THERMODYNAMIC EQUILIBRIA OF THE EXTRACTION OF CHROMIUM(VI) WITH TRI-N-OCTYLPHOSPHINE OXIDE FROM AQUEOUS SOLUTIONS

ABSTRACT

The distribution of chromium( VI ) between aqueous solutions and the kerosene solutions of tri-n-octyl-phosphine oxide (TOPO) have been studied at 25 °C and pH 2-4, in which range the predominant forms of Cr(VI) are HCrO₄ and Cr₂O₇ ^2?. The extraction equilibrium is influenced by the total chromium(VI) concentration, aqueous pH value, and total extractant concentration. The thermodynamic equilibria among all species in the aqueous phase were used for the analysis of distribution data, and the activity coefficients of ionic species were estimated according to Debye-Hiickel or Bromley equation. By numerical method, the complexes of Cr(VI ) with TOPO formed in the organic phase were found to be H₂CrO₄ (TOPO) and H₂Cr₂O₇ (TOPO) ₃. The corresponding extraction constants were 2019 and 3.69× 10⁸, respectively.     

Extraction of molybdenum(VI) from sulfate solutions by LIX 622

The application of LIX 622 (oxime derivative) as an extraction reagent of molybdenum (VI) from sulfate media was studied. The extraction system was studied as a function of contact time, temperature, aqueous pH, diluent of the organic phase and metal and extractant concentrations. The extraction is exothermic and it is dependent on the organic diluent, aqueous pH and reagent concentration. The data have been analysed numerically to determine the stoichiometry of extracted species and their equilibrium constants. It was found that molybdenum was extracted into the organic phase by a complex mechanism which involves the formation of three species (MoO₂L₂, MoO₄H₃HL⁺HSO₄⁻ and MoO₄H₂HL, where L represents the extractant). Molybdenum stripping by acidic and ammonium hydroxide solutions was also studied. © 2000 Society of Chemical Industry     

Extraction of vanadium(V) from sulfate solutions by ACORGA M5640

ACORGA M5640 (hydroxy‐oxime derivative) has been applied as an extraction reagent for vanadium(V) from sulfate media. The extraction system was studied as a function of contact time, temperature, aqueous pH, diluent of the organic phase, and metal and extractant concentrations. The extraction reaction is endothermic and it is dependent on the organic diluent, aqueous pH and extractant concentration. The data have been analysed numerically to determine the stoichiometry of extracted species and their equilibrium constants. It was found that vanadium was extracted into the organic phase by a complex mechanism which involves the formation of two species (VO₂R and VO₂R. HR, where R represents the extractant). Vanadium stripping by acidic and ammonium hydroxide solutions was also studied. Copyright © 2003 Society of Chemical Industry     

Liquid-Liquid Extraction of Uranium(VI) from Aqueous Solution using 1-Hydroxyalkylidene-1,1-diphosphonic Acids

The extraction of uranium(VI) from aqueous solutions has been investigated using 1-hydroxyhexadecylidene-1,1-diphosphonic acid (HHDPA) and 1-hydroxydodecylidene-1, 1-diphosphonic acid (HDDPA), which were synthesized and characterized by elemental analysis and by FT-IR, ¹H NMR, ³¹P NMR spectroscopy. In this article, we propose a tentative assignment for the shifts of those two ligands and their specific complexes with uranium(VI). We carried out the extraction of uranium(VI) by HHDPA and HDDPA from [carbon tetrachloride?+?2-octanol (v/v: 90%/10%)] solutions. Various factors such as contact time, pH, organic/aqueous phase ratio, and extractant concentration were considered. The optimum conditions obtained were: contact time?=?20 min, organic/aqueous phase ratio?=?1, pH value?=?3.0, and extractant concentration?=?0.3 M. The extraction yields are more significant in the case of the HHDPA which is equipped with a hydrocarbon chain, longer than that of the HDDPA. Logarithmic plots of the uranium(VI) distribution ratio vs. pH_eq and the extractant concentration showed that the ratio of extractant to extracted uranium(VI) (ligand/metal) is 2:1. The formula of the complex of uranium(VI) with the HHDPA and the DHDPA is UO₂(H₃L)₂ (HHDPA and DHDPA are denoted as H₄L). A spectroscopic analysis showed that coordination of uranium(VI) takes place via oxygen atoms.     

