Kinetic studies on the extraction of uranium(VI) from phosphoric acid medium by bulk liquid membrane containing di-2-ethylhexyl phosphoric acid

To go through the first stage of industrial solvent extraction process in order to recover uranium from phosphate rocks by liquid membrane techniques, as a simple model, the kinetics of facilitated transport of uranium(VI) from a dilute phosphoric acid medium into more concentrated phosphoric acid media as a receiving phase through a bulk liquid membrane containing di-2-ethylhexyl phosphoric acid as a carrier was studied. The influence of phosphoric acid concentration in the source and receiving phases, carrier concentration, type of solvent, stirring speed and temperature were investigated. The kinetic parameters (k _e, k _s, t _max, J _max) were calculated for the interface reactions assuming two consecutive, irreversible first-order reactions. The activation energy values were calculated as 29.40 and 19.51 kJ mol^?1 for extraction and stripping, respectively. The values of calculated activation energy indicated that both the extraction and stripping processes were controlled by mixed regime (both kinetic and diffusion). In addition, the influence of adding trioctyl-phosphine oxide into the membrane phase as a synergic agent on the transport kinetics was determined.     

Kinetic Study of Mercury(II) Transport through a Bulk Liquid Membrane Using Cyanex 301 as Carrier

A kinetic study of Hg(II) ions transport through a bulk liquid membrane (BLM) was investigated. The commercially available liquid bis(2,4,4‐trimethyl(pentyl) dithiophosphinic acid) (Cyanex 301) was employed as mobile carrier. The influences of the carrier concentration in the liquid membrane, HNO₃ concentration in the feed phase, type of organic solvent, composition of the receiving phase, and stirring speed on mass transfer were studied. Various solvents including CH₂Cl₂, CHCl₃, C₂H₄Cl₂ and CCl₄ were used as organic membrane. Among the solvents, CHCl₃ provided the superior results. The kinetic parameters (k₁, k₂, R_m^max, t^max, J_d^max, and J_a^max) were calculated for the interface reaction assuming two consecutive, irreversible first‐order reactions. The analysis of Hg(II) accumulation in liquid membrane and the rate‐controlling step under different experimental conditions were elucidated. The experiments demonstrated that Cyanex 301 is an appropriate carrier for Hg(II) transport through liquid membrane.     

Carrier‐Mediated Transport of Hg(II) through Bulk and Supported Liquid Membranes

The transport of Hg (II) ions from an aqueous solution into an aqueous receiving solution through bulk and supported liquid membranes containing a calix[4]arene derivative 1 as a carrier was examined. The kinetic parameters of bulk liquid membrane studies were analyzed assuming two consecutive, irreversible first‐order reactions. The influence of temperature, stirring rate, carrier concentration and solvent on the kinetic parameters (k₁, k₂, R_m ^max, t_max, J_d ^max, J_a ^max) has also been investigated. The membrane entrance rate, k₁, and the membrane exit rate, k₂, increased with increasing temperature and stirring rate. The activation energy values are calculated as 4.87 and 48.63 kj mol^?1 for extraction and reextraction, respectively. The values of calculated activation energy indicate that the process is diffusionally controlled by species. Also, the transport behavior of Hg²⁺ from aqueous solution through a flat‐sheet supported liquid membrane has been investigated by the use of calix[4]arene derivative 1 as carrier and Celgard 2500 as the solid support. A Danesi mass transfer model was used to calculate the permeability coefficients for each parameter studied. The highest values of permeability were obtained with 2‐nitrophenyloctyl‐ether (NPOE) solvent and the influence was found to be in the order of NPOE>chloroform>xylene.     

Transport of U(VI) from sulphuric acid medium across supported liquid membrane (SLM) containing di-(2-ethylhexyl) phosphoric acid (D2EHPA)/n-dodecane as a carrier

This paper reports on the supported liquid membrane (SLM) based transport studies of U(VI) from sulphate medium using di-(2-ethylhexyl) phosphoric acid/n-dodecane as carrier. Polytetrafluoroethylene membrane was used as solid support and H₂SO₄ as receiver phase. The effects of various parameters such as receiver phase concentration, feed acidity, carrier concentration, U(VI) concentration, membrane thickness and membrane pore size on U(VI) transport had been investigated. With increase in H₂SO₄ concentrations and pH of feed solution there is an increase in U(VI) transport across the SLM. Similarly with increase in membrane thickness the U(VI) transport decrease whereas in case of pore size variation reverse results are obtained. The membrane thickness variation results showed that the U(VI) transport across the SLM is entirely diffusion controlled and the diffusion coefficient the D _(o) was calculated as 1.36 × 10^?7 cm² s^?1. Based on optimized condition, a scheme had been tested for selective recovery of U(VI) from ore leach solution containing a large number of other metal ions.     

