyl-6,7-dihydro pyrazolo[3,4-d]pyrimidin-5-yl)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 19 were the most active compounds with IC₅₀ values ranging from 30.68 to 60.72 μM compared with Doxorubicin as positive control with the IC₅₀ value 71.8 μM.     

The Solvent Extraction of Heptavalent Technetium by Tributyl Phosphate

Abstract

The solvent extraction of heptavalent technetium from aqueous nitric or hydrochloric acid by tributyl phosphate in n-dodecane (TBP-NDD) has been studied over a wide range of TBP and acid concentrations at 25, 50, and 60°C. The extraction was found to proceed according to the reaction 3TBP + H⁺ + TcO₄ ^? → (HTcO₄ · 3TBP). A discussion of possible reaction mechanisms is presented, along with values for ΔG, ΔH, ΔS, and the equilibrium constant for the extraction reaction. Finally, evidence for the coextraction of technetium by uranyl ions is discussed.     

Facile synthesis,novel structure,multicolor luminescence,and potential applications of lanthanide ions doped bismuth titanate phosphors

A variety of lanthanide ions doped bismuth titanate (Bi₄Ti₃O₁₂) luminescent materials with eminent down-conversion (DC) and up-conversion (UC) luminescence performance have been fabricated via a facile sol-gel approach. The XRD, XPS, and EDX elemental mapping results confirm the phase structure of orthorhombic Bi₄Ti₃O₁₂ (BTO), and the lanthanide activator ions occupy the Bi³⁺ lattice sites in the BTO crystal. Under UV or NIR excitation, the Eu³⁺, Yb³⁺/Ln³⁺ (Ln = Er, Tm, and Ho) doped Bi₄Ti₃O₁₂ samples exhibit characteristic red, green, blue, and green emissions. The luminescent mechanisms of the BTO:Eu³⁺ and BTO:Yb³⁺/Ln³⁺ samples are discussed based on the energy level diagrams. The doping concentrations of Eu³⁺, Yb³⁺, Er³⁺, Tm³⁺, Ho³⁺ ions and annealing temperature and time are optimized, whose optimal values are determined to be 14, 8, 1, 0.4, 1 mol% and 800 ^oC, 4 h. The as-obtained LED devices fabricated by Bi₄Ti₃O₁₂:Eu³⁺ and Yb³⁺/Ln³⁺ phosphors exhibit dazzling multicolor visible light emissions from different Ln³⁺ ions. The results indicate that the as-obtained Ln³⁺ doped BTO phosphors may be potentially utilized in LED devices and solid-state lighting. Furthermore, the Eu³⁺ and Er³⁺ co-doped BTO samples exhibit different DC and UC luminescence spectral profiles when excited at various UV, visible, or NIR wavelengths, revealing their eminent feasibility and great potential in anti-counterfeiting applications.     

Tunable emission and applications of Ln3+ doped NaGd(WO4)2 nanocrystals via a facile solvothermal process

Double tungstate crystal has outstanding capabilities of gain media for the application in mode-locked ultrafast lasers. Among them, NaGd(WO₄)₂:Ln³⁺ is widely using in laser, pH sensing or lighting devices. However, general synthetic methods require high temperature, long reaction time or adjustment of solution pH, which is seriously hinder their related applications. Here, we synthesized NaGd(WO₄)₂:Ln³⁺ nanocrystals through a solvothermal strategy. The synthesis was designed to avoid the solvent effect of water. Our nanoparticles with a rod shape and average size is ∼3.8 × 46.3 nm. Furthermore, Terbium and Europium ions co-doped in a single NaGd(WO₄)₂ host has been obtained, energy migration from Terbium ions to Europium ions also implemented. A series of emission colours (from green to white) were obtained. At last, a distinguished performance NaGd(WO₄)₂:0.03Tb,0.03Eu based UV-LED equipment was realized. Their adjustable emissions, convenient preparation method and special morphology reveal that NaGd(WO₄)₂:Ln³⁺ is a potential candidate for solid-state lasers and UV-LEDs applications.     

