Solvent extraction of thorium(IV) with dibutyldithiophosphoric acid in various organic solvents

The extraction of thorium(IV) from perchlorate solutions with di-n-butyldithiophosphoric acid (HBudtp) in various organic solvents occurs through an ion exchange mechanism. The extracted species in the organic phase is an eight-coordinate complex Th(Budtp)₄. The higher values of the distribution ratio obtained in HBudtp-benzene-water system than in HBudtp-n-butanol-water system are explained by higher solubility of the complex species in nonpolar solvents. The position of the extraction curves in the pH-range lower than 0.7 reduces the complexation of thorium(IV) with Budtp^– in the aqueous phase and also the hydrolysis process.     

Sorption of Th(IV) from aqueous solution to GMZ bentonite: effect of pH, ionic strength, fulvic acid and electrolyte ions

Bentonite has been studied extensively because of its strong sorption and complexation ability. In this study, GMZ bentonite (China) was studied as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that the sorption of Th(IV) is strongly dependent on pH and ionic strength at pH <5, and is independent of ionic strength at pH >5. Outer-sphere surface complexation or ion exchange in inter-layer sites of the montmorillonite fraction of the GMZ bentonite may be the main sorption mechanism of Th(IV) onto GMZ bentonite at low pH values, whereas the sorption of Th(IV) at pH >5 is mainly dominated by inner-sphere surface complexation or surface precipitation. The presence of soil fulvic acid has a positive influence on the sorption of Th(IV) on GMZ bentonite at pH <5. The competition between Th(IV) with aqueous or surface adsorbed cation ions (e.g., herein Li⁺, Na⁺ and K⁺) and surface functional groups of GMZ bentonite is important for Th(IV) sorption on GMZ bentonite. The results of high sorption of Th(IV) suggest that the GMZ bentonite is a suitable backfill material in nuclear waste management.     

Ion exchange of radium and barium in zeolites

The sorption of radium, barium and mixture of both elements has been studied in the zeolites 3A, 5A and Y. The ratio zeolite; solution was 100 mg: 10 cm³ and the pH was 3. Carrier-free radium was completely retained in all studied zeolites. When 0.0016 meq of barium/cm³ were added, the sorption of radium decreased in the zeolite 5A only and when 0.014 meq of barium/cm³, the radium sorption was reduced in all the studied zeolites. The sorption of barium was similar to that of radium. The amounts of sodium and calcium removed from the zeolites and the proton quantity fixed to them allowed us propose the ion exchange mechaniosm. The changes and ionic radii of the species exchanged did not play an important role. However, the location of the ions in the crystalline network of each zeolite is probably an important parameter for the exchange.     

Study of scandium and thorium sorption from uranium leach liquors

Scandium and thorium sorption from simulated uranium leach liquors by phosphorous containing ion exchange resins was studied. Increase of thorium concentration resulted in a decrease of scandium sorption by 26–65%. Tulsion CH 93 resin was chosen for Sc separation from uranium leach liquors. It was shown that 180 g L^?1 Na₂CO₃ allowed for elution 94.1% of Sc and 98.9% of Th in dynamic conditions. Using (NH₄)₂SO₄ (50 g L^?1) + ACBM (180 g L^?1) mixture for primary Sc/Th separation at the resin/eluent ratio of 1:5 resulted in thorium desorption degree as high as 66–69%, whereas scandium loss did not exceed 10%.     

Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

Effects of phosphate and Cr<Superscript>3+</Superscript> on the sorption and transport of Th(IV) on a silica column

Six column experiments were performed, and six breakthrough curves (BTCs) and six displacement (desorption) curves (DPCs) were obtained, which demonstrate the effects of phosphate and Cr³⁺ on the sorption and transport of Th(IV) on a silica column at pH 3.0 and Th(IV) concentration 8·10⁻⁶ mol/l of the influent. It was found that in the presence of phosphate sorbed preliminarily on the silica column, the amount of Th(IV) sorbed on the silica column is significantly increased. The breakthrough is significantly delayed relative to those in the absence of phosphate; the effect of simultaneous injection of Cr³⁺ on Th(IV) breakthrough is not significant and while the maximum concentration of Th(IV) of BTC is significantly decreased and reached about 70% of the input concentration; a minor proportion of Th(IV) sorbed on the silica column in the presence or absence of phosphate is not readily displaced with 0.01 mol/l KNO₃ aqueous solution at pH 3. Transport and sorption studies of Th(IV) are important, since all thorium isotopes are radioactive, and Th(IV) is an analogue of tetravalent actinides. There is a need to understand the potential for migration from radioactive waste storage and mill tilling sites.     

