Relativistic bond lengthening of UO 2 2+ and UO2

Summary Relativistic calculations on UO₂ [1] have shown that relativity leads to substantial bondlengthening in this compound, in contrast to the bond contraction found almost exclusively for other compounds. The bond lengthening isnot caused by the relativistic expansion of the 5f valence AO of U, which is the primary bond forming orbital on U in UO₂. The origin of the bond lengthening can be traced back to the semi-core resp. subvalence character of the U 6p AO. The valence character of 6p shows up in an increasing depopulation of the 6p upon bond shortening, and hence loss of mass-velocity stabilization. The core character of 6p shows up in large off-diagonal mass-velocity matrix elements 5p|h _MV|6p which are shown to have an overall bond lengthening effect. The larger expansion in UO₂ than in UO ₂ ²⁺ is due to destabilization of U levels in UO₂, caused by repulsion of the two additional 5f electrons.The present analysis corroborates the picture of relativistic bond length effects of Ref. [2].     

Electronic structure and spectrum of UO2 2+ and UO2Cl4 2-

A theoretical study is presented of the electronic spectra of the UO(2) (2+) and UO(2)Cl(4) (2-) ions, based on multiconfigurational perturbation theory (CASSCF/CASPT2), combined with a recently developed method to treat spin-orbit coupling [P.-A. Malmqvist et al., Chem. Phys. Lett. 357, 230 (2002); B. O. Roos and P.-A. Malmqvist, Phys. Chem. Chem. Phys. 6, 2919 (2004)]. The results are compared to the experimental spectroscopic data obtained for uranyl ions in Cs(2)UO(2)Cl(4) crystals from Denning [Struct. Bonding (Berlin) 79, 215 (1992)] and to previous theoretical calculations performed using a combined configuration-interaction spin-orbit treatment [Z. Zhang and R. M. Pitzer, J. Phys. Chem. A 103, 6880 (1999); S. Matsika and R. M. Pitzer, J. Phys. Chem. A. 105, 637 (2001)]. As opposed to the latter results, the calculations performed in this work point to a significant effect of the weakly bound equatorial chlorine ligands on the excitation energies.     

Complexation study of dibenzo-18-crown-6 with UO2 2+ cation in binary mixed non-aqueous solutions

The complexation reaction of macrocyclic ligand, dibenzo-18-crown-6 (DB18C6) with UO₂ ²⁺ cation was studied in ethylacetate-1,2-dichloroethane (EtOAc/DCE), acetonitrile-1,2-dichloroethane (AN/DCE), methanol-1,2-dichloroethane (MeOH/DCE) and ethanol-1,2-dichloroethane (EtOH/DCE) binary solutions at different temperatures using the conductometric method. The conductance data show that the stoichiometry of the complex formed between DB18C6 and UO₂ ²⁺ cation is affected by the nature of the solvent systems. A non-linear behaviour was observed for changes of log K _f of (DB18C6.UO₂)⁺² complex versus the composition of the binary mixed solvents. The values of thermodynamic quantities (?S°_c, ?H°_c) for formation of (DB18C6.UO₂)⁺² complex were obtained from temperature dependence of the stability constant using the van’t Hoff plots. The results show that in most cases, the complex is enthalpy stabilized and in all cases entropy stabilized and both parameters are affected by the nature and composition of the mixed solvents. In addition, the complex formation between dicyclohexyl-18-crown-6 (DCH18C6) and UO₂ ²⁺ cation was studied in pure AN and the results were compared with those of the (DB18C6.UO₂)⁺² complex.     

Electronic spectroscopy and ionization potential of UO2 in the gas phase

The electronic spectroscopy of UO(2) has been examined using multiphoton ionization with mass-selected detection of the UO(2) (+) ions. Supersonic jet cooling was used to reduce the spectral congestion. Twenty-two vibronic bands of neutral UO(2) were observed in the range from 17,400 to 32,000 cm(-1). These bands originated from the U(5fphi(u)7ssigma(g))O(2) X (3)Phi(2u) and (3)Phi(3u) states. The stronger band systems are attributed to metal-centered 7p<--7s transitions. Threshold ionization measurements were used to determine the ionization potentials of UO and UO(2). These were found to be higher than the values obtained previously from electron impact measurements but in agreement with the results of recent theoretical calculations.     

