A new solvent system for the separation of Th4+, UO 2 2+ and Zr4+ in the presence of common anions by thin-layer chromatography

Summary A TLC method has been developed for separating Th⁴⁺, UO₂ ²⁺ and Zr⁴⁺ in the presence of some common anions using a dimethylamine/acetone/formic acid mobile phase. Capacity factors, separation factors and resolution for the separation of Th⁴⁺ from UO₂ ²⁺ have been evaluated. The effect of the pH of the sample on R_F values of Th⁴⁺, UO₂ ²⁺, Ni²⁺ and Cu²⁺ has also been examined.     

Metal Chelates of Cerium (III), Thorium(IV) and Dioxouranium(VI) with Some Heterocyclic AZO Dyes; Potentiometric and Spectrophotometric Studies

ABSTRACT

The stepwise formation constants of Ce³⁺, Th⁴⁺ and UO₂ ²⁺ complexes with four azo compounds based on I-phenyl-2, 3-dimethylpyrazoline-5-one nucleus namely; 4-phenylazo- (2-hydroxy, 5-x) 1-pheny1-2, 3-dimethy1-pyrazoline-5-one, where x= H (1), OH (II), COOH (III) and NH₂ (IV) have been determined potentiometrically at different temperatures and ionic strengths in 30% (v/v) ethanol-water solutions, then the thermodynamic parameters are calculated.

Negatives values of both ∠H and ∠G are obtained indicating the exothermic and spontaneous nature of complexation reactions, whereas positive values of ∠S show that entropy consideration favour complex formation. The study at different ionic strengths shows that an increase in the latter causes a decrese in the pK values. The azo compounds are also tested as new reagents for the spectrophotometric determination of Ce³⁺, Th4⁺ and UO₂ ²⁺ ions in synthetic and natural solutions by extensive investigation of the optimum conditions favoring the formation of colored complexes.     

Simultaneous mixture analysis by using non-linear spectrophotometric data and linear iterative target transformation factor analysis

Non-linear absorption spectral data obtained from ternary mixtures of analytes are analyzed by using a linear model, iterative target transformation factor analysis (ITTFA). The use of transformed original variables is used to correct non-linearities in the original data. Absorbance below a certain limit (k) is described as linear and above this limit as non-linear. The extension of the regressor variables is the squared absorbances above the linear range. The variation of the prediction error as a function of the number of the factors and the k-values were considered and the minimum prediction error was evaluated for reaching to optimum. Except the natural non-negativity constraint the correlation constraint also is used on concentration vector in each iteration of ITTFA algorithm. The reliability of the method is evaluated using model data for ternary mixtures by spectral overlapping and different degrees of non-linearity. Simultaneous spectrophotometric determination of Eu³⁺, UO₂²⁺ and Th⁴⁺ with arsenazo III as chromogenic reagent is used as experimental model systems with non-linearity behavior of Eu³⁺and UO₂²⁺ components. The application to both synthetic and real data sets with different degrees of non-linearity demonstrate the ability of the proposed methodology to obtain better results than original data and ITTFA. The relative standard errors of prediction for proposed method in comparison with using the PLS calibration on original and extended data are nearly smaller.     

Uranyl-catalyzed chemiluminescent reaction of U4+ oxidation by dioxygen in aqueous HClO4 solution

Chemiluminescence (CL) accompanying the reaction of U⁴⁺ with O₂ in 0.0004–0.1M HClO₄ was studied. It was found that the electron-excited uranyl ion (UO₂ ²⁺)^* is the CL emitter. The fact that the reaction rate and the CL yield increase as the solution acidity decreases was explained by different reactivities of the U _aq ⁴⁺ aquation and the products of its stepwise hydrolysis, UOH³⁺ and U(OH)₂ ²⁺, toward O₂. Based on the results of analysis of the chain-radical mechanism of the reaction between U⁴⁺ and O₂, it was concluded that transfer of an electron from the UO₂ ⁺ ion to the oxidizing agent (a ·OH radical) is the most plausible elementary step of the reaction of (UO₂ ²⁺)^* formation. It was found that the reaction rate, as well as the CL yield, increase substantially in the presence of uranyl ion. Catalytic action of UO₂ ²⁺ was explained by the formation of a UO₂ ²⁺·UO₂ ⁺ complex, which reduces the rate of the UO₂ ⁺ disproportionation reaction (UO₂ ⁺ is an intermediate of the reaction and is involved in chain propagation), and by regeneration of the active center, UO₂ ⁺, in the reaction of UO₂ ²⁺ with U⁴⁺. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1522–1528, September, 2000.     

