SOLVENT EXTRACTION OF Ni(ll) WITH THE ACTIVE COMPONENT OF LIX 54

ABSTRACT

The solvent extraction of Ni(II) with the active component of the commercial extractant Lix 54 in different synergic mixtures, using tri-n-octylphosphine oxide (TOPO), tri-n-laurylamine (TLA), di-(2-ethylhexyl)phosphoric acid (HDEHP), tributylphosphate (TBP) and 4-methylpyridine as synergic reagents is compared in this work, the highest synergic effects corresponding to the presence of TOPO and 4-methylpyridine. For this reason, the extraction of Ni(ll) from a 1.0 mol.dnr³ KN0₃media by the mixture of the active component of Lix 54 and 4-methylpyridine has been extensively studied in this work. The results have been treated both graphically and numerically in order to find a suitable chemical model of the species responsible for the extraction as well as their extraction constants.     

KINETICS AND MECHANISM OF THE INTERFACIAL MASS TRANSFER OF Zn2+, Co2+, Ni2+ IN THE SYSTEM: BIS(2-ETHYLHEXYL)PHOSPHORIC ACID,n-DODECANE - KNO3, WATER

ABSTRACT

The mass transfer rate of Zn(II), Co(II) and Ni(II) between aqueous nitrate solutions and n-dodecane solutions of the organic soluble ligand HDEHP has been investigated using a forced convection, constant interfacial area stirred cell. The distribution ratios necessary to evaluate the kinetic experiments have been determined and the equilibrium constants which describe the heterogeneous complex formation reaction between Zn²⁺, Co²⁺, Ni²⁺ and HDEHP have been evaluated. The results have been interpreted according to two limiting models: 1) the mass transfer rate is controlled by slow reversible interfacial reactions, 2) the mass transfer is controlled by interfacial film diffusion. Both models are adequate to Interpret the experimental data. The conclusion Is reached that, if interfacial chemical reactions are rate controlling, rate constants of interfacial complex formation reactions independent of the nature of the cation are obtained. This result supports a reaction mechanism which is rate controlled by the microscopic diffusion of the cation through a viscous and structured layer of interfacial water adjacent to the liquid interface     

INTEKFACIAL ACTIVITY OF 2-HYDH0XY-5-ALKYLBEKZALDEHYDE OXIMES AHD MECHANISM AND KINETICS OF COPPER EXTRACTION

Different adsorption isotherms such as the Gibbs, Szyszkowski,Frumkln and Temkin and polynomial were found as fits well to experimental interfacial tension isotherms for 2-hydroxy-5-alkylbenzaldehyde oximes at octane/water and xylene/water interfaces. The values of surface excess computed according to them increase as the length of the alkyl chain length increases for xylene/water system. Different behaviour was found at octane/water interface.

The interfacial activity data were used to predict reaction orders against hydroxyoxime for different proposed mechanisms of copper extraction from acid sulphate solution.It was shown that an interfacial mechanism is very probable for compounds with long alkyl chains. For these compounds the extraction limiting step is the reaction between hydroxyoxime molecules present near the interface and the intermediate 1:1 complex.     

INFLUENCE OF THE ACETATE MEDIUM ON THE EXTRACTIONOF Co(II) BYDI-2ETHYLHEXYL PHOSPHORIC ACID

The distribution of Co(II) between aqueous sodium nitrate medium or acetate-buffered medium and kerosene solutions of di-2-ethylhexyl phosphoric acid has been studied.

Under these conditions it has been possible to observe that the ions existing in the aqueous medium play a significant role in the extraction of metal. Thus, the main species extracted from nitrate medium is Co(DEHP)₂(HDEHP)₂, whereas in the presence of low concentrations of acetate a dimerized species (CoAc)₂ (DEHP) ₂ (HDEHP)₄ is extracted, but (Co₂Ac₃DEHP) (HDEHP)₃ at high acetate concentrations.     

