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1.
The polarography of uranyl ion in 2,3-cresotic acid solution has been studied at 25°C under varying conditions of ligand concentration and pH. The ligands species were proved to be a 2,3-cresotate anion. The half-wave potential vs. pH value interpreted on the basis of pK value for the acid ionization, and resulted in agreement with the deduction. The mole ratio of metal to ligand was found to be 1:1 and 1:2 by conductometric titration. At pH < pK1, the complex species of UO2(H2A)2+ and UO2(HA)+ was identified. At pK1 < pH < pK2, the co-existence of UO2(HA)+, UO2(OH)(HA)2? and UO2(A)22– was confirmed. At pH > pK2, the complex species of UO2(OH) (A)23– was formed.  相似文献   

2.
Novel anilino-pyrimidine fungicides, pyrimethanil maleic salt, and pyrimethanil fumaric salt (C28H30N6O4) were synthesized by a chemical reaction of pyrimethanil with maleic acid/fumaric acid. The low-temperature heat capacities of the two compounds were measured with an adiabatic calorimeter from 80 to 350 K. The heat capacities of pyrimethanil fumaric salt are bigger than that of pyrimethanil maleic salt in the measurement temperature range. The thermodynamic function data relative to 298.15 K were calculated based on the heat capacity-fitted curves. The melting points, the molar enthalpies (Δfus H m), and entropies (Δfus S m) of fusion of pyrimethanil maleic salt and pyrimethanil fumaric salt were determined from their DSC curves. The values indicate that pyrimethanil fumaric salt was more thermostable than pyrimethanil maleic salt. The constant-volume energies of combustion (Δc U m o ) of pyrimethanil maleic salt and pyrimethanil fumaric salt were measured using an isoperibol oxygen bomb combustion calorimeter at T = (298.15 ± 0.001) K. From the Hess thermochemical cycle, the standard molar enthalpies of formation of the two compounds were derived and determined to be Δf H m o (pyrimethanil maleic salt) = ?459.3 ± 4.9 kJ mol?1 and Δf H m o (pyrimethanil fumaric salt) = ?557.2 ± 4.8 kJ mol?1, respectively. The results suggest that pyrimethanil fumaric salt is more chemically stable than pyrimethanil maleic salt.  相似文献   

3.
Two homeotypic hydrated uranyl arsenates, (UO2)[(UO2)(AsO4)]2(H2O)4, UAs4, and (UO2)[(UO2)(AsO4)]2(H2O)5, UAs5 were synthesized by hydrothermal methods. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. Their crystal structures were solved by direct methods and refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (UAs4, UAs5) wR2=0.116, 0.060, for all data, and R1=0.046, 0.033, calculated for 3176, 5306 unique observed reflections (|Fo|>4σF) respectively. UAs4 is monoclinic, space group P21/c, Z=4, a=11.238(1), b=7.152(1), c=21.941(2)Å, β=104.576(2)°, V=1706.8(1)Å3, Dcalc=4.51 g/cm3. UAs5 is orthorhombic, space group Pca21, Z=4, a=20.133(2), b=11.695(1), c=7.154(1)Å, V=1684.4(1)Å3, Dcalc=4.65 g/cm3. Both structures contain sheets of arsenate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO2)(AsO4)]1− and the uranophane sheet anion-topology. The sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with an arsenate tetrahedron on each of two adjacent sheets, resulting in open-frameworks with isolated H2O groups in the larger cavities of the structures. The uranyl arsenate sheet in UAs4 is relatively planar, and is topologically identical with the uranyl phosphate sheet in (UO2)[(UO2)(PO4)]2(H2O)4. The uranyl arsenate sheet in UAs5 is the same geometrical isomer as in UAs4, but is highly corrugated, exhibiting approximately right angle bends of the sheet after every second uranyl arsenate chain repeat.  相似文献   

4.
Study of the sulphosalicylate complexes of copper(II), nickel(II), cobalt(II) and uranyl(II) by means of cation-exchange resins.The conditional stability constants of the 1:1 complexes of the sulphosalicylate ions (L3-) with copper(II), nickel(II), cobalt(II) and uranyl ions have been determined in a sodium perchlorate solution (0.1 M) and at various pH values by a cation-exchange method based on Schubert's procedure. The limits of application of the method are discussed. The variation with pH of the conditional stability constants can be explained by the existence of the complexes: CuH2L, CuHL, CuL-; NiH2L+, NiHL, NiL-; CoHL, CoL-; UO2H2L+, UO2HL, UO2L-, UO2LOH2-. The stability constants of these complexes are reported. Distribution diagrams of the various complexes of each element with pH and total concentration of sulphosalicylate parameters are given.  相似文献   

