ACIDS. PART 1. P,P"-DI(2-ETHYLHEXYL) METHANEDIPHOSPHONIC ACID

ABSTRACT

Two novel extractants, P,P'-di(2-ethylhexyl) methanediphosphonic acid (H2DEH[MDP]) and P.P'-dioctyl methanediphosphonic acid (H2DO[MDP]) have been synthesized at high purity and yield. H₂DEH[MDP] was selected for metal extraction studies because of its better physical properties. An investigation of the extraction of alkaline earth cations, Fe(III) and representative tri-, tetra- and hexavalent actinide ions from nitric acid solutions into o-xylene solutions of H₂DEH[MDP] at different concentrations was performed. With a few exceptions, the acid dependencies of the extraction of the above metal species strongly resembles those measured in the uptake of the same metals by the chelating ion exchange resin Diphonix®, which contains gem-diphosphonic acid groups chemically attached to a polymeric matrix. H₂DEH[MDP] exhibits practically no selectivity among the alkaline earth cations. The almost lack of acid dependency observed with Fe(lll) and tetra- and hexavalent actinides indicates that these ions are chelated by H₂DEH[MDP] mostly through the P=0 groups of the extractant. With Fe(lll) and the actinides, variable slopes of the extractant dependencies were measured, their values being strongly dependent on the acidity of the aqueous phase. Typically, the slope of the extractant dependency has a value of about two if the metal is extracted from high acidity solutions. This value becomes progressively lower as the aqueous acidity is reduced, tending to almost zero for acidities around 0.1 M. This phenomenon has been attributed to the formation of metal complexes having different stoichiometrics, ligand protonation and solubility in the aqueous phase.

H₂DEH[MDP] possesses an extraordinary affinity for actinides and Fe(III). In analogy with the Diphonix resin, this property can be exploited for actinide preconcentration and separation from complex matrices of analytical interest and from mixed waste solutions.     

LIQUID - LIQUID EXTRACTION OF GALLIUM(m) FROM ACIDIC NITRATE MEDIA WITH BIS(2-ETHYLHEXYL) PHOSPHINIC ACID IN TOLUENE

ABSTRACT

The distribution equilibria of gallium(III) between bis(2-ethylhexyl) phosphinic acid dissolved in toluene and acidic aqueous nitrate media has been investigated as a function of the concentration of extractant in organic phase and concentration of hydrogen ion and gallium(III) ion in aqueous phase. The extraction characteristics of bis(2-ethythexyl) phosphinic acid are compared with that of bis(2-ethylhexyl) phosphoric acid to get further information. The stoichometry of the extracted species is determined on the basis of slope analysis and IR spectra. Gallium is extracted by a cation exchange mechanism as GaRs₃ by bis(2-ethylhexyl) phosphinic acid and as GaRs₃-HR by bis(2-ethylhexyl) phosphoric acid. Temperature dependence of the extraction equilibrium is examined by temperature variation method. Both extraction processes are endothermic in nature and increase in temperature is favorable.     

RECOVERY OF URANIUM FROM ACID MEDIA BY MACROPOROUS BIFUNCTIONAL PHOSPHINIC ACID RESIN

ABSTRACT

The extraction of uranium from various acid media such as nitric acid, sulphuric acid, hydrochloric acid, phosphoric acid and perchloric acid by a macroporous bifunctional phosphinic acid resin (MPBPA) has been studied. The distribution coefficients for the extraction of uranium by the MPBPA resin are compared with the corresponding values reported in literature for the conventional sulphonic acid resin. The results clearly indicate the suitability of the MPBPA resin to recover uranium from different types of acid solutions of widely ranging acidities.     