Kinetics of Solvent Extraction of Iron(III) from Sulfate Medium by Purified Cyanex 272 using a Lewis Cell

Abstract

The kinetics of the forward and backward extraction of the title process have been investigated using a Lewis cell operated at 3 Hz and flux or (F) – method of data treatment. The dependences of (F) in the forward extraction on [Fe³⁺], [H₂A₂]_(o), pH, and [HSO₄ ^?] are 1, 0.5, 1, and ?1, respectively. The value of the forward extraction rate constant (k _f ) has been estimated to be 10^?7.37 kmol^3/2 m^?7/2 s^?1. The analysis of the experimentally found flux equation gives the following simple equation: F _f =10^0.13 [FeHSO₄ ²⁺] [A^?], on considering the monomeric model of BTMPPA and the stability constants of Fe(III)‐HSO₄ ^? complexes. This indicates the following elementary reaction occurring in the aqueous film of the interface as rate determining: [FeHSO₄]²⁺+A^?→[FeHSO₄.A]⁺. The very high activation energy of 91 kJ mol^?1 supports this chemical reaction step as rate-determining. The negative value of the entropy change of activation (?94 J mol^?1 K^?1) indicates that the slow chemical reaction step occurs via the S_N2 mechanism.

The backward extraction rate can be expressed by the equation: F _b =10^?5.13 [[FeHSO₄A₂]]_(o) [H⁺] [H₂A₂]_(o) ^?0.5. An analysis of this equation leads to the following chemical reaction step as rate-determining: [FeHSO₄A₂]_(int)→[FeHSO₄A]+A_(i) ^?. However, the activation energy of 24 kJ mol^?1 suggests that the backward extraction process is intermediate controlled with greater contribution of the diffusion of one or the other species as a slow process. The equilibrium constant obtained from the rate study matches well with that obtained from the equilibrium study.     

Equilibrium and kinetic studies on the extraction of gadolinium(III) from nitrate medium by di‐2‐ethylhexylphosphoric acid in kerosene using a single drop technique

The liquid–liquid extraction of Gd(III) from aqueous nitrate medium was studied using di‐2‐ethylhexylphosphoric acid (HDEHP) in kerosene. On the basis of the slope analysis data, the composition of the extracted species was found to be [Gd A₃(HA)] with the extraction equilibrium constant (K_ex) = (1.48 ± 0.042) × 10^?12 mol dm^?3. The results of the effect of temperature on the value of the equilibrium extraction constant indicated the endothermic character of the extraction system. The kinetics of the forward extraction of Gd³⁺ from nitrate medium by HDEHP in kerosene was investigated using the single drop column technique. The rate of flux (mass transfer per unit area) was found to be proportional to [Gd(III)], [H₂A₂]_(o), [NO₃^?], and [H⁺]^?1 in the liquid drop organic phase. The forward extraction rate constant, k_f, was 2.24 × 10^?3 m s^?1 using the equation: Copyright © 2005 Society of Chemical Industry     

SYNERGIC EXTRACTION OF AMMONIACAL Ni

The synergic extraction of Ni from ammoniacal sulfate solution by mixtures of LIX 64N and Kelex 100 was studied using slope analysis, continuous variation, and mathematical modeling. This extractant pair was discovered as part of a study to find extractants that perform ?at the higher pH level needed for leaching Cu, Ni, and Co, and thus eliminate ammonia stripping/recharging steps in current processes. Ni was more efficiently extracted at higher pH with the LIX 64N/Kelex mixture than with either extractant alone. A model is proposed based on four different stoichiometrics, each contributing to the overall reaction. Those four Ni/LIX 64N/ Kelex species are 1/2/0, 1/0/3, 1/1/1, and 1/2/1. Ammonia is coextracted, but can be selectively scrubbed with 2 g/L H₂S0₄ Ni can be selectively stripped from the Ni- and Cu-loaded extractants with 10 g/L H₂S0₄ then Cu is stripped with 150 g/L H₂S0₄ A continuous process was simulated with a batchwise circuit, which showed no loss of extraction efficiency in 10 cycles.     

