SOLVENT IMPREGNATED RESINS CONTAINING DI(2-ETHYL-HEXYL)PHOSPHORIC ACID.II. STUDY OF THE DISTRIBUTION EQUILIBRIA OF Zn(II), Cu(II) AND Cd(II).

ABSTRACT

The extraction of Zn(II), Cu(II) and Cd(II) from nitrate solutions at 0.1 M ionic strength by impregnated resins containing di(2-ethylhexyl)phosphoric acid has been studied at 25 °C.

The distribution coefficient was determined as a function of both pH and extractant concentration in the resin phase. The data were analyzed graphically using the slope analysis method, and numerically using the program LETAGROP-DISTR. The composition of the extracted species in the resin phase has been determined.

Analysis of the results showed that the extraction of these metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML₂(HL) _q where q takes different values depending on the metal. An extraction reaction is proposed and the extraction constants of these species are given.

Finally, a comparison between the extraction of Zn(II), Cu(II) and Cd(II) by di(2-ethylhexyl)phosphoric acid into Amberlite XAD2 and the extraction using organic solvents has been made.     

IMPREGNATED RESINS CONTAINING DI-(2-ETHYLHEXYL) THIOPHOSPHORIC ACID FOR THE EXTRACTION OF PALLADIUM(H). II. SELECTIVE PALLADIUM(II) RECOVERY FROM HYDROCHLORIC ACID SOLUTIONS

ABSTRACT

The extraction of Pd(II) from HC1 solutions by impregnated resins containing di-(2-ethylhexyl) thiophosphoric acid (DEHTPA or HL) on the Amberlite XAD2 polymeric support has been studied. Graphical and computer analysis with the program LETAGROP-DISTR demonstrated that the Pd(II) extraction can be explained by the formation of metal complexes in the resin phase having the composition PdL₂(HL)₂. DEHTPA/XAD2 resins extracted Pd(II) in the presence of other metals: Pt(IV), Rh(III), Cu(II), Fe(III) as well as Zn(II). The stripping of Pd(II) loaded on the organic phase and the lifetime of the resins were also investigated.     

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.     

LIQUID-LIQUID EXTRACTION OF GOLD(III) AND ITS SEPARATION OVER COPPER(II), IRON(III), AND ZINC(II) USING THIOUREA DERIVATIVES FROM CHLORIDE MEDIA

ABSTRACT

Selective liquid-liquid extraction of Au(III) from aqueous chloride media (1 mol/L NaCl) into cumene by thiourea derivatives namely 2a-c (N-thiocarbamoylbenzamidine derivatives), 3a-f (N-benzoylthiourea derivatives) has been investigated in detail. Marked differences in the metal extraction are noted using these organic compounds with respect to their structural variation. The extraction behaviour of Au(III) with extractants 2a-c and 3a-f followed the order : 2b> 2a>2c and 3e≈ 3c≈ 3d >3a >3f≈3b, respectively. The organic reagent 2a and 3c were selected for further detailed studies owing to their better strippability behaviour. Optimum conditions such as structure of the organic extractant, aqueous phase pH, diluent, time of equilibration, metal concentration, extractant concentration, effect of other metal cations were established for extraction separation of Au(III). Experimental data have been treated graphically and numerically by means of the computer programme LETAGROP-DISTR, and can be explained by assuming the formation of the species AuCl₃L and AuCl₃L₂ for 2a-c and AuCl₃L₂ for 3a-f derivatives. The lack of interference from even appreciable amounts of possible base metals such as Cu(II), Zn(II) and Fe(III) may be considered an outstanding advantage of the method for separation of gold from these metals using 2a and 3c.     

Potentiometric Studies on Ternary Complex Formation between Cu(II), Ni(II), Zn(II), Cd(II), nitrilotriacetic acid and amino acid

The formation of ternary complexes of the type MAB (where M = Cu(II), Ni(II), Zn(II) or Cd(II); A = nitrilotriacetic acid and B = glycine, α-alanine or dl-aspartic acid) has been shown by potentiometric studies. The nature of titration curves indicates that the secondary ligand B is added stepwise to the initially formed metal nitrilotriacetates. The formation constants (log K_MAB) and the free energies of formation (ΔF°) of the mixed complexes have been calculated at 25 ± 1 °C and m̈ = 0.10 (KNO₃) at different pH values. The formation constants of the resulting 1:1:1 ternary complexes follow the order Cu(II) > Ni(II) > Zn(II) > Cd(II).     