Dysprosium pertraction through facilitated supported liquid membrane using D2EHPA as carrier

The pertraction of dysprosium (Dy) through a supported liquid membrane (SLM) system consisting of PTFE (polytetrafluoroethylene) support, D2EHPA (di-2-ethylhexyl phosphoric acid) dissolved in kerosene as membrane solution, and HNO₃ solution as stripping solution, was studied. The experiments were designed by the Taguchi method in order to investigate the effects of initial Dy concentration, feed phase pH, different stripping solution concentration, and D2EHPA concentration in the membrane phase on Dy pertraction. Optimal experimental conditions for Dy pertraction were obtained using an analysis of variance (ANOVA) (feed concentration: 130 mg L^?1, D2EHPA concentration: 0.90 M, feed phase pH: 5, stripping phase concentration: 2 M). In addition, the stability of the carrier in terms of its leaching from the membrane support was studied over a period of 6 days and was found to be satisfactory over that time.     

Pertraction of methylene blue using a mixture of D2EHPA/M2EHPA and sesame oil as a liquid membrane

An experimental study on the pertraction of methylene blue (MB) through a supported liquid membrane (SLM) using a mixture of mono-(2-etylhexyl) ester of phosphoric acid (M2EHPA) and bis-(2-etylhexyl) ester of phosphoric acid (D2EHPA) and sesame oil as the liquid membrane (LM) was performed. Parameters affecting the pertraction of MB such as initial MB concentration, carrier concentration, feed phase pH, and stripping phase concentration were analyzed. Optimal experimental conditions for MB pertraction (permeability of 5.63 × 10^?6) were obtained after a 7 h separation with the MB concentration in the feed phase of 80 mg L^?1, D2EHPA/M2EHPA concentration in membrane phase of 40 vol. %, feed pH of 6, and acetic acid concentration in the stripping phase of 0.4 mol L^?1. Kinetics of transport and stability of the SLM system were also studied and the mass transfer coefficient for this system was evaluated. Scanning electron microscopy (SEM) was used to morphologically characterize the membrane surface.     

Equilibrium and kinetics study of Gd(III) and U(VI) adsorption from aqueous solutions by modified Sorrel’s cement

Modified Sorrel’s cement was prepared by the addition of ferric chloride. The modified cement (MF5) was analyzed and characterized by different methods. Adsorption of Gd(III) and U(VI) ions in carbonate solution has been studied separately as a function of pH, contact time, adsorbent weight, carbonate concentration, concentration of Gd(III) and U(VI) and temperature. From equilibrium data obtained, the values of Δ H, Δ S and Δ G were found to equal −30.9 kJ ⋅ mol⁻¹, −85.4 J ⋅ mol⁻¹ ⋅,K⁻¹, and −5.4 KJ ⋅ mol⁻¹, respectively, for Gd(III) and 18.9 kJ ⋅ mol⁻¹, 67.8 J ⋅ mol⁻¹ K⁻¹ and −1.3 KJ ⋅ mol⁻¹, respectively, for U(VI). The equilibrium data obtained have been found to fit both Langmuir and Freundlich adsorption isotherms. The batch kinetic of Gd(III) and U(VI) on modified Sorrel’s cement (MF5) with the thermodynamic parameters from carbonate solution were studied to explain the mechanistic aspects of the adsorption process. Several kinetic models were used to test the experimental rate data and to examine the controlling mechanism of the adsorption process. Various parameters such as effective diffusion coefficient and activation energy of activation were evaluated. The adsorption of Gd(III) and U(VI) on the MF5 adsorbent follows first-order reversible kinetics. The forward and backward constants for adsorption, k ₁and k ₂ have been calculated at different temperatures between 10 and 60^∘C. Form kinetic study, the values of Δ H ^* and Δ S ^* were calculated for Gd(III) and U(VI) at 25^∘C. It is found that Δ H ^* equals −14.8 kJmol⁻¹ and 7.2 kJmol⁻¹ for Gd(III) and U(VI), respectively, while Δ S ^* were found equal −95.7 Jmol⁻¹K⁻¹ and −70.5 Jmol⁻¹K⁻¹ for Gd(III) and U(VI), respectively. The study showed that the pore diffusion is the rate limiting for Gd(III) and (VI).     

