Solvent extraction studies on tetravalent selenium

A systematic study has been carried out on the extraction of SeI₄, by various water-immiscible organic solvents. Extraction has been investigated as a function of H₂SO₄ and Kl concentrations. It has been found that Se(IV) extraction is appreciably increased by addition of iodide ion to sulfuric acid solutions. On the other hand, the presence of water-miscible alcohols and acetone was found to enhance Se(IV) extraction from H₂SO₄–Kl solutions. In the light of the results, an extraction mechanism is suggested.     

Solvent extraction of tetravalent selenium

Summary A systematic study has been carried out on the extraction of SeI₄, by various water-immiscible organic solvents. Extraction has been investigated as a function of H₂SO₄ and KI concentrations. It has been found that the Se(IV) extraction is appreciably increased by addition of iodide ion to sulphuric acid solutions. In addition, the presence of water-miscible alcohols and acetone was found to enhance Se(IV) extraction from H₂SO₄-KI solutions. In the light of the obtained results an extraction mechanism is suggested.

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Untersuchungen zur Extraktion von vierwertigem Selen

Zusammenfassung Es wurde eine systematische Untersuchung zur Extraktion von SeI₄ mittels verschiedener mit Wasser nicht mischbarer organischer Lösungsmittel unternommen. Es wurde die Abhängigkeit der Extraktion von der Konzentration an H₂SO₄ und KI untersucht, wobei sich zeigte, daß die Se(IV)-Extraktion durch Zusatz von Iodid-Ionen zur schwefelsauren Lösung beträchtlich zu steigern ist. Weiters wurde gefunden, daß der Zusatz von wassermischbaren Alkoholen oder Aceton ebenfalls die Extraktion aus H₂SO₄-KI-Lösungen verbessert. Auf Basis dieser Resultate wird ein Extraktionsmechanismus vorgeschlagen.

     

Studies on the extraction behaviour of zirconium from mixed aqueous media with TBP

A systematic study is presented on the extraction of Zr(IV) by tri-n-butylphosphate from H₂SO₄, HNO₃, HCl and HBr solutions as well from binary mixtures of H₂SO₄ and halogen acids. It has been found that Zr(IV) extraction is appreciably increased by addition of halogen acid to sulphuric acid solutions. On the other hand, the presence of water-miscible alcohols and acetone was found to enhance Zr(IV) extraction from HCl and HNO₃ solutions. An investigation of extracted Zr complexes from pure acids and mixed aqueous media enabled an explanation of the observed enhancements. In the light of the obtained results, an extraction mechanism is suggested.     

Matrix-dependent instability of selenium(IV) stored in teflon containers

Solutions of selenium(IV) standards with different acid matrices were stored in containers constructed of boosilicate glass, conventional polyethylene, and fluorinated ethylenepropylene (teflon FEP). After 50 days of storage in FEP, there were highly significant losses of Se(IV) from standards in either 5% HCl/5% H₂SO₄, or 5% H₂SO₄. Increasing the hydrochloric acid concentration, e.g., 15% HCl/5% H₂SO₄, greatly reduced this loss. Addition of selenium-75 (selenate-free) indicated that the losses did not result from physical adsorption onto container surfaces. It is shown that the losses were caused by oxidation of Se(IV) to Se(VI).     

LIX 84 as an extractant for throium(IV), uranium(VI) and molybdenum(VI)

The extraction order of Th(IV), U(VI) and Mo(VI) based on pH_0.5 values is Mo(VI)>U(VI)>Th(IV). Quantitative extraction has been observed for U(VI) by mixture of 10% (v/v) LIX 84 and 0.1M dibenzoylmethane at pH 4.2 and by mixture of 10% LIX 84 and 0.05M HTTA in the pH range 5.5–7.3 and for Mo(VI) by 10% LIX 84 from chloride media at pH 1.5. The order of extraction of Mo(VI) from 1N acid solutions is HCl>H₂SO₄>HNO₃>HClO₄ and extraction decreases very rapidly with increase in the concentration of HCl as compared to that from H₂SO₄, HNO₃ and HClO₄ acid solutions. The diluents C₆H₆, CCl₄ and CHCl₂ are found to be superior ton-butyl alcohol and isoamyl alcohol for extraction of Mo(VI). Influence of concentration of different anions on the extraction of U(VI) and Mo(VI) has been studied. Very little extraction has been observed in case of Th(IV) by LIX 84 or its mixtures with other chelating extractants or neutral donors.     