UO 2 2+ sorption on bentonite

The capacity of bentonite and purified bentonite to remove UO ₂ ²⁺ ions from aqueous solutions has been investigated. The UO ₂ ²⁺ uptake in these clays was determined for 0.2 and 0.002M uranyl nitrate solutions. It was found that under these conditions (0.2M) the maximum UO ₂ ²⁺ uptake was 1.010±0.070 meq UO ₂ ²⁺ /g of bentonite and 0.787±0.020 meq UO ₂ ²⁺ /g of purified bentonite. In purified bentonite UO ₂ ²⁺ sorption is irreversible up to 50 hours as no desorption was observed. Such is not the case in the natural bentonite. X-ray diffraction, thermal analyses, and transmission electron microscopy were used to characterize the solids. The uranium content was determined by neutron activation analysis.     

Studies on ion exchange equilibria and kinetics: V. UO 2 2+ −Na+−H+ ternary cation exchange kinetics

The kinetics of particle-diffusion controlled ion exchange in the ternary system of cations UO ₂ ²⁺ –Na⁺–H⁺–001×7 strong acidic resin has been studied. In the [R–H⁺]/(Na⁺+UO ₂ ²⁺ ) system, the change of the amount of Na⁺ in the resin phase with time showed a high peak. In the [R–Na⁺]/(H⁺+UO ₂ ²⁺ ) system, the change of the amount of H⁺ in the resin phase with time also showed a high peak. In the [R₂–UO ₂ ²⁺ ]/(H⁺+Na⁺) system, the change of amount of H⁺ in the resin phase with time showed merely a small peak. This kinetic character of the ternary ion exchange system in the finite solution volume has been analyzed according to the Nerst-Planck equation, and on the whole, the trend of the experimental results is consistent with the resulting numerical solution of the set of Nerst-Planck equations.     

Accurate ionization potentials for UO and UO2: a rigorous test of relativistic quantum chemistry calculations

Accurate ionization potential (IP) measurements provide essential thermodynamic information and benchmark data that can be used to evaluate the validity of electronic structure models. Calculations of the first IP of UO2 using relativistic methods consistently predict values that are approximately 0.7 eV higher than the accepted experimental value. The present measurements validate the theoretical calculations and show that the previous determinations corresponded to the ionization of thermally excited molecules. Similarly, new measurements of the IP for UO show that the currently accepted value is too low by 0.4 eV.     

Thermodynamic study of complex formation between dibenzo-18-crown-6 and UO2 2+ cation in different non-aqueous binary solutions

In the present work the complexation process between UO₂ ²⁺ cation and the macrocyclic ligand, dibenzo-18-crown-6 (DB18C6) was studied in ethylacetate–dimethylformamide (EtOAc/DMF), ethylacetate–acetonitrile (EtOAc/AN), and ethylacetate–tetrahydrofuran (EtOAc/THF) and ethylacetate–propylencarbonate (EtOAc/PC) binary solutions at different temperatures using the conductometric method. The results show that the stoichiometry of the (DB18C6 . UO₂)²⁺ complex in all binary mixed solvents is 1:1. A non-linear behavior was observed for changes of log K_f of this complex versus the composition of the binary mixed solvents. The stability constant of (DB18C6 . UO₂)²⁺ complex in various neat solvents at 25 °C decreases in order: THF > EtOAc > PC > AN > DMF, and in the binary solvents at 25 °C is: THF–EtOAc > PC–EtOAc > DMF–EtOAc ≈ AN–EtOAc. The values of thermodynamic quantities (?H°_c, ?S°_c) for formation of this complex in the different binary solutions were obtained from temperature dependence of its stability constant and the results show that the thermodynamics of complexation reaction between UO₂ ²⁺ cation and DB18C6 is affected strongly by the nature and composition of the mixed solvents.     