Study of the kinetics of the transport of Cu(II), Cd(II) and Ni(II) ions through a liquid membrane

The coupled transport of Cu(II), Cd(II) and Ni(II) ions through a bulk liquid membrane (BLM) containing pyridine-2-acetaldehyde benzoylhydrazone (2-APBH) as carrier dissolved in toluene has been studied. Once the optimal conditions of extraction of each metal were established, a comparative study of the transport kinetics for these metals was performed by means of a kinetic model involving two consecutive irreversible first-order reactions. The kinetic parameters (apparent rate constants of the metal extraction and re-extraction reactions (k ₁, k ₂), the maximum reduced concentration of the metal in the liquid membrane (), the time of the maximum value of R _o ( t _max) and the maximum entry and exit fluxes of the metal through the liquid membrane ( and ) of the extraction and stripping reactions were evaluated and results showed good agreement between experimental data and theoretical predictions. Complete transport through the membrane took place according to the following order: Cd(II)>Cu(II)>Ni(II), with similar kinetic parameters obtained for Cu(II) and Cd(III). The transport behaviour of Ni(II) was different to that of Cu(II) and Cd(III), probably due to the different stoichiometry of the nickel complex compared to those of the other metal ions and the different chemical conditions required for its formation. The influence of the sample salinity on the transport kinetics was studied. k ₁ values decreased slightly when the feed solution salinity was increased for Cu(II) and Ni(II), but not for Cd(II). Values of k ₂ were practically unaffected. The proposed BLM was applied to the preconcentration and separation of metal ions (prior to their determination) in water samples with different saline matrices (CRM, river water and seawater), and good agreement with the certified values was obtained.     

Extraction of Uranium(VI) using D2EHPA/TOPO based supported liquid membrane

This work concerns the extraction of U(VI) using supported liquid membrane (SLM) by di-(2-ethylhexyl) phosphoric acid (D2EHPA) and tri-n-octyl phosphine oxide (TOPO) with polyvinylidene difluoride (PVDF) as a membrane support. The influence of ionic strength (S), stirring rate (V) and extraction time (t) were studied. The effect of membrane thickness on the permeability and extraction yield of uranium was investigated. A comparative study was carried out using a 2³ full factorial design between SLMs with one membrane and two membranes, and to achieve the best conditions of recovery procedure, obtaining the mutual interaction among variables and optimizing these variables. The recovery of U(VI) is almost quantitative, and the supported liquid membrane with two membranes in series is effective.     

Transport of titanium(IV) ions across di-2-ethylhexylphosphoric acid-CCl4 supported liquid membranes

Transport study for Ti(IV) ions using di-2-ethylhexylphosphoric acid (D2EHPA) (carrier)-CCl₄ (diluent) liquid supported membrane in microporous polypropylene hydrophobic film has been performed. The parameters studied are effects of carrier, H₂SO₄, stripping agent (NH₄F) concentrations and temperature variation on flux and permeability coefficients of the metal ion. The optimum concentrations of transport found are 2.04 mol·dm^–3 D2EHPA, 1.0 mol·dm^–3 H₂SO₄ in the feed and 1 mol·dm^–3 NH₄F as stripping agent. The maximum flux and permeability coefficient determined are 1.32·10^–5 mol·m^–2·s^–1 and 8.02·10^–12 mol·m^–2·s^–1, respectively. The transport of this metal ion is increased with increase in temperature. The mechanism of transport appears to be based on coupled counter ion transport phenomenon.     

Sequential Voltammetric Determination of Uranium,Cadmium and Lead by Using the ex situ Bismuth Film Electrode: Application to Phosphate Fertilizers

A sequential voltammetric procedure for the determination of uranium, cadmium and lead was investigated at an ex situ bismuth film electrode (BiFE). First, the adsorptive stripping voltammetry was applied to assay the U(VI)‐cupferron complex in the differential pulse mode (detection limit of 1.0 µg L^?1, 200 s accumulation time). Through the manipulation of the same aliquot of the sample, efforts were made to quantify cadmium and lead by square wave anodic stripping voltammetry. Detection limits of 2.03 µg L^?1 for Cd (II) and 2.43 µg L^?1 for Pb (II) were calculated (100 s accumulation time). The methodology was successfully applied to phosphate fertilizer samples after open vessel wet decomposition (HNO₃/H₂O₂). The following value ranges were evaluated: U (VI) 37.2–150 mg kg^?1, Pb (II) 78.3–204 mg kg^?1 and Cd (II) 44.1–71.6 mg kg^?1. Validation was performed by using the standard reference materials SRM‐695 – phosphate fertilizer – and SRM‐1643e – water.     