Metal chelates of ampicillin versus amoxicillin: synthesis,structural investigation,and biological studies

Solid chelates derived from some alkaline earth and transition metal complexes with ampicillin (Hamp, a) and amoxicillin (Hamox, b) were synthesized and characterized using elemental analysis, molar conductivity, IR, magnetic susceptibility, and thermogravimetric studies. Both drugs behave as tetradentate ligands coordinating to metal through amino, imino, and carboxylate as well as through β-lactamic carbonyl. All chelates have octahedral geometry except Cu(II) complexes which have square planar structure and uranium has pentagonal bipyramidal coordination. ¹H- and ¹³C-NMR of the Zn(II) and UO₂(VI) chelates are compared with the free ligands. The antimicrobial activity of the prepared chelates was determined.     

A Photochemical Study of Uranyl Ion Interaction with the Triton X-100 Micellar System

This is a report on the spectroscopic characteristics of UO²⁺₂in the excited state in Triton X-100 micellar medium. It also indicates some important results of viscosity and surface tension measurements of the system which have direct relevance to the spectroscopic investigation in the excited state. The quenching of the UO²⁺₂fluorescence due to Triton X-100, upon micellization in the aqueous medium, reveals two kinds of microenvironments of the fluorophore from the Stern–Volmer plot. This has been verified by flash photolytic measurements. A blue shift of the quenched emission spectrum is ascribed to the collisional encounter of UO²⁺₂with the head groups of Triton X-100.     

Hydrolysis of dioxouranium(VI): a calorimetric study in NaClaq and NaClO4 aq, at 25 °C

We report the results of a calorimetric study on the hydrolysis of UO₂²⁺ in different ionic media (NaClO_4 aq, NaCl_aq) at 25 °C. Experiments in NaCl were performed at different ionic strength, at I≤1 mol l⁻¹. The species considered in both ionic media were UO₂(OH)⁺, (UO₂)₂(OH)₂²⁺ and (UO₂)₃(OH)₅⁺, and in addition (UO₂)₃(OH)₄²⁺ and (UO₂)₃(OH)₇⁻ in NaCl_aq. The dependence on ionic strength of enthalpy changes in NaCl_aq was expressed by the simple linear equation ΔH_pq=ΔH°_pq+aI^1/2 (a, empirical parameter). Comparison with literature findings is given and some recommended values are reported.     

Extraction of impurities of rare-earth elements from uranium dioxide using bromine trifluoride for their preconcentration and analytical determination

The behavior of impurities of rare-earth elements in the fluorination of UO₂ with bromine trifluoride is studied by the radioactive tracer method using¹⁵²Eu radionuclide. It is demonstrated that uranium is completely removed as hexafluoride, whereas impurities of rare-earth elements quantitatively remain in the crucible because of the nonvolatility of their fluorides. Based on this fact, the concentrations of rare-earth elements in UO₂ is determined. Results of analysis are in agreement with the data that were obtained using the conventional technique for the extraction of rare-earth elements from UO₂     

CMPO/[Cnmim][NTf2]体系对Eu3+和UO22+的萃取行为

讨论了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)/1-烷基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([C_nmim][NTf₂],n=2,8,12)萃取体系分别对硝酸溶液中的铕离子(Eu³⁺)和铀酰根离子(UO₂²⁺)的萃取行为。主要研究了硝酸浓度、接触时间、温度、CMPO浓度对CMPO/[C_nmim][NTf₂]体系萃取性能的影响,并选取CMPO/[C2mim][NTf₂]体系对模拟高放废液中的镧锕元素进行了萃取分离。结果表明:随着离子液体侧链长度增长,萃取平衡时间逐渐延长;CMPO/[C2mim][NTf₂]体系对Eu³⁺的萃取是放热反应,萃取率随酸度增加而逐渐降低,对UO₂²⁺则是吸热反应,萃取率随酸度增加而逐渐升高;通过机理研究,推测出对Eu³⁺的萃取反应是离子交换,而对UO₂²⁺的萃取反应则是中性配位;CMPO/[C2mim][NTf₂]体系能有效的萃取模拟高放废液中的镧系、锕系元素,且在高酸下有一定的镧锕分离效果。     

HYDROLYSE DE SPIROPHOSPHORANES I. Dérivés du Tétraoxa-1,4,6,9 Phospha V-5 Spiro (4–4) et de l'Heptaméthyl-2,2,4,7,7,8,8 Trioxa-1,6,9 aza 4 Phospha V-5 Spiro (4,4) Nonane

Abstract

L'hydrolyse de tétraoxaspirophosphoranes (1) et de trioxazaspirophosphoranes (2) conduit essentiellement soit [sgrave] des mono et des diesters phosphoniques (cas de 1) soit [sgrave] des monoesters phosphoniques (cas de 2). Le rôle de differents facteurs sur la réaction d'hydrolyse (solvant, température, groupements R extracycliques, nature du cycle) a été précisé. Un cas particulier de labilité de liaison P^v–C a été mis en évidence.