5.
利用化学种态分析软件CHEMSPEC计算了低浓缩铀靶辐照后溶液中铀(U)的化学种态分布及其主要裂变元素对U化学种态的影响。结果表明,在单组分体系中,pH值和铀酰浓度都会显著影响U的化学种态分布。随着铀酰浓度的增大,溶液中将会生成多核配合物;在较高的NO3-浓度下,U在溶液中主要以UO22+和UO2NO3+的形式存在。CO2对不同浓度铀的种态分布影响结果表明,当铀酰浓度较低时,铀的化学种态多以碳酸铀酰的形式存在;当铀酰浓度较高时,铀的化学种态多以氢氧铀酰或柱铀矿沉淀的形式存在。计算发现,当裂片元素Tc、I、Mo的浓度小于0.01mol·L-1并分别以TcO4-、I-、MoO42-的种态存在时,这些裂片元素不改变铀的各化学种态的分布。  相似文献   

6.
Presented here are two isostructural uranyl coordination polymers [UO2(EDO)(H2O)]·H2O (1) and [UO2(BDO)(H2O)]·2H2O (2) (EDO2-=ethylene-1,2-dioxamate; BDO2-=butylene-1,2-dioxamate) with identical stepwise zigzag chain structure and distinct interchain hydrogen bonding interaction, prepared from hydrothermal reaction of DEEDO or DEBDO (DEEDO=diethyl ethylene-1,2-dioxamate; DEBDO=diethyl butylene-1,2-dioxamate) with uranyl ions. The monomeric uranyl-based fluorescence emissions of compounds 1 and 2 are red-shifted by about 6 and 5 nm respectively, compared to that of uranyl nitrate hexahydrate. Compound 1 has stronger emission than compound 2, but both their emissions exhibit triple-exponential decay. The photophysics of uranyl oxalate trihydrate was also investigated for comparison. The selective crystallization of compound 1 in alkaline solution was applied to the sequestration of uranyl ions, showing a kinetic preference.  相似文献   

7.
利用化学种态分析软件CHEMSPEC计算了低浓缩铀靶辐照后溶液中铀(U)的化学种态分布及其主要裂变元素对U化学种态的影响。结果表明,在单组分体系中,pH值和铀酰浓度都会显著影响U的化学种态分布。随着铀酰浓度的增大,溶液中将会生成多核配合物;在较高的NO3-浓度下,U在溶液中主要以UO22+和UO2NO3+的形式存在。CO2对不同浓度铀的种态分布影响结果表明,当铀酰浓度较低时,铀的化学种态多以碳酸铀酰的形式存在;当铀酰浓度较高时,铀的化学种态多以氢氧铀酰或柱铀矿沉淀的形式存在。计算发现,当裂片元素Tc、I、Mo的浓度小于0.01 mol·L-1并分别以TcO4-、I-、MoO42-的种态存在时,这些裂片元素不改变铀的各化学种态的分布。  相似文献   

8.
The hydrated neutral uranyl phosphate, (UO2)3(PO4)2(H2O)4, was synthesized by hydrothermal methods. Intensity data were collected using Mo radiation and a CCD-based area detector. The crystal structure was solved by direct methods and refined by full-matrix least-squares techniques to agreement indices wR2=0.116 for all data, and R1=0.040, calculated for the 2764 unique observed reflections (∣Fo∣≥4σF). The compound is orthorhombic, space group Pnma, Z=4, a=7.063(1) Å, b=17.022(3) Å, c=13.172(3) Å, V=1583.5(5) Å3. The structure consists of sheets of phosphate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO2)(PO4)] and the uranophane sheet anion topology. The sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with a phosphate tetrahedron on each of two adjacent sheets, resulting in an open framework with isolated H2O groups in the larger cavities of the structure.  相似文献   

9.
The effect of gel composition, absorbed dose and pH of the solution on the uranyl ion uptake capacity of N-isopropylacrylamide/maleic acid copolymeric hydrogels containing 0–3 mol% of maleic acid at 48 kGy have been investigated. Uranyl uptake capacity of hydrogels are found to increase from 18.5 to 94.8 mg [UO22+]/g dry gel as the mole % of maleic acid content in the gel structure increased from 0 to 3. The percent swelling, equilibrium swelling and diffusion coefficient values have been evaluated for poly(N-isopropylacrylamide/maleic acid) hydrogels at 500 ppm of uranyl nitrate solution.  相似文献   