Synthesis of CaWO4:Ln3+ nanocomposites with high transparency via ligand-assisted re-precipitation method

A facile method to synthesis of CaWO₄:Ln³⁺ nanocrystals and transparent CaWO₄:Ln³⁺/polystyrene (PS) or polymethyl methacrylate (PMMA) copolymer films with outstanding luminescent property and high transparency is proposed. The average diameter of CaWO₄:Ln³⁺ nanorods is 3.3 ± 3 nm, and the average length is 40.3 ± 20 nm. The as-prepared CaWO₄:Ln³⁺/PS or PMMA copolymer films with high solids loading (>5 vol%) exhibit excellent near-ultraviolet absorption and outstanding visible transparency under the naked eye. The experiment results about the relationship between the solids loading and the film transparency are compared and analyzed. These optical results suggest that our nanorod has a versatile strategy for producing highly transparent functional luminescent composites, which indicates the promising applications in the field of optoelectronics in the future.     

Highly efficient near-infrared (NIR) luminescent tris-β-diketonate Yb3 + complex in solution and in PMMA

In the series of binary tris-β-diketonate complexes [Ln(L)₃(Phen)] (HL = (Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidene)-1H-pyrazol-5(4H)-one; Phen = 1,10-phenanthroline; Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5), the relatively lower ligands-based ³ππ^⁎ energy level (18,727 cm^− 1) results in the highly efficient NIR luminescence (Ф_Yb^Yb = 1.37% and Ф_Yb^L = 1.06%) of Yb^3 +-based 3 in solution and the higher NIR quantum yield (Ф_Yb^Yb = 1.77% and Ф_Yb^L = 1.31%) in PMMA (Poly(methyl methacrylate) besides the improved physical properties.     

Solvent Extraction Chemistry and Kinetics of Zirconium

Abstract

The solvent extraction behavior of zirconium in the HN03-tributyl phosphate (TBP) system can be explained based on the existence of four principal aqueous species, Zr⁴⁺, ZrOH³⁺, Zr₃(OH)⁸⁺ ₄, and oxo-polymers. The Zr⁴⁺ and ZrOH³⁺ species are extractable and are in equilibrium with inextractable Zr₃(OH)⁸⁺ ₄. The oxo-polymers are formed by heat, are-inextractable, and are not: in equilibrium with the other species. The aqueous equilibria and their equilibrium quotients have been previously determined. In the present study, these equilibria were used along with both tracer and macro zirconium concentrations (oxo-polymers excluded by extraction and back scrubbing) to determine the distribution equilibrium constants for both the Zr⁴⁺ and ZrOH³⁺ ions. The four equilibrium constants give excellent fits to both tracer and macro-zirconium distribution data.

The concentrations of the extractable zirconium species which are calculated from the equilibria have been used to begin examining the extraction kinetics of zirconium in the HNO₃-TBP system. In relatively concentrated nitric acid, approximately 3 M and greater, Zr⁴⁺ ion predominates, and the rate of extraction of zirconium increases as approximately the second power of the TBP concentration. In low acid (1 M and less) ZrOH³⁺ ion predominates, and the rate of extraction of zirconium increases as approximately the third power of the nitrate concentration. This is in significant contrast with the behavior of uranium, which shows only a small dependence of the extraction rate on TBP concentration, and no dependence on nitrate concentration. This suggests that operation of a kinetic separations system at low TBP and nitrate concentrations will significantly improve separations over those achieved at equilibrium.     

Upconversion luminescence properties of NaBi(MoO4)2:Ln3+, Yb3+ (Ln = Er,Ho) nanomaterials synthesized at room temperature