Electrocapillary Activity and Adsorptive Accumulation of U(VI)‐Cupferron and U(VI)‐Chloranilic Acid Complexes on Mercury Electrode

Interfacial activity of uranium(VI)‐cupferron and uranium(VI)‐chloranilic acid (CAA) complexes (in 0.1 M acetate buffer pH 4.6 or 0.1 M NaClO₄ respectively) on polarized mercury electrode at 110 mV, 10 mV or ?240 mV respectively vs. saturated calomel electrode (SCE), and under conditions of the application of adsorptive stripping voltammetric techniques was studied. It revealed a competitive effect of interfacial activity of the mentioned complexes consisting in a nonmonotonous effect of the bulk concentration of U(VI) on the adsorption of the mentioned complexing reagents at their constant concentrations. At concentrations lower than 5×10^?5 mol L^?1 the complexes U(VI)‐cupferron or U(VI)‐CAA exhibited a relatively strong electrosorption providing the adsorption coefficients β of the order 10⁴ L mol^?1, the maximum surface excess Γ_m ≈ 5 to 10 μmol m^?2 and average Frumkin interaction coefficients reaching their absolute values 2 to 2.6.     

Ethylene Adsorption and Oxidation Kinetics in the Reactions with Pd(II)/SiO2 and Cr(VI)/SiO2: Consideration of Substrate Distribution between the Gas Phase,Silica Gel,and Reaction Centers

The kinetics of ethylene oxidation by PdCl₂ and CrO₃ complexes supported on silica gel (300 K, closed batch reactor) and the adsorption of C₂H₄ by silica gel and metal complex reaction centers (M ⁿ ) were studied. A new version of the kinetic distribution method was applied to determine the rate constants of ethylene reactions with metal complexes with consideration for the equilibrium distribution of C₂H₄ among the reactor gas phase, silica gel, and M ⁿ . The rate constant of a first-order reaction with respect to Cr(VI) (k _e) remained constant as [M ⁿ ] was increased up to 0.15 mol % with the absence of detectable ethylene adsorption by chromium(VI). In the case of Pd(II)/SiO₂, strong ethylene adsorption by palladium(II) was found, and k _e was an exponential function of [M ⁿ ]. This exponential function is indicative of an increase in the specific activity of Pd(II) with palladium concentration on SiO₂. Taking into account the adsorption of ethylene (physisorption on SiO₂ and chemisorption on Pd(II)), we found an analogy between the kinetic behaviors of Pd(II) in reactions with ethylene on silica gel and with ethylene and other hydrocarbons in solutions.     

Extraction of U(VI) by cyanex-272

Extraction of U(VI) from HNO₃, HCl and HClO₄ media using cyanex-272 (bis[2,4,4 trimethyl pentyl] phosphinic acid)/n-dodecane has been carried out. In the case of HNO₃ and HClO₄ media, the distribution ratio (D) value first decreases and then increases, whereas from HCl medium it first decreases and then remains constant with increase in H⁺ ion concentration. At lower acidities, U(VI) was extracted as UO₂(HA₂)₂ by an ion exchange mechanism, whereas at higher acidities as UO₂(NO₃)₂ ^.2(H₂A₂) following a solvation mechanism. The D for U(VI) by cyanex-272, PC-88A and DEHPA at low acidities follows the order cyanex-272 > PC-88A > DEHPA. Also, cyanex-272 was found to extract U(VI) more efficiently than TBP at 2M HNO₃. The effect of diluents on the extraction of U(VI) by cyanex-272 followed the order cyclohexane > n-dodecane > CCl₄ > benzene. The loading of U(VI) into cyanex-272/n-dodecane from 2M HNO₃ has shown that at saturation point, cyanex-272 was 78% loaded. No third phase was observed at the saturation level. The stripping of U(VI) from the loaded organic phase was not possible with water, it was poor with acetic acid and sodium acetate but quantitative with oxalic acid, ammonium carbonate and sodium carbonate.     

