The direct spectrophotometric determination of uranium(VI) in trialkylamine extracts with dibenzoylmethane

A spectrophotometric determination with dibenzoylmethane is described for uranium(VI) in trialkylamine sulphate extracts from sulphate leach liquors, without return of the uranium to an aqueous medium. The proposed method is less sensitive (apparent molar absorptivity, 3.8 × 10⁴ l mol^-1 cm^-1) than the Br—PADAP method but is more tolerant to sulphate and other ions found in leach liquor systems.     

Extraction of uranium(VI) with octyldodecylsulfoxide (ODoSO)

Complexes of Hf with polyaminopolycarboxylic acids viz. diethylene-triamine-penta-acetic acid (DTPA) and its dimethoxy derivative DMDTPA have been studied using paper chromatography at different acidities. Kinetic stabilities of the complexes have also been looked at. Behaviors of these two ligands in complexing with Hf(IV) have been found to be similar. The extent of complexation reduces slowly with acidity and increase with time and reaches a maximum around 70-80% after about 24 hours.     

Extraction of uranium(VI) with bis(octylsulfinyl)methane

The liquid-liquid extraction of uranium(VI) from aqueous nitric acid with bis(octylsulfinyl)methane (BOSM) has been studied over a wide range of conditions. The extracted species appear to be UO₂(NO₃)₂·2BOSM. It was found that the extraction increased with increasing nitric acid concentration up to 8.5 mol/l and then descreased. Extraction also increased with increasing extractant concentration. The influence of temperature and salting-out agent concentration on the extraction equilibrium has also been investigated, and the enthalpy of the extraction reaction was estimated.     

Extraction of uranium from aqueous solution by phosphonic acid-imbedded polyurethane foam

Phenylphosphonic acid was imbedded into the matrix of the polyurethane foam during the fabrication process of the polymer. The extraction of uranium by phosphonic acid-imbedded polyurethane foam and blank polyurethane (i.e., foam without phosphonic acid functional groups) was investigated. Phosphonic acid-imbedded foam showed superior extractability of uranium from solutions with pH=7.0+/-1.5 over a wide range of temperature.     

Adsorption modeling of antimony(V) on diphenylthiocarbazone loaded polyurethane foam

The uptake behavior of Sb(V) onto diphenylthiocarbazone (H2DZ) loaded polyurethane foam (PUF) from aqueous solutions of different acids in the presence of KI have been studied. The maximum adsorption was found from 0.5N HNO₃ containing 0.2M KI. The maximum equilibrium was achieved within twenty minutes shaking time. The sorption behavior followed the Freundlich and Langmuir adsorption isotherms. The Freundlich constants 1/n and K_f are 0.57 and 3.26^.10^-2 mol^.g^-1, respectively. The Langmuir constants M and b are 2.18^.10^-4 mol^.g^-1 and 2.4^.10⁴ l^.g^-1, respectively. The value of sorption free energy (E) evaluated from D-R isotherm is 10.8 kJ^.mol^-1 indicating the ion exchange type chemisorption of Sb(V) on H2DZ loaded PUF. The thermodynamic parameters of enthalpy (H), entropy (S) and Gibbs free energy (G) have also been investigated and found to be -51.8 kJ^.mol^-1, -127.3 J^.mol^-1.deg^-1 and -13.8 kJ^.mol^-1, respectively. The negative values of (H) and (G) indicate that the sorption is exothermic and spontaneous in nature. The effect of anions and cations and sorption mechanism are discussed.     

Extraction of uranium(VI) and plutonium(IV) with some aliphatic amides

Extraction of uranium(VI) and plutonium(IV) has been studied with N,N-dibutyl derivatives of hexanamide (DBHA), octanamide (DBOA) and decanamide (DBDA) at various fixed temperatures of 20, 30, 40 and (50±0.1)°C. The equilibrium constants for the uptake of nitric acid (K_h, a measure of their relative basicities) by these amides were evaluated by the usual method. The equilibrium constants for the extraction of uranium as well as plutonium with all the three amides follow their order of basicity (K_h) viz. DBHA (0.09)<DBOA (0.10)<DBDA (0.13) with log K values of 1.31, 1.43 and 1.73 for uranium and 3.55, 3.65 and 4.17 for plutonium, respectively. It has been observed that whereas uranium(VI) is extracted as a disolvate (similar to TBP and sulfoxides), plutonium(IV) has been found to be extracted as a trisolvate. The thermodynamic parameters evaluated by the usual temperature coefficient method indicate that the extraction reactions of uranium as well as plutonium are stabilized by negative enthalpy change only.     