Liquid-liquid extraction and recovery of indium using Cyanex 923

The extraction of In(III) from HCl, H₂SO₄, and HNO₃ media using a 0.20 mol l⁻¹ Cyanex 923 solution in toluene is investigated. In(III) is quantitatively extracted over a fairly wide range of HCl molarity while from H₂SO₄ and HNO₃ media the extraction is quantitative at low acid concentration. The extracted metal ion has been recovered by stripping with 1.0 mol l⁻¹ H₂SO₄. The stoichiometry of the In(III): Cyanex 923 complex is observed to be 1:2. The extraction of In(III) is insignificantly changed in diluents namely toluene, n-hexane, kerosene (160-200 °C), cyclohexane, and xylene having more or less the same dielectric constants, whereas, it decreases with increasing polarity of diluents such as cyclohexanone and chloroform. The extractant is stable towards prolonged acid contact and there is a negligible loss in its extraction efficiency even after recycling for 20 times. The extraction behavior of some commonly associated metal ions namely V(IV), Ti(IV), Al(III), Cr(III), Fe(III), Ga(III), Sb(III), Tl(III), Mn(II), Fe(II), Cu(II), Zn(II), Cd(II), Pb(II), and Tl(I) has also been investigated. Based on the partition data the conditions have been identified for attaining some binary separations of In(III). These conditions are extended for the recovery of pure indium from zinc blend, zinc plating mud, and galena. The recovery of the metal ions is around 95% with purity approximately 99%.     

Extraction of molybdenum(VI) by 4-(5-nonyl)pyridine in benzene from aqueous mineral acid solutions containing thiocyanate ions

Extraction of Mo(VI) by 4-(5-nonyl)pyridine (NPy) in benzene from mineral acid solutions containing thiocyanate ions has been investigated at room temperature (23±2°C). From mineral acid (HCl, HNO₃, and H₂SO₄) solutions alone Mo(VI) is not extracted quantitatively while the presence of small amounts of KSCN in the system augments the extraction by a large factor. Stoichiometric studies indicate that ion-pair type complexes (NPyH)₂·[MoO₂(SCN)₄] are responsible for the extraction. Separation factors determined at fixed extraction conditions (0.1M Npy/C₆H₆–0.1M acid +0.2M KSCN) reveal that Ag(I), Cu(II), Co(II), Zn(II), Hg(II) and U(VI) are co-extracted while a clean separation from alkali metals, alkaline earths and some transition metals like Ln(III), Zr(IV), Hf(IV), Cr(III), Cr(VI) and Ir(III) is possible. Some of the complexing anions like oxalate, citrate, acetate, thiosulfate or ascorbate do not affect the degree of extraction of Mo(VI) allowing it to be recovered from diverse matrices.     

Extraction of europium from mixed acids and mixed aqueous—Organic media

The extraction of Eu with Amberlite LA-2, TBP and HDEHP from HF, HCl, HBr, H₂SO₄, CH₃ COOH and KI solutions was investigated. The extraction of Eu with TBP and LA-2 is small over a wide range of concentrations. The extraction of Eu with HDEHP from HCl, HBr, and H₂SO₄ is inversely proportional to the third power of the acid concentration, while the extraction from KI is proportional to the square of the extractant concentration. The extraction by the three extractants from H₂SO₄ in presence of small amounts of hydrogen halides is small. These extraction data can be used to separate Eu from Th and many of the fission products. The presence of water-miscible alcohols and acetone generally increases the extraction of Eu from H₂SO₄ and KI solutions.     

Plutonium extraction from mixed aqueous media. Plutonium—Uranium separation

A systematic study is presented on Pu IV extraction with tri-n-butyl phosphate and trilaurylamine from binary mixtures of H₂SO₄ with HCl and HBr. The addition of sulfuric acid to the mentioned mineral acid solutions, was found to affect appreciably D_Pu, which recommended some useful purification procedures. The effect of water-miscible alcohols on the extraction of plutonium from HCl and HNO₃ solutions was also investigated.     

Extraction of sulfuric acid with TOPO

A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H₂SO₄ as a function of H₂SO₄ concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media.     

Investigation on Concentrated Ⅴ（Ⅳ）/Ⅴ（Ⅴ） Redox Reaction by Rotating Disc Voltammetry

The kinetic characteristics of the concentrated Ⅴ（Ⅳ）/Ⅴ（Ⅴ） couple have been studied at a glassy carbon electrode in sulfuric acid using rotating-disc electrode and cyclic voltammetry. The kinetics of the Ⅴ（Ⅳ）/Ⅴ（Ⅴ） redox couple reaction was found to be electrochemically quasi-reversible with the slower kinetics for the Ⅴ（Ⅴ） reduction than that for the Ⅴ（Ⅳ） oxidation. And, dependence of diffusion coefficients and kinetic parameters of Ⅴ（Ⅳ） species on the Ⅴ（Ⅳ） and H2SO4 concentration was investigated. It is shown that the concentration of active species Ⅴ（Ⅳ） should be over 1 mol·L^-1 for the redox flow battery application. Further, with increasing the Ⅴ（Ⅳ） and H2SO4 concentration, the diffusion coefficients of Ⅴ（Ⅳ） were gradually reduced whereas its kinetics was improved considerably, especially in the case of Ⅴ（Ⅳ） and H2SO4 up to 2 and 4 mol·L^-1.     