A CHEMICAL MODEL OF THE SOLVENT EXTRACTION SYSTEM: NITRIC ACID- URANYL NITRATE- WATER - TRI-n-BUTYL PHOSPHATE (TBP) - DILUENT

ABSTRACT

A mathematical model founded on the equilibrium constants expressions has been developed for the simultaneous extraction of nitric acid and uranyl nitrate with TBP in alkane diluents. The model uses chemical activities of nitric acid and uranyl nitrate in the aqueous phase and the stoichiometric concentrations of their TBP solvates in the organic phase. The apparent formation constants of the species (TBP)₂, (TBP)₂HNo₃, TBPHNO₃, and UO₂(NO)₃ 2TBP, present in the organic phase, have been established. The model fits well the distribution results over the whole concentration range of the extraction isotherms, and extractant concentrations 5–10% TBP. The starting data are the chemical activities of nitric acid and uranyl nitrate in the aqueous phase and their stoichiometric concentrations in the organic phase.     

SOLVENT EXTRACTION OF PALLADIUM(II) WITH A SCHIFF BASE AND SEPARATION OF PALLADIUM FROM Pd(II)-Pt(VI) MIXTURE

ABSTRACT

A new Schiff base extractant, N,N'-bis[l-phenyl-3-methyl-5-hydroxy-pyrazole-4-benzylidenyl]-l,3-propylene diamine (H₂A) was synthesized and characterized. The extraction mechanism of palladium(II) from HNO₃ or HClO₄ medium with H₂A in chloroform or toluene was investigated. The influences of the Schiff base concentration in the organic phase, the concentration of palladium, the pH and anions (Cl^?, S0₄ ^?, NO₃ ^?, ClO₄ ^?) in the aqueous phase and the temperature on the distribution ratio for palladium (II) have been examined. The extracted complex has been confirmed by chemical analysis, thermoanalyses and IR spectroscopy. It was found that palladium is extracted according to the following extraction reaction:

The extraction equilibrium constants of palladium(II) were 8·4 and 21·3 in chloroform and toluene diluents, respectively. The values for the enthalpy and standard free energy of extraction were also obtained. The separation of Pd(II) from the mixed solution of Pd(II)-Pt(IV) was achieved by adjusting the pH.     

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.     

Liquid Emulsion Membrane (LEM) Process for Vanadium (IV) Enrichment: Process Intensification

Abstract

A liquid emulsion membrane (LEM) system for vanadium (IV) transport has been designed using di‐2‐ethylhexyl phosphoric acid (D2EHPA), dissolved in n‐dodecane as carrier. The selection of extractant, D2EHPA, was made on the basis of conventional liquid‐liquid extraction studies. The work has been undertaken by first carrying out liquid‐liquid extraction studies for vanadium (IV) to get stoichiometric constant (n), and equilibrium constant (K_ex), which are important for process design.

Transport experiments were carried out at low vanadium (IV) concentration (ppm level). The studies on liquid emulsion membrane included i) the influence of process parameters i.e. feed phase pH, speed of agitation, treat ratio, residence time and ii) emulsion preparation study i.e., organic solvent, extractant concentration, surfactant concentration, internal strip phase concentration. When the strip phase concentration was 2 mol/dm³ (H₂SO₄) and feed phase pH 3 better extraction of vanadium was obtained. Higher V_m/V₁ gave higher extraction of vanadium (IV). A simplified, design engineer friendly model was developed.     

EXTRACTION OF MOLYBDENUM(VI) BY PRIMENE JMT

ABSTRACT

Distribution of molybdenum (VI) between aqueous sulfuric acid solution and an organic solution containing Primene JMT has been studied.

The aqueous solutions consist of ammonium molybdate with acid concentration in a pH range 2 - 6.5, the concentration of amine in the organic phase being 0.1 mol/dm³ in benzene. The presence of various species in the aqueous phase is considered and the equilibrium composition of substances in the organic phase is determined. The extraction mechanism is discussed.     

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.     

Removal of Cu2+ from Water Using Liquid-Liquid Microchannel Extraction

The very good extraction selectivity of Cu²⁺ from water was demonstrated with a new microchannel equipment, by employing di-(2-ethylhexyl)phosphoric acid (D2EHPA) as an extractant and kerosene as a solvent. The effects of different experimental parameters on the extraction efficiency E, the volumetric mass transfer coefficient K_La, and the entrainment were experimentally investigated. The results showed that the extraction efficiency increased with increasing temperature, extractant concentration, phase ratio (organic/aqueous), and pH. The total flow rate, phase ratio, and pH were found to have a great effect on the mass transfer, whereas the temperature and the extractant concentration showed little effect.     

The Extraction of TcO− 4 and Pd(II) by Dihexyl-N,N-diethylcarbamoylmethylphosphonate from Nitric Acid

Abstract

The extraction behavior of TcO^? ₄ and Pd(II) from aqueous HNO₃ was studied using dihexyl-N,N-diethylcarbamoylmethylphosphonate. Distribution ratios were studied as a function of contact time; concentration of solute, acid, and extractant; and extraction temperature. Extraction measurements of TcO^? ₄ were also made using H₂SO₄ in the aqueous phase. It was found that the extractant dependency for TcO^? ₄ is third power. Distribution measurements for TcO^? ₄ as a function of temperature in the range of 0–50°C led to a calculation of the thermodynamic quantity ΔH. A third-power extractant dependency for Pd(II) is suggested but is not strongly corroborated. Interpretation of Pd(II) data was hindered by slow kinetics (approximately 1 h to reach equilibrium and variations in distribution ratios with aqueous Pd(II) concentration.     