Polymetallic complexes. part iii. schiff base complexes of cobalt(ii), copper(ii), cadmium(ii) and mercury(ii)

Eight polymetallic complexes have been synthesised of the composition M₂L₂._nB [M = Co(II), n = 4, B=H₂O, M = Cu(II), Cd(II) and Hg(II), n = 0] M₂L_2'.nB [M = Co(II), n = 4, B = H₂O; M = Cu(II), Cd(II) and Hg(II), n = 0], LH₂ = bi-bidentate Schiff base derived from benzoin with m-phenylenediamine; L'Hz = tridentate Schiff base derived from benzoin with o-aminophenol. Elemental analysis, conductance, magnetic susceptibility, i.r. and electronic spectral measurements have been done to characterise the complex compounds. A dinuclear octahedral configuration has been assigned to the cobalt(II) complexes and a dinuclear square planar structure to the copper(II) complexes. A tetrahedral configuration has been attributed to the cadmiurn(II) and mercury(II) complexes.     

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.     

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.     

Solvent-Extraction Behavior of Cobalt(II), Nickel(II), Copper(II), and Palladium(II) with Tri-n-butylphosphate

Abstract

A systematic study of the extraction behavior of cobalt(II), nickel(II), copper(II), and palladium(II) with TBP from thiocyanate system in various ranges of acid concentrations has been performed. The thiocyanate medium leads to enhanced extractions in all these cases compared to those in the previously used chloride medium. For palladium, the chloride and nitrate systems have been critically examined. Sixty-two per cent extraction occurs from 4 M hydrochloric acid using 100% TBP in a single run and the extraction becomes quantitative (>99%) after four successive equilibrations. A simpler method has been proposed for rapid extraction of palladium(II) as the thiocyanate complex. Quantitative extraction occurs in the presence of 1.2% thiocyanate solution from 0.5 to 2 M hydrochloric acid (initial) up to pH 8.0. The extractable species of cobalt(II), nickel(II), copper(II), and palladium(II) from thiocyanate medium are probably similar and of the type [M(CNS)₄]^2? [K·TBP·3H₂O]₂ ⁺ (buffer solution) and [M(CNS)₄]^2? [H·TBP·3H₂O]⁺ ₂ (acid solution). A simple extraction scheme has been worked out for the separation of palladium(II) from iron(III), cobalt(II), nickel, manganese(II), copper(II), and platinum.     

Stability constants of adipate complexes of copper(II), nickel(II), zinc(II), cobalt(II), uranyl(II) and thorium(IV) determined by electrophoresis

Stability constants of Copper(II), Nickel(II), Cobalt(II), Zinc(II), Uranyl(II) and Thorium(IV) adipates have been determined by paper electrophoresis. Adipic acid (0.005 mol dm^?3) was added to the background electrolyte: 0.1 mol dm^?3 HClO₄. The proportions of (CH₂)₄COOH COO^? and (CH₂)₄C₂O⁼₂ were varied by changing the pH of the electrolyte. These anions yielded the complexes Zn(CH₂)₄COOH COO⁺, Co(CH₂)₄COOH COO⁺, Ni(CH₂)₄COOH COO⁺, Th(CH₂)₄COOH COO³⁺, Th[(CH₂)₄COOH COO]₄, Cu(CH₂)₄ C₂O₄ and UO₂[(CH₂)₄(C₂O₄)]^2?₂, whose stability constants are found to be 10^2.8, 10^2.8, 10^3.2, 10^5.2, 10^15.3, 10^2.7 and 10^11.8 respectively (μ = 0.1, temp. 40°C).     

SYNTHESIS AND USES OF THE AMIDES EXTRACTANTS

Carboxylic acids amides (RR' NCOCR” ) malonic acid amides ( RR' NC0CH₂ C0NRR' ) and substituted malonic acid amides ( RR,NC0CHR“ C0NRR ) are extractants of the actinides ions. They show good prospects for use in the nuclear industry because of their complete incinerability. In addition, their degradation products interfer much more less in the separation processes when compared with organophosphorus extractants. The synthesis and the purification of two typical extractants: N-N-di( 2-ethylhexyl) butyraraide ( C₄H₉ CHC₃H₅CH₂) NC0C₃H₇and N,N' -dimethyl N,N' -dibutyl 1,3 diamide 2( 3-oxa) nonyl propane ( C₄H₉CH₃NC0) ₂CHC₂H₄OC₆H_1,3 are described. The purities, checked by NMR, elemental analysis and potentiometry, were in the range 98 to 99.5% The yields for monoamides were in the range 70 to 90% and for the diamides 20 to 40%     

有机磷一元酸钴(Ⅱ)络合物构型选择中的取代基效应

记录了几个有机磷-元酸钻络合物正辛烷溶液在400~750nm范围内的吸收光谱．研究了苯乙烯膦酸单正辛基酯，单2-乙基已基酯和单1-甲基庚基酯，2-乙基已基膦酸单2一乙基已基酯和二-2-乙基已基磷酸萃取剂．对每一种萃取剂，钴萃合物以一定程度由无水时的四面体构型转变为有水时的八面体构型．用这些酸的取代基的空间位阴和电子效应解释了钴萃合物的构型选择．     

