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排序方式: 共有249条查询结果,搜索用时 296 毫秒
1.
A. A. Zazhogin A. P. Zazhogin A. I. Komyak A. I. Serafimovich 《Journal of Applied Spectroscopy》2003,70(6):827-831
Based on the analysis of electronic absorption and luminescence spectra, the processes of complexing in an aqueous solution of uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) on gradual addition of small amounts of acetone have been investigated. In a pure aqueous solution, uranyl exists as the UO2·5H2O complex. It is shown that addition of acetone to the solution leads to displacement of some water molecules from the first coordination sphere of uranyl and formation of uranyl nitrate dihydrate complexes, UO2(NO3)2·2H2O. It has been established that the stability of these complexes is determined by the decrease in both the water activity and the degree of hydration of uranyl and nitrate. This is the result of the local increase in the concentration of the molecules of acetone (due to its hydrophobicity) in those regions of the solution in which there are uranyl and nitrate ions. The experimental facts supporting the proposed mechanism are given. 相似文献
2.
Using the chemiluminescence oxidation of U(IV) and H2O2 with xenon trioxide as a model, it has been found that during the photolysis of solutions of UO2SO4 in sulfuric acid in the absence of any organic compounds, the accumulation of U(SO4)2 and H2O2 takes place as a result of the reaction of the primary products of the photoreduction of uranyl ion,i.e., UO2
+ and the OH radical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 751–754, April, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project 93-03-12291. 相似文献
3.
4.
The polarographic behaviour of dithiodiacetic acid and that of U(VI) in a solution containing dithiodiacetic acid as complexing agent have been investigated. For the dithiodiacetic acid system, two waves appear over the pH range studied. The prewave is kinetic in nature and the mainwave is diffusion-controlled. However, as U(VI) is added into the dithiodiacetic acid system, the polarogram changes due to the existence of a complex. The current-potential curve of the first wave is not the normal S shape. This is due to the superposition of the first wave of the ligand and the wave due to the reduction of the U(VI) in the complex to U(V). The second wave is due to the reduction of the complex The first wave is an adsorption-controlled current and the second wave is partly diffusion-controlled and partly adsorption-controlled. We propose an electrode reaction mechanism for both systems and the complex species. The dissociation constant of the complex HASSAUO+2 is found to be of the order of 10?4. 相似文献
5.
1 INTRODUCTION Tri-butyl phosphate (TBP) has been widely used as the extraction reagent in U-Th fuel to separate uranium from thorium. But di-butyl phos- phate (DBP) and butyl phosphate (MBP), the radio- lytic products of TBP, exhibit some coordinated ability to the fission elements, such as Zr and Nb. The substitutes for TBP have being studied for several decades[1~4]. The physical and chemical properties of amides are similar to those of TBP and they selectively extract U(Ⅵ… 相似文献
6.
制得二(1,8-萘啶氮氧化物)合硝酸钍和铀酰配合物,元素分析确定其组成为Th(C_3H_6N_2O)_2(NO_3)_4和UO_2(C_3H_6N_2O)_2(NO_3)_2。通过红外光谱、荧光光谱、摩尔电导、差热热重分析等方法,研究了配合物的性质。 相似文献
7.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
8.
Tenu R. Gentil S. Baudu S. Counioux J. J. 《Journal of Thermal Analysis and Calorimetry》1999,58(1):89-101
The binary system H2O—UO2(NO3)2 was studied by solubility measurements and constant heat flow thermal analysis. Temperature and composition of the eutectic transformation between ice and uranyl nitrate hexahydrate were accurately defined. A new hydrate with 24 molecules of water decomposes at –21°C according to the peritectoid reaction<UO2(NO3)2·24H2O> <UO2(NO3)2·6H2O> + 18<H2O>The quasi-ideal model was applied to the solid—liquid equilibria, using the following reaction hypothesis:((UO
2
2+
)) + 2((NO
3
–
))+ h((H2O)) ((UO2OH+aq)) + ((H3O+aq + 2((NO
3
–
aq))A complete calculation of the binary system was carried out with a global ionic hydration number h equal to 9 in the aqueous solutions. It allowed to the melting enthalpies of uranyl nitrate hydrates.
This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
9.
Monika S. K. Fuchs Alexey M. Shor Notker Rsch 《International journal of quantum chemistry》2002,86(5):487-501
The parallel density functional program PARA GAUSS has been extended by a tool for computing solvent effects based on the conductor‐like screening model (COSMO). The molecular cavity in the solvent is constructed as a set of overlapping spheres according to the GEPOL algorithm. The cavity tessellation scheme and the resulting set of point charges on the cavity surface comply with the point group symmetry of the solute. Symmetry is exploited to reduce the computational effort of the solvent model. To allow an automatic geometry optimization including solvent effects, care has been taken to avoid discontinuities due to the discretization (weights of tesserae, number of spheres created by GEPOL). In this context, an alternative definition for the grid points representing the tesserae is introduced. In addition to the COSMO model, short‐range solvent effects are taken into account via a force field. We apply the solvent module to all‐electron scalar‐relativistic density functional calculations on uranyl, UO22+, and its aquo complexes in aqueous solution. Solvent effects on the geometry are very small. Based on the model [UO2(H2O)5]2+, the solvation energy of uranyl is estimated to be about ?400 kcal/mol, in agreement with the range of experimental data. The major part of the solvation energy, about ?250 kcal/mol, is due to a donor–acceptor interaction associated with a coordination shell of five water ligands. One can interpret this large solvation energy also as a compounded effect of an effective reduction of the uranyl moiety plus a solvent polarization. The energetic effect of the structure relaxation in the solution is only about 8 kcal/mol. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
10.
Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones 下载免费PDF全文
Wen‐Bo Lan Xiao‐Feng Wang Li‐Ping He Yan‐Bin Meng Jun Li Bin Qiu Chang‐Ming Nie 《应用有机金属化学》2018,32(3)
The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein. 相似文献