EXTRACTION OF DIVALENT METALS WITH BIS(2,4,4 TRIMETHYLPENTY) PHOSPHINIC ACID

The extraction of Cd(II), Cu(II) and Zn(II) from 0.1 mol dm^minus3 aqueous nitrate solutions with bis(2,4,4-trimethylpentyl)phosphinic acid (HBTMPP) dissolved in Isopar-H has been studied with relation to the total extractant concentration, the equilibrium pH and the total metal concentration in the aqueous phase.

The stoichiometry of the extracted species and their equilibrium constants have been determined by graphical and numerical methods and appear to be CdA₂ (HA)₂ and CdA₂ (HA)₃ for Cd(II), CuA₂(HA)₂ for Cu(II) and ZnAzHA and ZnAz(HA)₂ for Zn(II). The extraction efficiency follows the order Zn(II)<Cu(II)<Cd(II)     

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.     

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.     

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf₂N) has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf₂N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

Solvent extraction of silver by LIX® 79: experimental equilibrium study

The extraction of silver(I) from argentocyanide aqueous cyanide solutions using LIX^® 79 has been studied. Different variables that could affect the extraction system were evaluated: equilibration time, aqueous pH, metal and extractant concentrations, and organic phase diluent. The extraction of the Ag(CN)₂^? complex with respect to other metal‐cyano complexes has also been studied on both synthetic and real leach solutions. Experimental data relating to silver have been analysed numerically to determine the stoichiometry of the extracted species and its equilibrium constant. It was found that silver(I) was extracted into the organic phase by the formation of the species RHAg(CN)₂ (LIX 79 = R). Copyright © 2004 Society of Chemical Industry     

Separation of Cobalt and Nickel with Phenylphosphonic Acid Mono-4-tert-octylphenyl Ester by Liquid Surfactant Membranes

Abstract

The separation of cobalt and nickel with liquid surfactant membranes (LSMs) was carried out in a stirred cell using a newly synthesized extractant. The effect of a surfactant on the kinetics of cobalt and nickel extraction was investigated to elucidate the role of a surfactant used in LSMs. The extraction equilibrium of these metals was also examined. Further, the interfacial tension between the organic and aqueous phases was measured to elucidate the adsorption equilibrium of a surfactant. It was found that the interfacial activity of the extractant is as high as that of a surfactant. In the extraction equilibrium study of these metals, extraction equilibrium constants were obtained for cobalt and nickel for the following equations:

Co²⁺ + 2(HR)₂=CoR₂(HR)₂ + 2H⁺ Ni²⁺ + 3(HR)₂=NiR₂2(HR)₂ + 2H⁺ The effects of the extractant and surfactant on the extraction rate of cobalt and nickel in LSMs were studied. The results were analyzed by a proposed model with an interfacial reaction, and rate constants were obtained for each metal. It was found that the new extractant has a very strong extractability for each metal compared with a conventional commercial extractant such as 2-ethylhexylphosphonic acid mono-2-elhylhexylester (commercial name, PC-88A) or di(2-ethylhexyl)phosphoric acid (D2EHPA). Further, a surfactant strongly affected the extraction rate and the separation of these metals, and a cationic surfactant was selected.     

Solvent Extraction Studies for Separation of Zn(II) and Mn(II) from Spent Batteries Leach Solutions

This study aims at assessing the possibility of using solvent extraction processes for separating Zn(II) and Mn(II) dissolved in aqueous solutions obtained by acid bioleaching of spent alkaline and Zn-C batteries. In this context, Cyanex 272 and DEHPA were tested as extractant agents, and the former was shown to have better performance. Hence, the effect of four factors (equilibrium pH, extractant concentration, A/O ratio, and temperature) into three response variables (extraction efficiency of Zn, Y_Zn; extraction efficiency of Mn, Y_Mn; separation factor, β) were tested according to a full factorial design (2⁴) with two replicated center points. Our study revealed that Y_Zn depends mainly on the extractant concentration, Y_Mn on the equilibrium pH and β on the equilibrium pH, extractant concentration, and A/O ratio as well as on second and third order interactions. One extraction step is sufficient to reach high extraction of zinc in synthetic solutions, but two stages were required for real leaching liquor. The extraction kinetics is fast (less than 15 min) for both metals, even when real liquor was tested. The organic solvent can be efficiently recovered using a stripping solution of H₂SO₄ 1 M and thus the process can be considered environmentally sustainable.