EXTRACTION OF URANIUM(VI) AND VANADIUM(V) WITH 4-ADIPOYL AND 4-SEBACOYL DERIVATIVES OF BIS(1-PHENYL-3-METHYL-PYRAZOLONE-5) AND EFFECT OF DECANOL ON THE DISTRIBUTION BEHAVIOUR OF THESE METAL IONS

ABSTRACT

The liquid-liquid extraction of U(VI) and V(V) with 4-adipoylbis(l-phenyl-3-methyl-pyrazolone-5) (H₂AdP)′ and 4-sebacoylbis(l-phenyl-3-methyl-pyrazolone-5) (H₂SP) was studied in the presence and absence of decanol (DOH). The studies show that in the absence of DOH the extracted species were (U0₂) ₂(AdP) ₂ U0₂(HSP) ₂, V0₂(HAdP) and V0₂(HSP). Addition of DOH to the organic phase resulted in enhancement of the extraction of V(V) at high HCI concentrations but reduced the extraction of U(VI) due to a change in extraction mechanism. Subsequently, ion-pair complex species VO₂(HAdP)DOH₂ ⁺)₂CI_- and V0₂(HSP)(DOH₂ ⁺)₂.2CI^- were extracted. The extraction constants K_cx and pH_1/2 for the various extraction systems were determined and used for explaining the various extraction mechanisms observed.     

RATE OF COPPER EXTRACTION AND INTERFACUL ACTIVITY OF MODEL β-DHCETONES

ABSTRACT

Interfacial tension isotherms and rate of copper extraction were studied for model β-diketones of LIX 54 and of pyrazolone type. The effect of the position and structure of the hydrophobic alky1 group upon interfacial activity and rate of extraction is discussed. The preadsorption of extractant molecules at the water/hydrocarbon interface is not needed to obtain a quick and effective extraction.     

EXTRACTION OF ZINC(II) ION BY DIDODECYLNAPHTHALENESULFONIC ACID (HDDNS) IN CARBON TETRACHLORIDE: THE ROLE OF AGGREGATION

The aggregation behavior of didodecylnaphthalenesulfonic acid (HDDNS) in carbon tetrachloride at 25.0 °C has been investigated by interfacial tension measurements, FT1R spectrophotometry, Karl Fischer titrations, and computer-aided analysis of the extraction of Zn(ll) ion from nitric acid solution. HDDNS forms hydrated aggregates at analytical HDDNS concentrations greater than 4.4 x 10^-6 M up to at least 0.1 M. Slope analysis of the extraction of Zn(ll) up to ca. 5% loading with 0.001-0.1 M HDDNS solutions indicates that the size of the aggregates lies in the range 5-8 and increases gradually with increasing HDDNS concentration. By use of the computer programs SXLSQ and SXLSQA the extraction of Zn(ll) up to ca. 40% loading may be described to within twice the experimental precision by formation of the three species H_nA_n ZnA_nH_n-2, and Zn2A_nH_n-4 (A = DDNS-anion) characterized by a common aggregation number n in the range 5-8. Under the conditions employed, organic-phase nonideality effects as estimated by the Hildebrand-Scott treatment applied in the program SXLSQA are much less useful in understanding the extraction behavior than mass-action and speciation effects.     

Simulations of vapor–liquid phase equilibrium and interfacial tension in the CO2–H2O–NaCl system

Direct interfacial molecular dynamics simulations are used to obtain the phase behavior and interfacial tension of CO₂–H₂O–NaCl mixtures over a broad temperature and pressure range (50°C ≤ T ≤ 250°C, 0 ≤ P ≤ 600 bar) and NaCl concentrations (1–4 mol/kg H₂O). The predictive ability of several existing water (SPC and TIP4P2005), carbon dioxide (EPM2 and TraPPE), and sodium chloride (SD and DRVH) models is studied and compared, using conventional Lorentz–Berthelot combining rules for the unlike‐pair parameters. Under conditions of moderate NaCl molality (～1 mol/kg H₂O), the predictions of the CO₂ solubility in the water‐rich and CO₂‐rich phase resemble those in the CO₂–H₂O system [Liu et al., J Phys Chem B. 2011;115:6629–6635]. Consistent with our previous work, the TraPPE/TIP4P2005 model combination gives the best overall performance in predicting coexistence composition and pressure in the water‐rich phase. Critical assessments are also made on the ranges of temperature and pressure where particular model combinations work better. The dependence of the interfacial tension on temperature and pressure is better predicted by the TraPPE/TIP4P2005 and EPM2/SPC models, whereas the EPM2/TIP4P2005 model overestimates this property by 10–20%, possibly due to the inadequacy of the combining rules. It is also found that the interfacial tension increases with salt concentration, consistent with experimental observations. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3514–3522, 2013     

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.     

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.     

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.     