Selective Separation of Scandium(III) and Yttrium(III) from other Rare Earth Elements using Cyanex302 as an Extractant

Abstract

Liquid‐liquid extraction and selective separation of scandium(III) and yttrium(III) with Cyanex302 (bis(2,4,4‐trimethylpentyl)monothiophosphinic acid) has been carried out by controlling the aqueous phase pH. Scandium(III) and yttrium(III) were completely recovered from the organic phase using 5.0 M and 4.0 M nitric acid respectively and determined spectrophotometrically as their complexes with Arsenazo(III). The influence of extractant concentration, equilibration time, nature of diluents, stripping agents, and diverse ions on the extraction of scandium(III) and yttrium(III) was investigated. The extractability of scandium(III), yttrium(III), and other rare earth elements was exploited for sequential separation of scandium(III)‐yttrium(III)‐lanthanum(III) and other rare earth elements viz. lanthanum(III), cerium(IV), praseodymium(III), neodymium(III), gadolinium(III), dysprosium(III), and ytterbium(III) in binary mixtures. The method presented is simple and rapid for isolation of scandium(III) and yttrium(III) from associated elements and has been successfully applied for their selective separation from complex matrices of USGS standard soil GXR‐2 and Japanese standard stream sediment sample Jsd‐3.     

SOLVENT EXTRACTION OF SCANDIUM(III), YTTRIUM(III), LANTHANIDES(III), ANDDIVALENT METAL IONS WITH SEC -NONYLPHENOXY ACETIC ACID

ABSTRACT

Such physicochemical properties of sec-nonylphenoxy acetic acid (CA-100) as the solubility in water, acid dissociation constant in water, dimerization constant in heptane, and distribution constant in organic solvent-water were measured by two-phase titration. The extraction behaviors of scandium (III), yttrium (III), lanthanides (III), and divalent metal ions from hydrochloric acid solutions with CA-100 in heptane have been investigated, and the possibilities of separating scandium (yttrium) from lanthanides and divalent metal ions have been carefully discussed. The stoichiometries of the extracted metal complexes were investigated by the slope-analysis technique. The effect of the nature of diluent on the extraction of yttrium (III) with CA-100 has been studied and correlated with the dielectric constant.     

THE EXTRACTION OF Am(III) FROM NITRIC ACID BY OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE - TRI-n-BUTYL PHOSPHATE MIXTURES

Abstract

The extraction behavior of Am(III) from nitric acid by octy1(phenyl)-N,N-diisobutylcarbamoyl methyphosphine oxides, OØD[IB]CMPO, in the presence of tributylphosphate, TBP, has been studied using diethylbenzene, decalin, and normal aliphatic hydrocarbon diluents. Relative to ØD[IB]CMPO alone, mixtures of TBP and OØD[IB]CMPO show a slight enhancement in the extraction of Am(III) from nitric acid solution above 2 M and a moderate decrease in extraction for lower acid concentrations. The net effect of TBP addition to OØD[IB]CMPO (as well as other selected carbamoyl methylphosphoryl extractants) is a relative insensitivity of the distribution ratio of Am(III) to HNO₃ concentration in the range of 0.5 M to 6 M and facilitated stripping of Am(III) with dilute acid. Since a continuous variation study of Am(III) extraction using mixtures of ØOD[IB]CMPO and TBP at a fixed total concentration revealed no evidence of a mixed complex, the TBP appears to be behaving primarily as a phase modifier

The most significant benefit gained from addition of TBP to ØD[IB]CMPO is the increased metal ion loading capacity and extractant compatibility with alicyclic and aliphatic diluents. The use of TBP to overcome phase compatibility with other bifunctional extractants of the carbamoylmethylphosphoryl type and the use of other phase modifiers with ØD[IB]CMPO have also been investigated.     

EXTRACTION OF NICKEL FROM AQUEOUS SULFATE SOLUTION INTO BIS(2,2,4-TRIMETHYLPENTYL)PHOSPHINIC ACID,CYANEX 272TM -EQUILIBRIUM AND KINETIC STUDIES

ABSTRACT

Equilibrium and kinetic studies have been carried out on the extraction of nickel from sulfate solutions using bis(2,2,4 trimethylpentyl) phosphinic acid HDTMPP, “Cyanex 272tm”- It was found that nickel extraction in HDTMPP was favored by the presence of sodium in the organic phase and that equilibrium nickel concentration could be written in terms of the pre-equilibrated extractant concentration

Kinetic studies were carried out using the rising drop method, reaction orders were determined with respect to the aqueous phase nickel concentration, Ni²⁺, the aqueous phase sodium concentration, Na ⁺ the pH, the organic phase dimer concentration ------ and the organic phase sodium salt concentration ---- In addition, it was found that the extraction kinetics could be explained in terms of an aqueous phase interfacial reaction accompanied by diffusion through the interface. Mass transfer coefficient values were determined indicating extraction rates for metal extraction into HDTMPP were the same order of magnitude as those found for HDEHP.     