SOLVENT EXTRACTION EQUILIBRIA OF LEAD(II) WITH ACIDIC ORGANOPHOSPHATE AND PHOSPHONATE

Distribution equilibria of lead(II) in the extraction with di(2-ethylhexyl)phosphoric acid and 2-ethylhexyl 2-ethylhexylphosphonic acid in toluene from aqueous ammonium nitrate solutions were measured at 303 K to elucidate the concentration dependencies of the reactant species on the distribution ratio. It was found that lead(II) is extracted as the mononuclear complex, PbR₂2HR, with the former extrac-tant while it is extracted not only as the complex, PbR₂2HR, but also as the complex, Pb(NO₃)R;HR, accompanied by simultaneous transfer of nitrate anion with the latter ex-tractant. The extraction equilibrium constants of these complexes were evaluated as well as the stability constants of lead(II) -nitrato complexes, Pb(NO₃)⁺, Pb(NO₃)₂and Pb(NO₃)^? ₃.     

STUDIES ON THE STRUCTURAL EFFECT OF DIALKY (ARYL) SULFIDES IN GOLD AND PALLADIUM EXTRACTION

A systematic study of the structural effects of dialkyl(aryl) sulfides on the extraction equilibra of Au (III) and Pd (II) are reported. Dialkylsulfides are excellent extractants with high capacities and selectivity for Au and Pd from HC1 solution. The extraction behavior of dialkyl(aryl)sulfides may be controlled by polar and steric substituents effect. The distribution data suggested that the extracted species were AuCl₃ R₂S and PdCl₂SUB 2R₂S, respectively.     

Kinetic behavior of lanthanide extraction with acidic phosphorus extractants

The kinetic behavior of lanthanide extraction from HAc–NaAc–EDTA media with three acidic phosphorus extractants(HL), bis(2-ethylhexyl)phosphoric acid (HDEHP), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH(EHP)) and bis(2,2,4-trimethylpentyl)phosphinic acid (H(DTMPP)) in n-octane solution is reported. The observed rate constants, k_o for the metals (M) lanthanum, neodymium, gadolinium, holmium and lutetium with these three extractants were determined under vigorous mixing. The rate equation for extraction was determined to be: A mechanism has been proposed for the extraction reaction under the experimental conditions. For a given metal the rate constant as a function of ligand followed the order HDEHP > HEH(EHP) > H(DTMPP), the decrease from HDEHP to H(DTMPP) being less than an order of magnitude. It was also found that the rate constants for these metals and yttrium bear an inverse relationship to the stability constants of their complexes with EDTA.     

AGGREGATION BEHAVIOR OF COBALT(II), NICKEL(II), AND COPPER(II) BIS(2-ETHYLHEXYL) PHOSPHATE COMPLEXES IN n-HEPTANE

ABSTRACT

The solution behavior of divalent transition metal-bis(2-ethylhexyl) phosphate (M(DEHP)₂, M = cobalt, nickel or copper) complexes in n-heptane have been investigated by vapor pressure osmometry, viscometry and dynamic light scattering. Co(DEHP)₂ complexes tend to form large macromolecular species with a mean aggregation number N_agg as large as 225, and the size of the macromolecular species decreases with increasing Co(DEHP)₂ concentration. In contrast, Cu(DEHP)₂ complexes tend to form small macromolecular species N_agg = 4-8 which increase in size with increasing Cu(DEHP)₂ concentration. On the other hand, Ni(DEHP)₂ complexes (and Ni(DEHP)₂-2H₂O complexes when the molar ratio of H₂O     

EXTRACTION EQUILIBRIUM OF MERCURY(II) WITH A SULFUR-CONTAINING CARBOXYLIC ACID.

ABSTRACT

The extraction behaviors of mercury(II) with dihexyl sulf ide(=DHS), 1,2-bis (hexylthio) ethane ( = BHTE) and ∝-butylthiolauric acid(= ∝-BTLA) from nitric acid and hydrochloric acid were compared at 30 ° C. It was found that in the case of the extraction from nitric acid, mercury(II) is almost quantitatively extracted by these extractants except DHS and that in the case of that from hydrochloric acids, the extractability for mercury(II) of these extractants was in the order:BHTE > DHS > ∝-BTLA. Further detailed studies were conducted in order to investigate the extraction behavior of ∝-BTLA for mercury(II) from chloride medium. It was clarified that ∝-BTLA does not behave as a cation-exchange extractant but as a solvating extractant owing to the strong affinity of a sulfur atom in ∝-BTLA to mercury(II), and that mercury(II) is extracted according to the following solvation mechanism by ∝-BTLA.

Extraction equilibrium constant was evaluated as K_e=5.5(dm³/mol).     