Studies on lanthanide ions doped upconversion nanomaterials are increasing exponentially due to their widespread applications in various fields such as diagnosis, therapy, bio-imaging, anti-counterfeiting, photocatalysis, solar cells and sensors, etc. Here, we are reporting upconversion luminescence properties of NaBi(MoO₄)₂:Ln³⁺, Yb³⁺ (Ln = Er, Ho) nanomaterials synthesized at room temperature by simple co-precipitation method. Diffraction and spectroscopic studies revealed that these nanomaterials are effectively doped with Ln³⁺ ions in the scheelite lattice. DR UV–vis spectra of these materials exhibit two broad bands in the range of 200–350 nm correspond to MoO₄²⁻ charge transfer, s-p transition of Bi³⁺ ions and sharp peaks due to f-f transition of Ln³⁺ ions. Upconversion luminescence properties of these nanomaterials are investigated under 980 nm excitation. Doping concentration of Er³⁺ and Yb³⁺ ions is optimized to obtain best upconversion photoluminescence in NaBi(MoO₄)₂ nanomaterials and is found to be 5, 10 mol % for Er³⁺, Yb³⁺, respectively. NaBi(MoO₄)₂ nanomaterials co-doped with Er³⁺, Yb³⁺ exhibit strong green upconversion luminescence, whereas Ho³⁺, Yb³⁺ co-doped materials show strong red emission. Power dependent photoluminescence studies demonstrate that emission intensity increases with increasing pump power. Fluorescence intensity ratio (FIR) and population redistribution ability (PRA) of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺ increases with increasing the Yb³⁺ concentration. Also, these values increase linearly with increasing the pump power up to 2 W. It reveal that these thermally coupled energy levels are effectively redistributed in co-doped samples due to local heating caused by Yb³⁺.     

SOLVENT EXTRACTION OF METALS WITH 4-DINITROBENZOYL-2, 4-DIHYDRO-5-METHYL-2-PHENYL-3H-PYRAZOL-3-ONE (DMPP)

ABSTRACT

The mechanism of the extraction of copper (II), nickel (II), cobalt (II) and thorium (IV) from aqueous buffer media with 4-dinitrobenzoyl1-2, 4-dihydro-5-methyl-2-phenyl-311-pyrazol-3-one (DMPP) in benzene has been investigated. The values of log K^*where K^*refers to the extraction equilibrium Mn⁺+-nHL ? MD_n+ nH⁺are Cu(II)& lpar; + 0.3), Co(II) (?6.65), Ni(II) (?5.04) and Th(IV) ( + 6.1). Solid complexes synthesized have the composition CuL₂· 2H₂O, NiL₂· 2H₂O and ThL₄respectively (L = anion of the ligand). DMPP seems to be superior to the corresponding 4-benzoyland 4-nitrobenzoyl derivatives of 2,4-dihydro-5-methyl-2-phenyl1-3 H-pyrazol1-3-one (MPP) and also better than thenoyltrifluoroacetone, the popularly employed fluorinated β-dike tone in the system investigated.     

Synthesis and properties of copolymers from diphenylacetylene having a hexaphenylbenzene moiety

Summary Copolymerization of diphenylacetylene having a hexaphenylbenzene group, 1-[p-(pentaphenyl)phenyl]-2-phenylacetylene (1), with a few other diphenylacetylene derivatives (i.e., diphenylacetylene, 1-phenyl-2-[p-(trimethylsilyl)phenyl] acetylene, 1-phenyl-2-[p-n-octylphenyl]acetylene, (2a–c, respectively) and properties of the formed copolymers were investigated. No polymer was obtained in homopolymerization of 1 with TaCl₅-n-Bu₄Sn catalyst owing to steric hindrance. On the other hand, copolymerization with 2a–c proceeded at various feed ratios to give copolymers in moderate yields. Copoly(1/2a) (feed ratio 25/75) was soluble in toluene and CHCl₃ and its weight-average molecular weight (M _w) was ca. 31×10⁴ and relatively high. Copoly(1/2b) and copoly(1/2c) (both feed ratios 5/95) were soluble in common organic solvents, and had a large M _w up to ca. 1×10⁶. These copolymers were yellow to orange solids. Oxidative cyclodehydrogenation of hexaphenylbenzene groups in copoly(1/2a) was attempted in order to convert them into more conjugated groups. Received: 24 January 2000/Accepted: 17 February 2000     

Application of N,N-Dialkyl Aliphatic amides in the Separation of Some Actinides

Abstract

N, N-dialkyl substituted alkyl amides are known to be good extractants of some actinides such as U, Pu, and Th. Their stability is comparable to that of TBP, and their degradation products do not interfere as do the degradation products of TBP. On the other hand, the principal disadvantage of the amides is their tendency to form poorly soluble U adducts in organic diluents.