Counter-current extraction process for recovery of U(IV) from phosphoric acid using octylphenyl acid phosphate (OPAP) extractant

The extraction of U(IV) from phosphoric acid by octylphenyl acid phosphate (OPAP) in kerosene was investigated. Parameters affecting the extraction of U(IV) from phosphoric acid were investigated. The effects of H₃PO₄, H₂SO₄, H₂O₂, Na₂CO₃ and (NH₄)₂CO₃ concentrations, phase ratio and temperature on the stripping of uranium from the organic phase were studied. Based on the bench-scale results, a continuous counter-current extraction flow sheet was developed and tested using a 16-stage horizontal type mixer settler. The continuous extraction scrubbing stripping showed that the extraction efficiency of the developed process is 99%, whereas the stripping efficiency is 97%.     

Micelle-assisted cerium(IV) oxidation of <Emphasis Type="SmallCaps">L</Emphasis>-sorbose in aqueous sulfuric acid

Spectrophotometric kinetic technique has been used to investigate the effect of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) surfactants on the redox reaction of cerium(IV)+l-sorbose in aqueous sulfuric acid media. The anionic SDS has no effect, whereas the reaction rate increases in the presence of cationic CTAB, which is due to favorable conditions provide by the cationic micelles. The reaction rate decreases with [H₂SO₄], and no acid-dependent path has been observed. At constant [H₂SO₄], the rate of the reaction is dependent on the first powers of the l-sorbose and cerium(IV) concentrations. The CTAB-assisted reaction is retarded by addition of electrolytes (Na₂SO₄, NaNO₃, and NaCl), which is attributed to the competition between electrolyte anions and cerium(IV)-sulfato species. Bromide ion (of CTAB or externally added in the form of NaBr) is not oxidized by the cerium(IV) (as a main or side reaction).     

Studies on extraction of zirconium(IV) by tricapryl methyl ammonium chloride from sulphate media and its separation from hafnium(IV)

The distribution of Zr(IV) between aqueous H₂SO₄ solutions and organic phases of tricapryl methyl ammonium chloride has been described. The dependence of extraction on acidity, metal and solvent concentration, diluent type and temperature was thoroughly investigated. The possible extraction mechanism is discussed in the light of results obtained. A method for the separation of Hf(IV) from Zr(IV) is also suggested.     

Studies on the solvent extraction behaviour of Pu(IV) from sulfuric acid medium into di-2-ethylhexyl phosphoric acid (HDEHP)

Extraction of plutonium(IV) from aqueous sulfuric and sulfuric-nitric acid into di-2-ethylhexyl phosphoric acid (HY) in the diluents n-dodecane, toluene or chloroform has been investigated. The composition of the Pu(IV) species extracted from H₂SO₄ was found to be PuH₂Y₆, which changed to Pu(NO₃)H₂Y₅ and Pu(NO₃)₂H₂Y₄ with increasing concentration of nitrate ion in the aqueous medium. These three species can be represented as PuY₂(HY₂)₂, Pu(NO₃)Y(HY₂)₂ and Pu(NO₃)₂(HY₂)₂, respectively, where Y represents the anion of monomeric HY, and HY₂ the anion of dimeric H₂Y₂. Synergism in the extraction of Pu(IV) by the addition of thenoyltrifluoroacetone (HTTA) to HY was also investigated and attributed to extraction of the additional species, Pu(TTA)Y(HY₂)₂ and Pu(TTA)₂(HY₂)₂. The addition of the neutral extractant tri-n-octylphosphine oxide (TOPO) to HY did not result in synergism in the extraction of Pu(IV) from aqueous sulfuric acid. With aqueous nitric acid under similar conditions, however, synergism was observed. The possible equilibria in these systems were identified and the corresponding equilibrium constants were determined.     

Extraction of some elements of the groups IV b and VI b with 1-phenyl-3-methyl-4-caproyl-pyrazolone-5 (PMCP) from aqueous mineral acid solutions

Solvent extraction of Cr(VI), Mo(VI), W(VI) and Hf(IV) with 1-phenyl-3-methyl-4-caproyl-pyrazolone-5 (PMCP) in methyl isobutylketone (MIBK), xylene and chloroform (CHCl₃) from mineral acid solutions was studied. Chromium(VI) is not extracted from any of the acids studied (HCl, H₂SO₄ and HClO₄). Molybdenum(VI) is quantitatively extracted by the reagent in xylene and CHCl₃ from HClO₄ and HNO₃ solutions. It is also extracted quantitatively by the reagent in MIBK from HCl, HNO₃ and H₂SO₄ solutions but the participation of the diluent as extractant is considerable. Tungsten(VI) is quantitatively extracted in xylene from 9M HClO₄ solution. MIBK used as diluent also affects its extraction with PMCP. Hafnium(IV) is not extracted from H₂SO₄ solutions while it extracts more than 99% at 3M HNO₃ and above. The extracted species likely are: MoO₂(PMCP)₂, WO₂(PMCP)₂ and Hf(PMCP)₄, respectively.     