Extraction studies of uranium(VI) and thorium(IV) with tributylphosphine oxide

Clay minerals occur widely in nature and play a very important role in agriculture, mineral recovery and chemical manufacturing. Among the many properties which affect clay behaviour, water binding and ion exchanging appear to be the most important. The study of the cation exchange capacity of soils is of great theoretical and practical importance since the CEC determines in many ways the behavior of nutrients, chemical amendments, and many toxic compounds entering the sols. Sorption interactions with montmorillonite and other clay minerals in soils are potantially important mechanisms for attenuating the mobility of heavy metal cations through the subsurface environment. In this work the cation exchange capacity (CEC) of montmorillonite from west Anatolia, and sorptions with montmorillonite for attenuating the mobility of uranium were studied. The CEC value was found to be 77 meq/100 g montmorillonite. The relative importance of test parameters e.g., contact time, particle size, pH and U(+6) aqueous speciation was determined. The results show that sorption on montmorillonite is a funtion of pH depending strongly on the aqueous U(+6) species. It reaches a maximum at near neutral pH(pH}7). At low and at high pH solutions the sorption values of uranium are poor. These sorption values were attributed to the formation of aqueous U(+6) carbonate complexes in alkaline conditions and the ionexchange process between UO₂ ⁺² species and interlayer cations on montmorillonite in acidic solutions.     

Extraction of uranium (VI) from sulfuric acid solution with TOPO

The extraction of uranium(VI) from sulfuric acid medium with tri-octylphosphine oxide (TOPO) in n-heptane was studied. Accompanied with the increase in the concentration of H₂SO₄, the distribution coefficient of uranium(VI) increased in the region of dilute sulfuric acid. When the concentration of H₂SO₄ surpassed 3.5 mol·dm⁻³, the distribution coefficient of uranium(VI) was at maximum. This result was due to the competition extraction between uranium(VI) and H₂SO₄. From the data, the composition of extracted species and the equilibrium constant of extraction reaction have been evaluated, which were (TOPOH)₂UO₂(SO₄)₂ (TOPO) and 10^7.6±0.15, respectively.     

Extraction of uranium(VI) by bis(hexylsulfinyl)methane

The extraction of uranium(VI) with bis(hexylsulfinyl)methane (BHxSM) from nitric acid aqueous solution has been investigated. It was found that the extraction increased with increasing nitric acid concentration up 8.5 mol/l and then decreased. Extraction distribution ratio also increased with the bis(hexylsulfinyl)methane concentration. The extraction species appear to be UO₂(NO₃)₂ ^.2BHxSM. The influences of temperature, salting-out concentration and oxalate concentration on the extraction equilibrium were also investigated, and the enthalpy of the extraction reaction was obtained. The result shows that the reaction of uranium(VI) extraction with BHxSM is an exothermic one.     

Extraction and spectrophotometric determination of uranium(VI) withN-phenylcinnamohydroxamic acid

Uranium(VI) reacts withN-phenylcinnamohydroxamic acid to form an orange-yellow complex in the pH range 5.5–8.5. The orange-yellow complex, having the composition of 12 (metal:ligand), is quantitatively extractable into ethyl acetate. The spectrum of the complex exhibits a maximum absorption at 400 nm with a molar absorptivity of 6500 M^–1·cm^–1. The coloured system obeys Beer's law in the concentration range 2–40g·ml^–1 of uranium(VI). The photometric sensitivity of the colour reaction is 0.037 g·cm^–2 of uranium(VI). Most of the common ions do not interfere and the method has been found to be simple, precise, and free from the rigid control of experimental conditions. The method has been applied to the determination of uranium in synthetic matrices and potable water.     

Extraction of palladium thiocyanate with polyurethane foam

Conditions for the extraction of the thiocyanate complex of palladium by polyether-type polyurethane foam are reported. Distribution ratios of more than 10(6) with a capacity of about 0.8 mole per kg of foam were obtained. The palladium could be rapidly recovered from the foam with high efficiency by use of ammonia solution. The efficiency of palladium extraction depends on how well the cation associated with the complex fits into the polyether segment of the polyurethane foam.     

Spectrophotometric determination of uranium in natural waters after preconcentration on TBP-plasticized dibenzoylmethane-loaded polyurethane foams

A method is presented for the spectrophotometric determination of uranium in natural waters after a preconcentration step involving percolation of a suitable aliquot of the water sample whose pH is adjusted to 6.0–6.5 through a TBP-plasticized dibenzoylmethane-loaded polyurethane foam bed. Uranium on the foam is eluted with 0.6M HCl solution and then determined spectrophotometrically using arsenazo III as a chromogenic reagent.     