A systematic investigation has been carried out on the extractive behavior of two typical alkyl amides of different structures with respect to the actinide ions UO₂ ²⁺, Th⁴⁺, Np⁺⁴, Pu⁺⁴, NpO₄₊ ², PuO²⁺ ₂, Pu³⁺, and Am³⁺, as well as with respect to the most significant fission products. The results obtained have been compared with those obtained using TBP in the same experimental conditions, verifying the applicability of amides in the separation of U from Th.     

Eu3+ -Nd2O3 blue pigmented solid solutions

Abstract

Usually, Nd₂O₃ shows a polymorphism based on the hexagonal Ln₂O₃ A type and cubic Ln₂O₃ C type structures, which have coordination numbers of 7 and 6 respectively. The Nd³⁺ (4f²) ion in an octahedral environment produces a reddish shade. In the present study, Eu_xNd_2-xO₃ compositions were prepared by ceramic and coprecipitation (from chloride solution) methods using several flux agents. Using the ceramic route, Nd₂O₃ C type structure was detected and the samples were colourless, but using coprecipitation, NdOCl crystallised from an amorphous coprecipitate at low temperature, developing the unusual monoclinic EuNd₂O₃ B type doped polymorph which is blue in colour. When enamelled using a conventional industrial tile glaze, these blue coprecipitated samples gave L*a*b* = 75/1/-11 in the CIE colour convention. Samples were characterised by X RD, U V-V-NIR spectroscopy, and SEM-EDX techniques.     

DISTRIBUTION BEHAVIOUR OF U(VI), Th(IV) AND Pa(V) FROM NITRIC ACID MEDIUM USING LINEAR AND BRANCHED CHAIN EXTRACTANTS

ABSTRACT

The extraction behaviour of 1M solutions of tri-2-ethylhexyl phosphate (TEHP), di-2-ethyl hexyl isobutyramide (D2EHIBA), tri-n-butyl phosphate (TBP) and di-n-hexyl hexanamide (DHHA) in n-dodecane towards U(VI), Th(IV) and Pa(V) in the presence of 220 g/L of Th from nitric acid medium has been studied. The limiting organic concentrations (LOC) of thorium (g/L) for 1 M TBP and 1 M DHHA are evaluated as 31, 20 ( at 1 M HNO₃) and 25,13 (at 4 M HNO₃) respectively. The distribution ratio (D) values of U(VI), Th(IV) and Pa(V) in the presence of thorium (220 g/L) at. 1 M HNO₃ suggest that branching in the alky group of amides suppresses the extraction considerably. In view of the selective extraction of U over Th by 5 % TBP in THOREX process at 4 M HNO₃, distribution behaviour is also studied employing a lower concenfration (0·18 M) of extractant for comparison purpose, Separation factor (S. F.) values for U(VI) over Th(IV) under different experimental conditions consistently varied in the order: D2EHIBA > DHHA > TEHP > TBP. The quantitative extraction of ²³³U from a synthetic mixture containing ²³³U (10^?5 M). ²³³Pa (10^?11 M) and thorium (220 g/L) at 1 M HNO₃ using 1 M solution of D2EHIBA in n-dodecane is achieved in three stages, Stripping and reusability studies of D2EHIBA have also been carried out.     

Solvent Extraction and Emulsion Separation in Magnetic Fields

Abstract

In two-phase emulsion separations, it is customary to employ large settling volumes (for mixer-settling apparatus) or large centrifugal forces (for centrifugal contactors). Improvement can sometimes be achieved by using an extractant with magnetic properties in the presence of a variable field. In the work reported in this paper, two different extractants (D-2EHPA and TBP) were employed in magnetic field experiments. These compounds are both stable and resistant to acid (15% H₂SO₄) and basic (NaOH, pH = 10) media. The test results for extraction of Cu²⁺ (with D-2EHPA) and UO₂ ²⁺ (with TBP) from aqueous media were positive. The emulsion separation for these two systems in the presence of a magnetic field was 160 times faster than in the gravitational field alone.