EXTRACTION AND SEPARATION OF HEAVY RARE EARTH(III) WITH EXTRACTION RESIN CONTAINING DI(2,4,4-TRIMETHYL PENTYL) PHOSPHINIC ACID (CYANEX 272)

ABSTRACT

Extraction resins, of the type of Levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(II1)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50°C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm₂O3 >99.97%, >80%; Er₂O₃ >99.9%, >94% and Yb₂O₃ >99.8%, >80% respectively, have been obtained from a feed having the composition Tm₂O₃ 60%, Er₂O₃ 10%, and Yb₂O₃ 3%, the others 27%.

The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.     

SOLVENT EXTRACTION OF ZINC(II) BY ORGANOPHOSPHORUS ACIDS COMPOUNDS FROM PERCHLORATE SOLUTIONS.

ABSTRACT

The extraction of zinc from perchlorate solutions at 0.1 mol.dm^?3 of ionic strength by di(2-ethylhexyl)phosphoric acid (HDEHP), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and di(n-octyl)phosphinic acid (H[DOP]) dissolved in toluene has been studied at 25 ° C.

The distribution coefficient was determined as a function of pH and HA concentrations and the data were analyzed both graphically and numerically using the computer program LETAGROP-DISTR.

The results showed that the data can be explained assuming the formation of ZnA₂(HA)₂ and ZnA₂HA in organic phase for all the extractants used. A correlation between extracted species and concentration of the various extractants has been found.

The predominance of the different species into the organic phase has been correlated with the difference between their extraction constants.

The anion of the ionic medium is not extracted into the organic phase.     

Extraction of scandium(III) using ionic liquids functionalized solvent impregnated resins

Ionic liquids (ILs) functionalized solvent impregnated resins (SIRs) were prepared using IL modified Merrified resin as the polymeric supports by impregnation of extractant for extraction of Sc(III). The ILs modified Merrifield resin were prepared via covalent anchoring of imidazolium salts onto Merrifield resin. The polymeric supports with imidazolium chloride group (RCl) and imidazolium hexafluorophosphate group (RPF₆) were characterized by FTIR, TGA, and elemental analysis. It was found that RCl and RPF₆ had tunable hydrophilicity and hydrophobicity, different acid stability, and swelling behaviors in solvents. The effect of Cyanex 923 extractant or [C₈mim][PF₆] IL impregnated on RCl and RPF₆ were studied. The results showed Cyanex 923 and [C₈mim][PF₆] exhibited stronger affinity to RPF₆ than to RCl. RPF₆ with Cyanex 923 was found to be effective in Sc(III) extraction. The extraction mechanisms of SIRs containing RPF₆ and Cyanex 923 with or without [C₈mim][PF₆] were cation exchange and neutral complexation, respectively. [C₈mim][PF₆] acted as an extraction media and was involved in the cation exchanged extraction reaction. Sc(III) can be selectively separated from Tm(III), Yb(III), and Lu(III) by the SIRs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO₃ concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.     

METAL EXTRACTION FROM NITRIC ACID SOLUTIONS BY (DIPHENYL-PHOSPHINYLMETHYL) PHENYLPHOSPHINIC ACID

ABSTRACT

The extraction of microquantities of Ca, Sr, Ba, Sc, Mn, Co, Cu, Zn, Ga, Cd, In, Pb, Bi, Zr, Hf, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U from HNO₃ solutions by (diphenylphosphinylmethyl)phenylphosphinic acid in organic diluents has been studied.

The effect of HNO₃ concentration in the aqueous phase and that of the extractant in the organic phase on the metal extraction are considered. (Diphenylphosphinylmethyl)phenylphosphinic acid possesses an extraordinary affinity for actinides and rare-earth elements. The extractive efficiency and selectivity of this compound toward rare-earth metal ions are compared with those of some multifunctional acidic and neutral organophosphorus extractants.     