Solvent influence upon complexation of N-phenylaza-15-crown-5 with UO2 2+ cation in binary mixed non-aqueous solvents

The complexation reaction of N-phenylaza-15-crown-5 (PhA15C5) with UO₂ ²⁺ cation was studied in acetonitrile–methanol (AN–MeOH), acetonitrile–butanol (AN–BuOH), acetonitrile–dimethylformamide (AN–DMF) and methanol–propylencarbonate (MeOH–PC) binary solutions, at different temperatures by conductometry method. The conductance data show that the stoichiometry of the complex formed between PhA15C5 with UO₂ ²⁺ cation in most cases is 1:1 [M:L], but in some solvent systems a 1:2 [M:L₂] complex is formed in solutions. The results revealed that, the stability constant of (PhA15C5·UO₂)²⁺ complex in the binary mixed solvents varies in the order: AN–BuOH>AN–MeOH>AN–DMF. In the case of the pure organic solvents, the sequence of the stability of the complex changes as: AN>PC>BuOH>DMF. A non-linear relationship was observed for changes of logK_f of (PhA15C5·UO₂)²⁺ complex versus the composition of the binary mixed solvents. The corresponding standard thermodynamic parameters (ΔH_c°, ΔS_c°) were obtained from temperature dependence of the stability constant. The results show that the values and also the sign of these parameters are influenced by the nature and composition of the mixed solvents.     

Collision-induced dissociation tandem mass spectrometry of desferrioxamine siderophore complexes from electrospray ionization of UO2(2+), Fe3+ and Ca2+ solutions

Desferrioxamine (DEF) is a trihydroxamate siderophore typical of those produced by bacteria and fungi for the purpose of scavenging Fe(3+) from environments where the element is in short supply. Since this class of molecules has excellent chelating properties, reaction with metal contaminants such as actinide species can also occur. The complexes that are formed can be mobile in the environment. Because the natural environment is extremely diverse, strategies are needed for the identification of metal complexes in aqueous matrices having a high degree of chemical heterogeneity, and electrospray ionization mass spectrometry (ESI-MS) has been highly effective for the characterization of siderophore-metal complexes. In this study, ESI-MS of solutions containing DEF and either UO(2)(2+), Fe(3+) or Ca(2+) resulted in generation of abundant singly charged ions corresponding to [UO(2)(DEF - H)](+), [Fe(DEF - 2H)](+) and [Ca(DEF - H)](+). In addition, less abundant doubly charged ions were produced. Mass spectrometry/mass spectrometry (MS/MS) studies of collision-induced dissociation (CID) reactions of protonated DEF and metal-DEF complexes were contrasted and rationalized in terms of ligand structure. In all cases, the most abundant fragmentation reactions involved cleavage of the hydroxamate moieties, consistent with the idea that they are most actively involved with metal complexation. Singly charged complexes tended to be dominated by cleavage of a single hydroxamate, while competitive fragmentation between two hydroxamate moieties increased when the doubly charged complexes were considered. Rupture of amide bonds was also observed, but these were in general less significant than the hydroxamate fragmentations. Several lower abundance fragmentations were unique to the metal examined: abundant loss of H(2)O occurred only for the singly charged UO(2)(2+) complex. Further, NH(3) was eliminated only from the singly charged Fe(3+) complex; this and fragmentation of C-C and C-N bonds derived from neither the hydroxamate nor the amide groups suggested that Fe(3+) insertion reactions were competing with ligand complexation. In no experiments were coordinating solvent molecules observed, attached either to the intact complexes or to the fragment ions, which indicated that both intact DEF and its fragments were occupying all of the coordination sites around the metal centers. This conclusion was based on previous experiments that showed that undercoordinated UO(2)(2+) and Fe(3+) readily added H(2)O and methanol in the ESI quadrupole ion trap mass spectrometer that was used in this study.     

Electrophoretic studies on the mixed nitrilotriacetate-penicillamine complexes of Pb2+ and UO 2 2+

A technique involving the use of paper electrophoresis is described for the study of binary and mixed-complex systems in solution. This technique is based on the movement of a spot of metal ion in an electric field with the complexants added in the background electrolyte at pH 8.5. The concentration of primary ligand (nitrilotriacetate) was kept constant, while that secondary ligand (penicillamine) was varied. A graph of log[penicillamine] versus mobility was used to obtain information on the mixed complexes and to calculate stability constants. The stability constants of mixed-ligand complexes lead(II)-nitrilotriacetate-penicillamine and uranyl(II)-nitrilotriacetate-penicillamine have been found to be 5.68 ± 0.09 and 6.56 ± 0.05 (logarithm stability constant values), respectively, at ionic strength 0.1 M and a temperature of 35°C. The text was submitted by the author in English.     