Physicochemical properties of alkali-metal exchanged type X zeolites

The changes in the physicochemical properties of a series of faujasite type X zeolites cation exchanged with K⁺, Rb⁺ and Cs⁺ have been studied by XRD, IR, thermoanalytical methods and sorption measurements. As a consequence of the enhanced scattering of X-rays by larger alkali metal cations, the percent relative intensity of the XRD peaks of cation exchanged zeolites was found to have decreased considerably. The framework IR spectra also showed analogous changes. The alkali metal exchange was found to enhance the thermal stability of the parent zeolite. The available void volume and specific surface area (obtained by low temperature nitrogen sorption) also decreased with the increase in the degree of exchange and cationic size. Equilibrium sorption capacities (298 K andP/P ₀=0.5) for water,n-hexane, cyclohexane and 1,3,5-trimethylbenzene also exhibited the same trend.NCL communication no. 6056.     

The removal of thorium from aqueous solutions using zeolites

The ability of zeolites to remove thorium-232 from naturally radioactive thorium nitrate solutions was studied by ion exchange, adsorption and surface phenomena. The best zeolites were a clinoptilolite from Mudhills, California, USA and a mordenite rich tuff from Eastgate, Nevada, USA. As the concentration of thorium in solution was increased the mechanism of thorium removal switches from that of partial ion-exchange to a surface precipitation. This was confirmed by electron probe microanalysis (EPMA) in conjunction with XRD and Energy Dispersive X-ray analysis (EDX). A Langmuir-type of adsorption occurred with the thorium-232 daughter isotopes at the same time as partial exchange/precipitation of the thorium parent which is in regular equilibrium with its natural daughters. Some experiments with²³⁴Th were carried out to confirm this hypothesis as well as column experiments to confirm the usefulness of the Th removal.     

Sorption characteristics of uranium onto composite ion exchangers

The composite ion exchangers were tested for their ability to remove UO₂ ²⁺ from aqueous solutions. Polyacrylonitrile (PAN) composites having natural zeolite, clinoptilolite, and synthetic zeolite, zeolite X, were used as an adsorbents. The influences of pH, U(VI) concentration, temperature and contact time on the sorption behavior of U(VI) were investigated in order to gain a macroscopic understanding of the sorption mechanism. The optimum adsorption conditions were determined for two composites. The sorption behaviors of uranium on both composites from aqueous systems have been studied by batch technique. Parameters on desorption were also investigated to recover the adsorbed uranium.     

Design and evaluation of a thorium (IV) selective optode

A novel optical sensor has been proposed for sensitive determination of thorium (IV) ion in aqueous solutions. The thorium sensing membrane was prepared by incorporating 4-(p-nitrophenyl azo)-pyrocatechol (NAP) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to thorium ion by changing color reversibly from yellow to red-brown in glycine buffer solution at pH 3.5. The proposed sensor displays a linear range of 8.66 × 10⁻⁶-2.00 × 10⁻⁴ M with a limit of detection of 6 × 10⁻⁶ M. The response time of the optode was about 8.8-12.5 min, depending on the concentration of Th (IV) ions. The selectivity of optode to Th (IV) ions in glycine buffer is good. The sensor can readily be regenerated by exposure to a solution mixture of sodium fluoride and 5-sulfosalicylic acid (dihydrate) (0.01 M each). The optode is fully reversible. The proposed optode was applied to the determination of thorium (IV) in environmental water samples.     

Thorium(IV) and zirconium(IV) complexes of oxygen donor ligands,Part 6. thorium(IV) complexes of 2,6-lutidine-N-oxide and tetramethylene sulphoxide

Summary The synthesis and physical properties of crystalline thorium(IV) complexes, Th(ClO₄)₄ · 6 LNO, ThX₄ · 2 LNO (X = Br or SCN), ThX₄ · 4 LNO (X = NO₃ or I) andTh(ClO₄)₄ · 10 TMSO, Th(NO₃)₄ · 6 TMSO, ThX₄ · 4 TMSO (X = Cl or Br), ThI₄ · 6 TMSO and Th(NCS)₄ · 2 TMSO (where LNO = 2,6-lutidine-N-oxide and TMSO = tetramethylene sulphoxide) are reported together with their i.r. spectra, molar conductivities, molecular weights, t. g. a. and d. t. a. data. In all the complexes, LNO and TMSO are bonded to thorium(IV) through oxygen. The coordination number of thorium(IV) in these complexes varies from six to ten depending upon the nature of the anions.Presented at the XVI Annual Convention of Chemists, Andhra University, Waltair, A. P. India, December 27–31, 1978.     

Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination

A new synthesized modified mesoporous silica (MCM-41) using 5-nitro-2-furaldehyde (fural) was applied as an effective sorbent for the solid phase extraction of uranium(VI) and thorium(IV) ions from aqueous solution for the measurement by inductively coupled plasma optical emission spectrometry (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ions were investigated in batch method. Under optimal conditions, the analyte ions were sorbed by the sorbent at pH 5.5 and then eluted with 1.0 mL of 1.0 mol L⁻¹ HNO₃. The preconcentration factor was 100 for a 100 mL sample volume. The limits of detection (LOD) obtained for uranium(VI) and thorium(IV) were 0.3 μg L⁻¹. The maximum sorption capacity of the modified MCM-41 was found to be 47 and 49 mg g⁻¹ for uranium(VI) and thorium(IV), respectively. The sorbent exhibited good stability, reusability, high adsorption capacity and fast rate of equilibrium for sorption/desorption of uranium and thorium ions. The applicability of the synthesized sorbent was examined using CRM and real water samples.     

Mesopores in USY Zeolites II

Microporous zeolites Na‐Y and K‐Y were converted into the NaNH₄‐Y and KNH₄‐Y modifications by ion exchange being active in dealumination. Removal of framework aluminium and silicon is accompanied by formation of secondary mesopores. Internal mesopores are formed in the centre of zeolite crystals and external pores at their surface. Formation of mesopores changes the sorption behaviour.Residual alkali metal cations as Na⁺ or K⁺ stabilise, however, the framework ≡Si‐O‐Al≡ bonds. Because of inhomogeneous distribution of sodium ions, in NaNH₄‐Y less internal but more external mesopores are formed. Potassium ions of KNH₄‐Y are more homogeneous distributed over the framework why a more balanced formation of secondary pores takes place.     

Extraction of thorium from aqueous nitric acid solution by bis-2-(butoxyethyl ether) (DBC)

The solvent extraction of thorium(IV) (4.3·10^–4M) from nitric acid solution by bis-2-(butoxyethyl ether) (butex or DBC) has been studied. It has been investigated as a function of nitric acid, extractant and metal ion concentration. The effect of equilibration time, diverse ions and salting-out agent on the extraction has also been examined. Among anions, fluoride, phosphate, oxalate and perchlorate have reduced the extraction. Cations such as Na(I), K(I), Ca(II), Zn(II), Al(III), Ti(IV), Zr(IV) except Sr(II) and Pb(II) do not interfere in the extraction. The extraction is enhanced upto 97% in three stages at 6M HNO₃ having 2.94M NaNO₃ as salting-out agent. The extraction is found to be independent of thorium concentration in the range studied (4.3·10^–4–4.3·10^–2M). The temperature (18–45°C) has an adverse effect on the extraction. A 1% solution of ammonium bifluoride is found to be a good stripping solution and recovery of thorium is >98%.     

Synthesis of NaX and NaY Zeolites from Tunisian Kaolinite as Base Catalysts: An Investigation of Knoevenagel Condensation

The synthesis of Faujasite‐type zeolites with high purity has been successfully performed from Tunisian kaolinite and the effects of different crystallization parameters on the final products were widely investigated. The alkaline fusion of kaolinite followed by hydrothermal treatment lead to zeolite NaX synthesis whereas the classic hydrothermal transformation of metakaolinite produces NaY zeolite. The results show that an increase in the synthesis temperature and time has improved the crystallization process of the zeolite NaX whereas the SiO₂/Al₂O₃ and the Na₂O/SiO₂ molar ratios were the key parameters to obtain a pure zeolite NaY. The highest specific surface areas obtained with the optimal crystallization conditions were 554 m2 g^?1 and 592 m2 g^?1 for respectively NaX and NaY zeolites. The basic properties of NaX and NaY zeolites were explored in the Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate at 140 °C as a test reaction in the absence of solvent. The influence of ion exchange with cesium cation on the catalytic activity of prepared catalysts was also investigated. It was found that the NaX provided higher activity than that of NaY catalyst due to its lower Si/Al ratio whereas a cesium exchange conferred higher basicity to the prepared Na‐faujasite.     