EXTRACTION OF Ni(It) BY DI-(2-ETHYLHEXlfL)PHUSPHOKIC ACID DISSOLVED IN TOLUENE

ABSTRACT

The extraction of Ni(II) from 1.0 mol-dm^-3aqueous NaNO₃medium by di-(2-ethylhexyl) phosphoric acid (HDEHP) dissolved in toluene has been studieo as a function of the total extractant concentration, the equilibrium pH and the total raetal concentration in the aqueous phase. Nickel distribution data have been interpreted in terms of the formation of NiR₂(HR)₂, and NiR₂species in the organic phase in the low pH range anc by the formation of Na-HUEHP micelles, due to the neutralization of the reagent in the organic phase, and the further exchange of Na⁺by Ni²⁺in these micelles in the high pH range for each of the total extractant concentrations used.     

EFFECTS OF GLYCEROL ON THE DRYING OF GELATIN AND SUGAR SOLUTIONS

ABSTRACT

The water diffusion coefficients D of gelatin, sucrose arid maltodextrin solutions were determined from the isothermal drying (desorption) rates as a function of water content u ( 0.1 < u < 1.0 ) and temperature (303, 323K) for various glycerol contents ( W_G = 0 – 0.43 kg-glycerol/kg-total solid). When W_G was above 0.2, D increased especially at low water contents (u < 0.25). The desorption isotherms were measured for the same systems. The equilibrium water content at a given water activity A_w decreased with an increase in W_G when A_w < 0.5. This indicates that adding glycerol weakens the water-solute interaction especially at low water contents. Glycerol also softened gelatin films and resulted in loss possibilities of surface cracks during drying.     

STUDIES ON EXTRACTION AND COORDINATION OF RARE EARTHS WITH β-KETOPHOSPHONATES

The rare earth extraction and coordination by three β-ke-tophosphonates with various structure, dibutyl 2-keto-2-phenyl-ethylphosphonate, (C₄H₉O)₂P(O)CH₂C(O)C₆H₅, (I), dibutyl 2-keto-pentylphosphonate, (C₄H₉O)₂P(O)CH₂C(O)C₃H₇, (II) and dibutyl 2-keto-3-methylbutylphosphonate, (C₄H₉O)₂P(O)CH₂C(O)CH(CH₃)CH₃, (III) from nitric acid medium have been described in this paper. The regularity of rare earth extraction with these β-ketophos-phonate reveals the same manner and resembles that of the common extractant, tributylphosphate (TBP). The extracted species has been deduced as Nd(NO₃)₃.3L and HNO₃-L by the slope method. By investigating the shift of P=0 and C=0 in IR spectra of the coordination compound prepared by saturated method, the predomination of P=0 has been established which coincides with the estimation from their extraction behavior.     

Extraction Behavior of Am(III) and Eu(III) from Nitric Acid Medium in Tetraoctyldiglycolamide-Bis(2-Ethylhexyl)Phosphoric Acid Solution

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-octyldiglycolamide (TODGA), bis(2-ethylhexyl)phosphoric acid (HDEHP), and n-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.     

AN INDIRECT APPROACH TO SYNERGISTIC EXTRACTION MECHANISMS: SPECTROSCOPY OF INDIUM ( III) LIPOPHILIC COMPLEXES EXTRACTABLE FROM PERCHLORATE MEDIUM BY TWO 1-PHENYL-3-HETHYL-4-ACYL-PYHAZOL-5-OLS AND TRI-N-OCTYLPHOSPHINE OXIDE

With the aim of improving our knowledge about the extraction of indium from perchlorate media, by 1-phenyl-3-methyl-4-acyl-pyrazol-5-ols, "HL" (HPMBP: acyl = benzoyl, HPMTP: acyl= thenoyl) and their mixtures with tri-n-octylphosphine oxide, "T0P0", in toluene, synthetic and extraction organic phases, and extractable complexes, have been studied by phosphorus-31 and proton

NMR, and IR spectroscopy. NMR measurements show that the reaction

generally assumed to describe the synergistic effect, does not occur in homogeneous organic phases, which implies an interfacial mechanism for the synergistic extraction.

In the extracted complexes, L^- behave in all cases as a bidentate ligand. However, while the three chelate rings of In L₃ (H₂O) are identical, there are only two chelate rings in InL₃ (TOPO) ₂, the bond of the third acylpyrazololato