The separation of tellurium and selenium by polyurethane foam sorbents

Tellurium and selenium can be sorbed from hydrochloric acid and hydrobromic acid solution by both polyether and polyester-based polyurethane foam. Although some acid is needed, the substitution of sodium chloride or sodium bromide increases the extraction significantly. Tellurium is extracted rapidly with > 99% sorbed in 2 min from 1.0/5.0M and 2.0/4.0M hydrochloric acid/sodium bromide. Selenium can also be sorbed quantitatively but much more slowly so that a separation is possible based on the relative rates of extraction. The capacity of polyether foam is 3% by weight of tellurium.     

Extraction study of uranium(VI) and thorium(IV) salicylates with triphenylarsine oxide

Triphenylarsine oxide is proposed as an extractant for the solvent extraction of uranium and thorium salicylates. The optimum extraction conditions are established by studying the various parameters such as pH, sodium salicylate concentration, triphenylarsine oxide concentration, diluents and shaking time. The probable extracted species as ascertained by logD-logC plots are UO₂(Hsal)₂·2TPAsO and Th(Hsal)₄·2TPAsO. The method is simple, fast, precise and permits the determination of uranium and thorium in monazite sand samples.     

Extraction of uranium(IV) and uranium(VI) by primary and tertiary-amines from sulphate solutions

In developing a method for possible low level isotopic enrichment, which uses to advantage the equilibrium isotope effect observed during U(1V)-U(VI) electron exchange reaction in sulphate solutions, details of a solvent extraction process involving high concentration of a mixture of U(IV) and U(VI) and at low acid concentrations, are described. The extraction behaviour of uranium under these conditions is discussed. During the extraction with amines, U(IV) tended to get oxidised in sulphate solutions.     

Extraction of uranium(VI) from nitric acid solution with hexyloctylsulfoxide (HxOSO)

The thermodynamic extraction of uranium(VI) with hexyloctylsulfoxide (HxOSO) has been studied. It was found that the distribution ratio increases with increasing nitric acid concentration up to 2.3 mol/l and then decreases. The distribution ratio also increases with increasing extractant concentration. The extracted species appears to be UO₂(NO₃)₂ ^.2HxOSO. The influences of temperature, sodium nitrate and oxalate concentrations on the extraction were also investigated, and the thermodynamic functions of the extraction reaction were obtained.     

Use of open-cell resilient polyurethane foam loaded with crown ether for the preconcentration of uranium from aqueous solutions

The preconcentration of uranium from aqueous solutions on open-cell resilient polyurethane foams (PUF) impregnated with crown ether as an organic extractant in different conditions was investigated. The data showed that 50 minutes is a sufficient time to attain equilibrium with a maximum extraction percentage for uranium ion on polyurethane foams loaded with crown ether. Also the extraction percentage of uranium is increased markedly with increasing the pH values up to pH ~ 6 and displayed the lowest extraction at 8>pH>6. The different isotherms of uranium sorption have shown that the sorption followed a Freundlich isotherm. Column studies have been carried out in order to extend these studies to the plant scale. From the data of column sorption and breakthrough curves, the height equivalent of theoretical plates (HETP), and breakthrough capacity which affect the efficiency of the column have been calculated and found to be 1.03 mm/plate, 64±5 and 58.3 mg uranium/gram polyurethane foam impregnated with crown ether, respectively.     

Extraction of zirconium and hafnium thiocyanate with polyurethane foam

Conditions for the extraction of zirconium and hafnium thiocyanate by polyether-type polyurethane foam were studied in detail. The composition of the extractable species was found to be dependent on both the thiocyanate and metal-ion concentrations. The extraction efficiency for zirconium and hafnium depended on the size of the counter-cation as well as on the type of anion.     

Selective extraction of cerium(IV) on tri-n-butyl phosphate and thenoyltrifluoroacetone loaded polyurethane foam

A method for the selective extraction of cerium (IV) on tri-n-butyl phosphate and thenoyltrifluoroacetone loaded foams is described. Parameters affecting the extraction of the metal ion, such as pH, reagent concentration and equilibration time have been investigated. Effects of ten diverse cations have also been studied. The method can be applied to preconcentrate and determine cerium in glasses.This work was performed at the University of Veszprém, Department of Radiochemistry, by A.R. acting as guest research fellow.     

Direct X-ray fluorescence detection of mercury on polyurethane foam sorbents

An improved method for conducting a sorption X-ray fluorescence analysis of mercury (II) in water with static and dynamic preconcentrations in the form of iodide complexes on polyurethane foam sorbents based on ethers has been proposed. It was shown that optimizing the conditions of measuring analytical signals enabled a significant (one order of magnitude or more) increase in the sensitivity of the detection of X-ray fluorescence and widening of the linear range of graduation dependence.