HYDRATION AND AGGREGATION NEUTRAL OXYGEN-DONOR EXTRACTANTS HYDRATION AND AGGREGATION OF MONOFUNCTIONAL SULFOXIDE AND OTHER NEUTRAL OXYGEN-DONOR EXTRACTANTS: THE D1(2-ETHYLHEXYL) SULFOXIDE,DODECANE, WATER SYSTEM

The nature of the hydration and aggregation of di(2-ethylhexyl) sulfoxide (DEHSO) dissolved in wet dodecane at 25 °C has been characterized using Fourier transform infrared (FTIR) spectrophotometry, Karl Fischer titrations, and tritium-tracer equilibrium measurements. Least-squares computer modeling of the water content of 0.01-to-0.4 M DEHSO solutions equilibrated with water (optionally containing nonextractable CaCl2 to adjust the water activity ay in the range 0.28 to 1.0) indicates that the expected 1:1 species DEHSO H₂0 predominates at low DEHSO concentration (K₁₁ = {DEHSO H₂0} / ({DEHS0]a_w.) = 0.12 ± 0.01) with additional formation of hyarated dimeric species at the higher DEHSO concentrations. Analysis of the water vibrational bands in the FTIR spectra of 0.01-to-0.4 M DEHSO solutions in equilibrium with pure water supports the formation of both the 1:1 species and a dimer, identified by its spectral characteristics as the 2:1 dimer monohydrate. By reference to the available literature on the hydration of weak bases, the results suggest that at least part of the ‘nom'deaiityrsquo; of solutions of weak-base extractants in wet nonpolar diluents may be explained by formation of the discrete 1:1 and 2:1 monohydrate species.     

Development of New Cationic Exchangers for the Recovery of Uranium (VI) from Concentrated Phosphoric Acid

The extraction of uranium (VI) from 5.3 mol.L^?1 phosphoric acid with a series of phosphoric, phosphinic, dithiophosphoric, or dithiophosphinic acid derivatives (0.5 mol.L^?1) in mixture with 0.125 mol.L^?1 TOPO in Isane IP 185 has been investigated. In the frame of the present work, eight acidic phosphorus and thiophosphorus compounds have been synthesized: bis(1,3-diisobutoxypropan-2-yl) phosphoric acid, bis(1,3-bis-(butylthio)propan-2-yl) phosphoric acid, bis(5,8,12,15-tetraoxanonadecan-10-yl) phosphoric acid, bis(1-butoxyheptan-2-yl) phosphoric acid, bis(undecan-6-yl) phosphoric acid, bis(2-(1,3-dibutoxypropan-2-yloxy)ethyl) phosphoric acid, bis(3-butoxy-2-(butoxymethyl)-2-methylpropyl) phosphinic acid, bis(1,3-dibutoxypropan-2-yl) dithiophosphoric acid. The properties of these molecules in mixtures with TOPO have been compared with those of other extractants such as bis(2-ethylhexyl) phosphoric acid, bis(2-ethylhexyl) dithiophosphoric acid, bis(2-ethylhexyl) phosphinic acid, Cyanex® 272, and Cyanex® 301. The replacement of phosphoric acid-type extractant by their phosphinic homologues dramatically decreases the affinity for uranium (VI) whereas the replacement of the phosphoric and phosphinic acid-type extractants by their dithio homologues affects positively the distribution coefficient of uranium (VI). It also appears that the steric hindrance effect is responsible for a significant decrease of the distribution coefficient of uranium (VI). Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science and Technology to view the free supplemental file.     

PHOTO-DEGRADATION OF HYDROPHOBIC DERIVATIVES OF PYRIDINECARBOXYLIC ACID AS COPPER EXTRACTANTS FROM CHLORIDE MEDIA

ABSTRACT

The photo-stability of 2-ethylhexyl pyridine-3-carboxylate and N,N′-di(2-ethylhexyl)pyridine-3,5-dicarboxamide as the model extractants of copper from chloride media were studied and compared with the photo-stability of di(2-ethylhexyl) pyridine-3,5-dicarboxylate, N,N,N′,N′-tetrahexylpyridine-3,5-dicarboxamide and the hydroxyoxime copper extractants. Also the resistance against the UV light the copper(II) complexes of tested extractants were done. The obtained results of photo-degradation indicate that the UV light degraded amide derivatives and esters of pyridine-3,5-dicarboxylic acid and pyridine-3-carboxylic acid. A comparison of the photo-stability of oximes and derivatives of pyridine-3,5-dicarboxylic acid and pyridine-3-carboxylic acid indicates that all tested derivatives of pyridinecarboxylic acid are more stable than hydroxyoxime copper extractants. The copper complexes of derivatives of pyridinecarboxylic acid are less stable than the copper complexes of hydroxyoxime.