Tetraoxaspirophosphoranes (1) and trioxazaspirophosphoranes (2) hydrolysis lead mainly and respectively to phosphonic mono or diesters and to phosphonic monoesters. The effect of differents factors (solvent, temperature, extracyclic R groups, nature of the ring) has been examined. In one case the P^v–C bond has been found to be particularly labile.     

The Use of the CS2N− 3/HSO− 3/O2 Reaction for the Analytical Determination of Dissolved Oxygen

Abstract

A new analytical Spectrophotometric method has been developed for the determination of dissolved O₂ in the range 4.6 × 10^?6?4.1 × 10^?5M, based on the CS₂N^? ₃/HSO^? ₃/O₂ reaction. In one single experiment 2.3 × 10^?5 M of oxygen can be determined with an uncertainty of ± 7 × 10^?7M for a confidence level of 95%.     

Hydroxy Naphthol Blue as a Spectrophotometric and Fluorometric Reagent for the Uranyl Ion

Abstract

The utility of hydroxy naphthol blue (HNB) as a spectrophotometric and fluorometric reagent for the uranyl ion has been investigated. In phthalate buffer (at a pH of 4.0), UO₂ ²⁺ forms a brown complex of low absorptivity with the red form of HNB. By following the decrease in HNB absorbance at 530 nm (which has ε = 4.1 × 10³) uranyl ion can be determined to levels as low as 1.1 × 10^?6 M (0.30 μg/ml). HNB also emits at 460 nm when excited at 365 nm at these pH values, while the UO₂ ²⁺ complex exhibits greatly reduced emission. Examination of the quenching of HNB emission by UO₂ ²⁺ allows the determination of uranyl ion to levels as low as 3.2 × 10^?6 M (0.86 μg/ml). A 1:1 type complex was formed between UO₂ ²⁺ and HNB, and a formation constant of 9.77 × 10³ (log K₁ = 3.99) was measured for the complex.     

CMPO/[Cnmim][NTf2]体系对Eu3+和UO22+的萃取行为

讨论了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)/1-烷基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([C_nmim][NTf_2],n=2,8,12)萃取体系分别对硝酸溶液中的铕离子(Eu~(3+))和铀酰根离子(UO_2~(2+))的萃取行为。主要研究了硝酸浓度、接触时间、温度、CMPO浓度对CMPO/[C_nmim][NTf_2]体系萃取性能的影响,并选取CMPO/[C_2mim][NTf_2]体系对模拟高放废液中的镧锕元素进行了萃取分离。结果表明:随着离子液体侧链长度增长,萃取平衡时间逐渐延长;CMPO/[C3+2mim][NTf_2]体系对Eu的萃取是放热反应,萃取率随酸度增加而逐渐降低,对UO_2~(2+)则是吸热反应,萃取率随酸度增加而逐渐升高;通过机理研究,推测出对Eu~(3+)的萃取反应是离子交换,而对UO_2~(2+)的萃取反应则是中性配位;CMPO/[C_2mim][NTf_2]体系能有效的萃取模拟高放废液中的镧系、锕系元素,且在高酸下有一定的镧锕分离效果。     

Extraction and Spectrophotometric Determination of Manganese(VII) with N1-Hydroxy-N1,N2-Diphenylbenzamidine

Abstract

Spectrophotometric determination of manganese(VII) at 614 nm after its extraction with N¹ -hydroxy-N¹,N²-diphenylbenzamidine into amyl alcohol at pH 7–8 is described. Beer's law was obeyed for 0.1–10 μg ml^?1 Mn(VII). The effects of experimental variables and of several diverse ions on the determination of manganese(VII) have been studied. The method has been applied to the determination of manganese in steels and in water extracts of a commercial tea and is found to be simple, precise and highly selective.     

Recovery of 177Lu from Irradiated HfO2 Targets for Nuclear Medicine Purposes

A new method of production of one of the most widely used isotopes in nuclear medicine, ¹⁷⁷Lu, with high chemical purity was developed; this method includes irradiation of the HfO₂ target with bremsstrahlung photons. The irradiated target was dissolved in HF and then diluted and placed onto a column filled with LN resin. Quantitative sorption of ¹⁷⁷Lu could be observed during this process. The column later was rinsed with the mixture of 0.1 M HF and 1 M HNO₃ and then 2 M HNO₃ to remove impurities. Quantitative desorption of ¹⁷⁷Lu was achieved by using 6 M HNO₃. The developed method of ¹⁷⁷Lu production ensures high purification of this isotope from macroquantities of hafnium and zirconium and radioactive impurities of carrier-free yttrium. The content of ^177mLu in ¹⁷⁷Lu in photonuclear production was determined. Due to high chemical and radionuclide purity, ¹⁷⁷Lu obtained by the developed method can be used in nuclear medicine.     