SYNERGISTIC EXTRACTION STUDIES OF Am(III) AND Eu(III) FROM PERCHLORIC ACID WITH 4-BENZOYL-2,4-DIHYDRO-5-METHYL-2-PHENYL-3H- PYRAZOL-3-THIONE (BMPPT) AND TRI-n-OCTYLPHOSPHINE OXIDE (TOPO) IN BENZENE

The extraction of Am(III) and Eu(III) from aqueous HCIO₄ by BMPPT and TOPO in benzene was studied. The ligand BMPPT gave no detectable extraction in the ranges studied, but when BMPPT and TOPO were combined, a synergistic extraction was observed with a selectivity for Ara(III) over Eu(III) (K_dAm = 7.5, Am/Eu = 68, pH 3.0, 0.01 M [TOPO], 0.30 M [BMPPT]). The slope of the acid dependency for Eu and Am was 1.6 ± 0.1 and 2.7 ± 0.1, respectively, over the pH range of 2 to 3.The slope of the BMPPT dependency was 2.7 ± 0.1 and 2.8 ± 0.1 over a 2- and 20-fold concentration range for Eu and Am, respectively; the slope of the TOPO dependency was 2.0 ± 0.1 and 2.2 ± 0.1 for Am and Eu, respectively, over a 20-fold concentration range.     

Recovery and Separation of Lanthanum(III), Aluminum(III), Cobalt(II), and Nickel(II) from Misch Metal by Solvent Extraction Using Bis(2-ethylhexyl) phosphinic Acid

Abstract

This paper describes use of bis(2-ethylhexyl) phosphinic acid as a reagent for extraction and mutual separation of lanthanum(III), aluminum(II), cobalt(II), and nickel(II) in 1.0 mol/L sodium nitrate. The extraction and stripping behavior of the four metal ions has been investigated using the extractant in Solvesso #150 as a diluent. The mutual separation and recovery of the metal ions from their mixtures has been tested by multistage extraction with a conventional separator funnel. A set of separation schemes has also been proposed for a continuous countercurrent multistage extraction which is comprised of ten extraction stages, four scrubbing stages, and seven stripping stages. Lanthanum(III) and aluminum(III) are coextracted but separated by selective stripping into different concentrations of hydrochloric acid. Cobalt(II) can be extracted with the nickel(II)-preloaded extractant solution, whereas nickel(II) remains in the aqueous phase. The successful separation of these metal ions from a misch metal-simulated sample is presented.     

METAL EXTRACTION BY ALKYL SUBSTITUTED DIPHOSPHONIC ACIDS. PART 4 P,P′-DI(2-ETHYLHEXYL) BUTANEDIPHOSPHONIC ACID

ABSTRACT

As part of an ongoing investigation of the properties of dialkyl substituted diphosphonic acids as solvent extraction reagents for metal cations, we have studied the extraction of alkaline earth cations, Fe(III) and representative actinides (Am(III), U(VI) and Th(IV)) at tracer-level concentration by o-xylene solutions of P,P′-di(2-ethylhexyl) butanediphosphonic acid, H₂DEH[BuDP]. The extractant and acid dependencies of these metal ions exhibited significant differences from those of the previously investigated analogous extractants in which the two phosphonate groups are separated by a methylene or an ethylene bridge. The aggregation of H₂DEH[BuDP] was investigated in toluene at 25° C by vapor pressure osmometry. H₂DEH[BuDP] was found to exist predominantly as a trimeric species in the 0.1-0.005 molal concentration range. Osmometric measurements and infrared spectra indicate that Ca(II) is extracted into H₂DEH[BuDP] solutions with little disruption of the structure of the extractant. Iron(III) causes significant deprotonation of the ligand and dramatically changes the apparent aggregation number. A comparison of the extraction of Ca(II), Am(III) and Fe(III) by H₂DEH[BuDP] with data obtained using bis(2-ethylhexyl) phosphoric acid (HDEHP) or 2-ethylhexyl 2-ethylhexylphosphonic acid (HEH[EHP]) as the extractant indicates that H₂DEH[BuDP] has characteristics similar to these monofunctional analogs. Infrared spectra of the Ca(II) and Fe(III) salts of H₂DEH[BuDP] show a shift of both v_asym (POO?) and v_sym (POO?) to lower frequencies relative to their values in the sodium salt. This indicates a symmetrical interaction between the metal ion and the phosphonate groups through chelate and/or bridging interactions.     