Pertraction of cadmium and zinc ions using a supported liquid membrane impregnated with different carriers

An experimental study on the removal of Cd²⁺ and Zn²⁺ through a supported liquid membrane using a mixture of mono-(2-etylhexyl) ester of phosphoric acid (M2EHPA) and bis-(2-etylhexyl) ester of phosphoric acid (D2EHPA) as carriers is presented. Parameters affecting the Cd²⁺ and Zn²⁺ pertraction such as feed concentration, carrier concentration, pH of the stripping phase, and TBP (tributyl phosphate) concentration were analyzed using the Taguchi method. Optimal experimental conditions for Cd²⁺ and Zn²⁺ pertraction were obtained using the analysis of variance (ANOVA) after a 6 h separation with the initial feed concentration of 8.9 × 10^?4 mol L^?1, carrier concentration of 20 vol. %, TBP concentration of 4 vol. %, and pH of 0.5. Then, under optimum conditions, a comparison of M2EHPA, D2EHPA, and bis-(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302) was performed. Effective pertraction of Cd²⁺ and Zn²⁺ using these carriers was observed in the following order: mixture of M2EHPA and D2EHPA, D2EHPA, Cyanex 302. It was also found that the presence of one metal ion in the feed solution reduces the pertraction rate of the other one.     

U(VI) adsorption by biochar fiber–MnO2 composites

The removal of U(VI) by biochar fibers from aqueous solutions has been investigated prior and after MnO₂ surface-deposition. The removal efficiency has been studied as a function of pH, U(VI) concentration, ionic strength, temperature and contact time. The fibers morphology and surface complexes were analyzed by SEM–EDX and FTIR, respectively. Evaluation of the experimental data indicates that the composite presents extraordinary adsorption capacity (q_max = 3.8 mmol g⁻¹, 904 mg g⁻¹), which is attributed to the formation of inner-sphere surface complexes, and that the adsorption reaction is a relatively fast, endothermic and entropy-driven process.

     

Kinetic study of l-isoleucine transport through a liquid membrane containing di(2-ethylhexyl) phosphoric acid in kerosene

A kinetic study of l-isoleucine transport through a liquid membrane containing di(2-ethylhexyl) phosphoric acid (D2EHPA) in kerosene is presented. The influences of pH in the aqueous feed solution, D2EHPA concentration in the organic phase, the stripping solution composition and H₂SO₄ concentration in the stripping solution were investigated, and the effects of stirring speed and temperature on the transport of l-isoleucine through a bulk liquid membrane (BLM) were studied. The kinetics of l-isoleucine transport could be analyzed in the formalism of a reversible pseudo-first-order reaction followed by an irreversible pseudo-first-order reaction. The pseudo-first-order apparent rate constants of the interfacial transport of l-isoleucine species are determined for the liquid membrane, at various temperatures. The apparent activation energy values are 21.3±1.9, 57.6±5.1 and 31.8±2.7 kJ mol⁻¹ for the extraction reaction, extraction back reaction and stripping reaction, respectively.     

Kinetics and mechanism of the cationic polymerization of trioxane. II. Consideration of hydride transfer

The occurrence of hydride-transfer reactions during the cationic polymerization of trioxane was demonstrated, and rate constants were obtained. The donor of hydride ions in the transfer reactions was the monomer. The hydride-transfer reaction was a first-order reaction with respect to the concentration of the monomer, and it was governed, just as polymerization and depolymerization were (Shieh, Y. T.; Chen. S. A. J. Polym. Sci. Part A: Polym. Chem. 1999, 37, 483–492) by morphological changes. The hydride-transfer rate constants were 5 orders of magnitude smaller than those for polymerizations and depolymerizations. The rate constants for the reactions, including the polymerizations, depolymerizations, and hydride transfers, were smaller for the active centers on the solid surface than for those in solution, that is, k^′_p was less than k_p, k^′_d was less than k_d, and k^′_ht was less than k_ht. As a reaction medium, benzene had special effects on the kinetics of the cationic polymerization of trioxane. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4198–4204, 1999     

Efficacious selective separation of U(VI) over Mo(VI) using novel 2,9-diamide-1,10-phenanthroline ligands: Liquid-liquid extraction and coordination chemistry

Uranium and molybdenum are important strategic elements. The production of ⁹⁹Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum. In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(VI) over Mo(VI). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(VI) over Mo(VI) gradually increased. The SF_U/Mo were around 10,000 at 4 mol/L HNO₃. Three stripping agents were tested with the stripping efficiency of Na₂CO₃ (5%) > H₂O > HNO₃ (0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(VI) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry, ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.