Equatorial and apical solvent shells of the UO2 2+ ion

First principles molecular dynamics simulations of the hydration shells surrounding UO(2)(2+) ions are reported for temperatures near 300 K. Most of the simulations were done with 64 solvating water molecules (22 ps). Simulations with 122 water molecules (9 ps) were also carried out. The hydration structure predicted from the simulations was found to agree with very well-known results from x-ray data. The average U=O bond length was found to be 1.77 A. The first hydration shell contained five trigonally coordinated water molecules that were equatorially oriented about the O-U-O axis with the hydrogen atoms oriented away from the uranium atom. The five waters in the first shell were located at an average distance of 2.44 A (2.46 A, 122 water simulation). The second hydration shell was composed of distinct equatorial and apical regions resulting in a peak in the U-O radial distribution function at 4.59 A. The equatorial second shell contained ten water molecules hydrogen bonded to the five first shell molecules. Above and below the UO(2)(2+) ion, the water molecules were found to be significantly less structured. In these apical regions, water molecules were found to sporadically hydrogen bond to the oxygen atoms of the UO(2)(2+), oriented in such a way as to have their protons pointed toward the cation. While the number of apical waters varied greatly, an average of five to six waters was found in this region. Many water transfers into and out of the equatorial and apical second solvation shells were observed to occur on a picosecond time scale via dissociative mechanisms. Beyond these shells, the bonding pattern substantially returned to the tetrahedral structure of bulk water.     

Characterization of UO 2 2+ exchanged Y zeolite

The present study discusses the incorporation of uranyl ion into Y-zeolite framework. The UO ₂ ²⁺ sorption was measured by neutron activation analyses. The Y-zeolite framework distorts in response to the cations present in the structure. Hence, depending on the amount and the location of the exchanged cations, the features of the X-ray diffraction pattern may vary. From the Rietveld analysis of these patterns, the positions occupied by the UO ₂ ²⁺ cations in the zeolite network were determined.     

Modeling Heterogeneity in UO2 Nanoparticles Using X-ray Absorption Spectroscopy

EXAFS provides the capability to interrogate nanoparticle (NP) structure in atomistic detail without relying on long-range crystallinity. There is a limitation in that EXAFS provides averaged structural information, making it difficult to separate a small amount of heterogeneous structure from bulk. In this work, models were developed to extract surface-specific information from conventional EXAFS measurements collected on UO₂ NPs of varying size. Specifically, the surface terminating species of UO₂ NPs was determined from comparison of coordination numbers with geometric models while the origin of static disorder was interrogated from user-defined simulations. Results show that the degree of oxygenation on the NP surface does not significantly deviate from bulk surface and that static disorder is highly enhanced in NP surface layers but cannot be attributed to surface relaxation effects alone. The approach described herein has the potential to be adapted to a range of inorganic NP systems to interrogate surface structure.     

Adsorption of UO2 2+ on natural composite materials

The prediction of the adsorption behavior of natural composite materials was studied by a single mineral approach. The adsorption of U(VI) on single minerals such as goethite, hematite, kaolinite and quartz was fully modeled using the diffuse-layer model in various experimental conditions. A quasi-thermodynamic database of surface complexation constants for single minerals was established in a consistent manner. In a preliminary work, the adsorption of a synthetic mixture of goethite and kaolinite was simulated using the model established for a single mineral system. The competitive adsorption of U(VI) between goethite and kaolinite can be well explained by the model. The adsorption behavior of natural composite materials taken from the Koongarra uranium deposit (Australia) was predicted in a similar manner. In comparison with the synthetic mixture, the prediction was less successful in the acidic pH range. However, the model predicted well the adsorption behavior in the neutral to alkaline pH range. Furthermore, the model reasonably explained the role of iron oxide minerals in the adsorption of U(VI) on natural composite materials.     