AGGREGATION OF P,P' -DI( 2-ETHYLHEXYL) METHANEDIPHOSPHONIC ACID AND ITS Fe(III) COMPLEXES ∗

ABSTRACT

The aggregation of P,P' -di( 2-ethylhexyl) methanediphosphonic acid, H2DEH[ MDP] dissolved in deuterated toluene has been investigated by small angle neutron scattering ( SANS) The title compound was shown to exist in solution as a dimer under all conditions. Dimer formation is independent of the acidity of the aqueous solution with which the organic solution is pre-equilibrated. Solutions of H₂ DEH[ MDP] containing increasing amounts of Fe( lll) extracted from aqueous solutions in the acidity range from 0.1 to 5 M were also investigated. The SANS results confirm the tendency of H2DEH[ MDP] -Fe( III) species in aromatic diluents to form rod-like aggregates characteristic by a constant cross section and a length which increases with increasing amounts of metal in the organic phase. Particle growth is independent of the acidity of the aqueous solutions from which the metal is extracted. These results are important for understanding the chemistry underlying the solvent extraction behavior H₂DEH[ MDP] and its practical application in separation procedures.     

SOLVENT EXTRACTION EQUILIBRIA OF GALLIUM (III) WITH ACIDIC ORGANOPHOSPHORUS COMPOUNDS FROM AQUEOUS NITRATE MEDIA

A comparative investigation on the solvent extraction equilibria of gallium(III) from aqueous nitrate media was conducted with three kinds of acidic organophosphorus compounds, di (2-ethylhexyl) phosphoric acid (D2EHPA), 2-ethylhexyl 2-ethyl-hexylphosphonic acid (EHEHPA) and di (2,4,4'-trimethylpentyl) phosphinic acid (DTMPPA), in toluene at 303 K. It was found that gallium(III) is extracted as 1:4 metal:reagent complexes with D2EHPA and EHEHPA and as a 1:3 complex with DTMPPA in the region of low loading ratio while it is extracted as 1:3 complexes with all reagents at high loading ratio. The extraction equilibrium constants with these extractants were evaluated for the former complexes as follows: K_e = 2.3xl0^-2, 8.5xl0^-3 and 1.3xl0^-4 for D2EHPA, EHEHPA and DTMPPA respectively.     

Cloud Point Extraction and Separation of Scandium and Yttrium (III) with Triton X‐114 in the Presence or Absence 8‐Hydroquiloline as an Added Chelate

Abstract

In this paper, the cloud point extraction and separation of scandium and yttrium (III) via use of Triton X‐114 with and without 8‐hydroquiloline (HQ) as an added chelate agent are investigated. The effects of various parameters, such as the aqueous phase pH, HQ concentration, Triton X‐114 concentration, heating temperature, and incubation time, on the cloud point extraction of scandium and yttrium (III) are studied. The results demonstrate that, there are different extraction and separation behaviors for scandium and yttrium (III) with and without HQ as an added chelate. And in contrast to solvent extraction, cloud point extraction is an excellent method to extract and separate scandium and yttrium (III).     

EXTRACTION OF ACTINIDES BY BIFUNCTIONAL PHOSPHINIC ACID RESIN

ABSTRACT

The extraction of U(VI), Am( III), Pu( IV), Np( IV) and ThIV) by bifunctional phosphinic acid resin of various cross linkages is reported as function of nitric acid concentration. From the comparison of the distribution coefficient values it is suggested that the recovery of these actinide elements from waste solutions as we II as their mutual separations is possible by using phosphinic acid resin.     

Mutual Influence of Iron(III) and Gold(III) as Macroconstituents in the Extraction Systems Forming Three Liquid Phases

Abstract

The extraction of a mixture of iron(III) and goId(III) by either pure or diluted (benzene as diluent) diisopropyl ether (IPE) from aqueous solutions of hydrochloric acid at 20°C was investigated. The dependence of metal extraction on the initial concentration of hydrochloric acid, iron(III), and IPE was studied under conditions of third phase formation. It was found that under certain conditions, gold(III) coextracted with iron(IH).