Trace Determination of Uranyl Ion Using a Blue Led as Excitation Source in Phase-Resolved Luminescence Spectroscopy

Abstract

A phase-resolved luminescence system based on the use of a light emitting diode (LED) is applied to the trace determination of uranyl ion (UO₂ ²⁺). The system performance is evaluated, phase resolved spectra of UO₂ ²⁺ are shown as well as its lifetime determination using multifrequency phase resolved measurements. Analytical figures of merit are also presented for this system. A limit of detection (LOD) of 10 μg/L is obtained at the blue LED excitation wavelength of 460 nm and its results compare well with a conventional system. Also, a linear dynamic range of ca. 5 orders of magnitude is observed. In situ quenching correction of the analytical signal was evaluated and was applied to a real sample for uranyl determination.     

Nouveaux Matériaux hybrides organiques–inorganiques obtenus par action du tétraethoxysilane avec des molécules hétérocycliques bi-fonctionnelles

New hybrid organic–inorganic materials have been obtained by the reaction of tetraethylorthosilicate (TEOS) with bi-functional heterocyclic molecules in ethanol using HCl as a catalyst at room temperature. This reaction has led to the formation of colored and transparent gels. The characterization of xerogels has been carried by infrared, ²⁹Si and ¹³C CP MAS-NMR, DTA–TGA, scanning electron microscopy, Brunauer–Emmet–Teller method (BET), and DRX. The obtained results show that organic molecules react with TEOS leading to gels, in which Si–N, Si–O, and Si–S bridges are formed. According to N₂-physisorption results, isotherms seem to have a similar sit, and classified as type IV according to the International Union of Pure and Applied Chemistry, synthesized X₁, X₂, and X₄ are mesoporous solids but X₃ is microporous. The BET surface area of these materials is important. It varied from 47 to 302 m²g^?1. The optic and magnetic properties of hybrids are also studied by Ultraviolet–visible spectroscopy and résonance para-électronique. The obtained results show that all materials are semiconductors, and X₂, X₃, and X₄ are paramagnetic but X₁ is diamagnetic.     

Setting up of an Isotope Analyser for Quantitative Determination of Percentage Abundance of 15N in Nitrogen Gas

Abstract

An ¹⁵N isotope analyser has been assembled for the quantitative determination of the percentage abundance of ¹⁵N isotope in nitrogen gas employing molecular optical emission spectroscopic technique. The (2,0) band of the second positive system of N₂ was excited in a high frequency discharge. The band heads of the isotopic species ¹⁴N¹⁴N and ¹⁴N¹⁵N molecules were resolved using a 0.5 m monochromator and their intensity peaks were measured. The ratio of the peak heights enabled the quantitative determination of ¹⁵N in the N₂ sample. The performance of the isotope analyser assembled was evaluated and it was found to be quite good as inferred from the analysis of primary standards. The analytical error in the ¹⁵N concentration-range 0.36 to 24% is <6% and rsd is <4%. A salient feature of the method adopted is that it is direct and does not call for the use of comparision standards.     

Naphthalene and pyrrole substituted guanidine in selective sensing of Cu2+, Hg2+, Pb2+ and CN− ions under different conditions

Naphthalene and pyrrole substituted guanidine 1 has been designed and synthesised. Compound 1 efficiently distinguishes Cu²⁺, Hg²⁺ and Pb²⁺ ions by exhibiting different responses in fluorescence. While compound 1 exhibited turn-on emission selectively in the presence of Hg²⁺ and Pb²⁺ ions in CH₃CN and CH₃CN–H₂O (1:1, v/v), respectively, it showed decrease in emission upon interaction with Cu²⁺ ion in CH₃CN. Furthermore, the Cu-1 ensemble has been established as a potential probe for selective detection of CN^? ion over a series of other anions involving colour change (in ordinary light: colourless to light yellow and under UV light: colourless to sky blue). Theoretical insight has been invoked to understand the mode of metal–ligand interaction.     

Determination of Oxygen to Uranium Ratio in Uranium Dioxide Nuclear Fuel by Differential Pulse Polarography

A differential pulse polarographic method for determination of oxygen to uranium ratio in uranium oxides is fully described. An accuracy ?2.62% to +4.35% was achieved by calibrating the method against standard U₃O₃, replicate test runs with UO₂, gave a precision of ±4.59% or better. The method is now successfully used in routine analysis for UO² fuel.