Liquid-liquid extraction of molybdenum(VI) and uranium(VI) by LIX 622

The order of extraction of Mo(VI) from 1M acid solutions by 5% (v/v) LIX 622 (HL) in benzene is HCl>HNO₃>HClO₄>H₂SO₄, and extraction decreases with increasing concentration of HCl and H₂SO₄, and increases slightly with increasing concentration of HNO₃ and HClO₄. The extracted species is shown to be MoO₂L₂ as established by IR data of organic extracts and the extracted species in the solid form. Extraction is almost quantitative at and above 10% LIX 622, and is found to be independent of [Mo(VI)] in the range of 10^–4 to 10^–3 M. The diluents CCl₄, CHCl₃ and C₆H₆ are found to be superior to solvents of high dielectric constant for extraction of Mo(VI). Extraction of uranium(VI) by 10% (v/v) LIX 622 in benzene was found to increase with increasing equilibrium pH (3.0 to 6.0), and becomes quantitative at pH 5.9. Tributyl phosphate acts as a modifier up to 2% (v/v). Thorium(IV) is almost not extracted by LIX 622 or its mixture. Separation of Mo(VI) and U(VI) is feasible.     

Leaching of uranium with the H2O2-Na2SO4-H2SO4 (HSS) system and the efficiency of Acigol Lake water

The applicability of a new leaching method, the HSS (H₂O₂-Na₂SO₄-H₂SO₄) system, in the extraction of uranium from Saricaolu-Bergama Region low grade ore, and the efficiency of Acigol Lake (Denizli)-Turkey water as a natural source of Na₂SO₄ has been investigated. The effect of H₂SO₄ concentration, temperature, leaching time, H₂O₂ and Na₂SO₄ concentrations and the amount of Acigol Lake water on the extraction of uranium was examined. HSS was found suitable for the extraction of uranium from Saricaolu-Bergama Region samples and it was observed that the acid consumption could be decreased by adding Na₂SO₄.     

Extraction studies of Pu(IV) with octylphenyl acid phosphate

Octylphenyl acid phosphate, the commercially available mixture of monooctylphenylphosphoric acid (MOPPA) and dioctylphenylphosphoric acid (DOPPA) in xylene medium has been employed as an extractant for distribution studies on Pu(IV) in different mineral acids including phosphoric acid. It was found possible to extract Pu quantitatively from an acid mixture comprising 2.5M H₃PO₄, 0.75M H₂SO₄ and 0.5M HNO₃. Quantitative stripping was observed with a mixture of 0.25M oxalic acid and 0.2M ammonium oxalate.Parts of this work have been reported at symposie (Refs^1,2)     

Evaluation of continuous hydride generation combined with helium and argon microwave induced plasmas using a surfatron for atomic emission spectrometric determination of arsenic,antimony and selenium

The direct coupling of continuous hydride generation with both Ar and He microwave induced plasmas (MIP) sustained in a surfatron has been optimized for the simultaneous determination of arsenic, antimony and selenium with atomic emission spectrometry. While a discharge tube of quartz was found suitable for the Ar plasma, the use of an Al₂O₃ tube led to improved performance of the He plasma. The He MIP was found to be less tolerant to the introduction of hydrogen than the Ar MIP, and correspondingly the hydride generation should be operated at a lower flow rate of 0.5% NaBH₄ solution. The introduction of the H₂O vapour produced during hydride generation into both discharges was found to greatly decrease the sensitivities and to degrade the measurement precision. It could be effectively removed with trapping by concentrated H₂SO₄. The detection limits (3σ) for As, Sb and Se are 1, 0.4 and 1 ng ml⁻¹ with the Ar MIP, and 2, 0.3 and 6 ng ml⁻¹ with the He MIP, respectively. The calibration curves are linear over three decades of concentration. The mutual interferences from As(III), Sb(III), Se(IV), Bi(III) and Sn(IV) were found to be negligible at interferent concentrations below 1 μg ml⁻¹ and in most cases the tolerable interferent concentrations are up to 20 μg ml⁻¹. The proposed method has been applied to the determination of As, Sb and Se in tea samples at μg g⁻¹ levels.