Ion exchange studies of U(VI) from aqueous Arsenazo-III solutions using AG-2X8, Dowex-50WX8 and Chelex-100 resins

The distribution of U(VI) between the anion exchanger AG-2X8, the cation exchanger Dowex-50WX8 and the chelating resin Chelex-100 and aqueous solutions of Arsenazo-III at different pH values was studied. The concentration of Arsenazo-III was in the range of 1.53·10^–4–1.23·10^–3M. Equilibrium pH was varied from 1.0 to 8.78 while U(VI) original concentration was held constant at 3.39·10^–4M. The effect of Arsenazo-III concentration and the variation of hydrogen ion concentration on U(VI) species formed in solution as well as the sorbed species was discussed. Use was made of IR spectroscopy to investigate the sorption behavior. The sorption of some interfering ions such as Th(IV), Zr(IV) and Ce(III) on the resins used at optimum conditions for the sorption of U(VI) was also investigated.     

Improving the efficiency in the detection of gamma activities in environmental soil samples: influence of the granulometry and soil density

Ti(OH)₄ and TiCl₄ modified bentonite (Ti–Na-bent) were applied in the removal of Th(IV) from aqueous solution. Effect of different factors such as pH, contact time, temperature, initial concentration of Th(IV) and efficiency of them for thorium adsorption are investigated. Ti–Na-bent showed high adsorption capacity (q_m?=?231.37 mg/g) and quick adsorption kinetics at lower pH. The adsorption mechanisms involved are: (1) Th⁴⁺, [Th(OH)_4?n]ⁿ⁺ complexed on the outer-sphere of Na-bent and Ti–Na-bent. (2) Ion exchange between Th⁴⁺, [Th(OH)_4?n]ⁿ⁺ and exchangeable cations of Na-bent and the H on the hydroxyl group of Ti(OH)₄. Ti–Na-bent manifested high adsorption capacity for Th(IV), good acid resistance and long-term adsorption stability.

     

Influence of acetate, chloride and nitrate ions on the sorption of cobalt by zeolite ZSM-5

Many factors affect the ion exchange process in zeolites. In this work the influence of different anions such as acetate, chloride and nitrate on the ion exchange of cobalt in zeolite ZSM-5 is discussed. After the ion exchange in the presence of those anions no change was found in the zeolite structure, by X ray diffraction and IR spectroscopy. The retention of cobalt by zeolite ZSM-5 at low concentrations (from 0.001 to 0.3N) was higher when the exchange was done with cobalt nitrate and chloride. This behavior was different in the case of 1N cobalt salts, since the highest sorption uptake was found when working with cobalt acetate and its sorption was directly proportional to its concentration.     

Changes in Porous Parameters of the Ion Exchanged X Zeolite and Their Effect on CO2 Adsorption

Zeolite 13X (NaX) was modified through ion-exchange with alkali and alkaline earth metal cations. The degree of ion exchange was thoroughly characterized with ICP, EDS and XRF methods. The new method of EDS data evaluation for zeolites was presented. It delivers the same reliable results as more complicated, expensive, time consuming and hazardous ICP approach. The highest adsorption capacities at 273 K and 0.95 bar were achieved for materials containing the alkali metals in the following order K < Na < Li, respectively, 4.54, 5.55 and 5.94 mmol/g. It was found that it is associated with the porous parameters of the ion-exchanged samples. The Li_0.61Na_0.39X form of zeolite exhibited the highest specific surface area of 624 m²/g and micropore volume of 0.35 cm³/g compared to sodium form 569 m²/g and 0.30 cm³/g, respectively. The increase of CO₂ uptake is not related with deterioration of CO₂ selectivity. At room temperature, the CO₂ vs. N₂ selectivity remains at a very high stable level prior and after ion exchange in co-adsorption process (X_CO2 during adsorption 0.15; X_CO2 during desorption 0.95) within measurement uncertainty. Additionally, the Li_0.61Na_0.39X sample was proven to be stable in the aging adsorption-desorption tests (200 sorption-desorption cycles; circa 11 days of continuous process) exhibiting the CO₂ uptake decrease of about 6%. The exchange with alkaline earth metals (Mg, Ca) led to a significant decrease of SSA and micropore volume which correlated with lower CO₂ adsorption capacities. Interestingly, the divalent cations cause formation of mesopores, due to the relaxation of lattice strains.