The solvent extraction of UO 2 2+ and Th4+ with petroleum sulfoxide

The influence of the concentration of nitric, hydrochloric and phosphoric acids, petroleum sulfoxides (PSO), salting-out agent, kind of diluent and temperature on the distribution ratio of U(VI) and Th(IV) has been systematically studied. It is found that the extraction regularity of PSO is similar to that of TBP. The distribution ratio in phosphoric acid is lower, but it increases with the increase of hydrochloric acid concentration and reaches a high value. The U(VI) exhibits the maximum distribution ratio at 3–4 mol/l HNO₃. The distribution ratio of U(VI) and Th(IV) increases rapidly in the presence of a salting out agent. The extracted compounds are determined to be UO₂(NO₃)₂2PSO and Th(NO₃)₄2PSO. The extraction enthalpies of U(VI) and Th(IV) with PSO were also calculated.     

Study of complex formation between dicyclohexyl-18-crown-6 and UO2 2+ cation in some binary mixed non-aqueous solvents using conductometric method

In the present work, the complexation process between UO₂ ²⁺ cation and the macrocyclic ligand, dicyclohexyl-18-crown-6 (DCH18C6) was studied in ethyl acetate/1,2-dichloroethane (EtOAc/DCE), acetonitrile/1,2-dichloroethane (AN/DCE), methanol/1,2-dichloroethane (MeOH/DCE) and ethanol/1,2-dichloroethane (EtOH/DCE) binary solutions at different temperatures using the conductometric method. The conductance data show that in most cases, the stoichiometry of the complex formed between DCH18C6 and UO₂ ²⁺ cation is 1:1 [M:L], but in some solvent systems also a 1:2 [M:L₂] complex is formed in solutions. The values of stability constant of (DCH18C6·UO₂)²⁺ complex which were obtained from conductometric data, show that the stability of the complex is affected by the nature and also the composition of the solvent system and in all cases, a non-linear behavior is observed for the variation of (log?K _f) of the (DCH18C6·UO₂)²⁺ complex versus the composition of the binary mixed solvents. The values of thermodynamic quantities $ \Updelta H_{c}^{\circ} $ and $ \Updelta S_{c}^{\circ} $ for formation of (DCH18C6·UO₂)²⁺ complex were obtained from temperature dependence of the stability constant using the van’t Hoff plots. The experimental results show that depending on the nature and composition of the solvent systems, the complex is enthalpy stabilized or destabilized, but in most cases, it is stabilized from entropy view point and both thermodynamic parameters are affected by the nature and composition of the binary mixed solutions.     

胶原-单宁树脂的制备及其对水溶液中UO2+2的吸附特性研究

以天然牛皮为原料,经胃蛋白酶处理制得水解胶原;通过胶原-黑荆树单宁-醛反应制备了胶原-单宁树脂(C-TR)吸附材料,并表征了材料的形貌,测定了材料的比表面积、热变形温度等性质。系统研究了C-TR对水溶液中UO22 的吸附特性。结果表明,C-TR对UO22 有较强的吸附能力。当温度为303K、pH=5.0、UO22 的初始浓度2.5mmol.L-1时,吸附容量达到1.49mmolU/g。升高温度,平衡吸附量增大。pH对吸附容量的影响较大,适宜的pH范围为5.0-6.0。C-TR对UO22 的吸附平衡符合Freundlich方程。吸附动力学可用拟二级速度方程来描述。C-TR对UO22 的吸附基本不受NaCl影响,该吸附材料可望用于海水中铀的富集和分离。     

Adsorptive features of polyacrylic acid hydrogel for UO2 2+

Polyacrylic acid hydrogel was synthesized by Free Radical polymerization and characterized by means of FTIR. The FTIR results show that the carboxylic groups in the complexes coordinated to the metal ions in the form of two dentate. The effects of contact time, solid/liquid ratio, pH value, and initial concentration on the adsorption of UO₂ ²⁺ ions onto polyacrylic acid were investigated. The adsorption of UO₂ ²⁺ ions was highly dependent on the initial pH of metal ions solution and initial metal ions concentration. The adsorption kinetic data indicated that the chemical adsorption was the swiftness processes, the adsorption equilibrium could be achieved within 15 min. And there are very good correlation coefficients of linearized equations for Freundlich model, which indicated that the sorption isotherm of the hydrogel for UO₂ ²⁺ can be fitted to the Freundlich model. It was found that the maximum adsorption quantity of UO₂ ²⁺ was 1,179 mg/g. After five times of repeated tests for the hydrogel it still remained its excellent adsorption.