10.
Two hydrated uranyl arsenates, Cs2(UO2)[(UO2)(AsO4)]4(H2O)2 (CsUAs) and Rb2(UO2)[(UO2)(AsO4)]4(H2O)4.5 (RbUAs), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using MoKα radiation and a CCD-based area detector. The crystal structure of RbUAs was solved by direct methods, whereas the structure model of the phosphate Cs2(UO2)[(UO2)(PO4)]4(H2O)2 was used for CsUAs; both were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (CsUAs, RbUAs) wR2=0.061,0.041, for all data, and R1=0.032,0.021, calculated for 5098, 4991 unique observed reflections (|Fo|>4σF), respectively. The compound CsUAs is orthorhombic, space group Cmc21, Z=4, a=15.157(2), b=14.079(2), c=13.439(2) Å, V=2867.9(1) Å3. RbUAs is monoclinic, space group C2/m, Z=4, a=13.4619(4), b=15.8463(5), c=14.0068(4) Å, β=92.311(1)°, V=2985.52(2) Å3. The structures consist of sheets of arsenate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO2)(AsO4)], that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two arsenate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H2O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. CsUAs is isostructural with its phosphate analogue, and has two Cs atoms and a H2O group in its structural cavities. RbUAs is not isostructural with its phosphate analogue, although it has a homeotypic framework. Its structural cavities are occupied by three Rb atoms and four H2O groups; one Rb position and three of the interstitial H2O groups are half-occupied. The partial occupancies of these positions probably result from the accommodation of the larger As atoms (relative to P) in the framework and resultant larger cavities.  相似文献   

11.
The preparation, spectroscopic characterization and thermal stability of neutral complexes of uranyl ion, UO2 2+, with phosphonate ligands, such as diphenylphosphonic acid (DPhP), diphenyl phosphate (DPhPO) and phenylphosphonic acid (PhP) are described. The complexes were prepared by a reaction of hydrated uranyl nitrate with appropriate ligands in methanolic solution. The ligands studied and their uranyl complexes were characterized using thermogravimetric and elemental analyses, ESI-MS, IR and UV–Vis absorption and luminescence spectroscopy as well as luminescence lifetime measurements. Compositions of the products obtained dependent on the ligands used: DPhP and DPhPO form UO2L2 type of complexes, whereas PhP forms UO2L complex. Based on TG and DTG curves a thermal stability of the complexes was determined. The complexes UO2PhP·2H2O and UO2(DPhPO)2 undergo one-step decomposition, while UO2PhP · 2H2O is decomposed in a two-step process. The thermal stability of anhydrous uranyl complexes increases in the series: DPhPO < PhP < DPhP. Obtained IR spectra indicate bonding of P–OH groups with uranyl ion. The main fluorescence emission bands and the lifetimes of these complexes were determined. The complex of DPhP shows a green uranyl luminescence, while the uranyl emission of the UO2PhP and UO2(DPhPO)2 complexes is considerably weaker.  相似文献   

12.
Two uranyl tellurates, AgUO2(HTeO5) (1) and Pb2UO2(TeO6) (2), were synthesized under hydrothermal conditions and were structurally, chemically, and spectroscopically characterized. 1 crystallizes in space group Pbca, a=7.085(2) Å, b=11.986(3) Å, c=13.913(4) Å, V=1181.5(5) Å3, Z=8; 2 is in P2(1)/c, a=5.742(1) Å, b=7.789(2) Å, c=7.928(2) Å, V=90.703(2) Å3, and Z=2. These are the first structures reported for uranyl compounds containing tellurate. The U6+ cations are present as (UO2)2+ uranyl ions that are coordinated by O atoms to give pentagonal and square bipyramids in compounds 1 and 2, respectively. The structural unit in 1 is a sheet consisting of chains of edge-sharing uranyl pentagonal bipyramids that are one bipyramid wide, linked through the dimers of TeO6 octahedra. In 2, uranyl square bipyramids share each of their equatorial vertices with different TeO6 octahedra, giving a sheet with the autunite-type topology. Sheets in 1 and 2 are connected through the low-valence cations that are located in the interlayer region. The structures of 1 and 2 are compared to those of uranyl compounds containing octahedrally coordinated cations.  相似文献   

13.
A new lead uranyl divanadate, PbUO2(V2O7), has been synthesized by high temperature solid-state reaction and its crystal structure was solved by direct methods using single-crystal X-ray diffraction data. It crystallizes in the monoclinic system with space group P21/n and following cell parameters: a=6.9212(9) Å, b=9.6523(13) Å, c=11.7881(16) Å, β=91.74(1)°, V=787.01(2) Å3, Z=4, ρmes=5.82(3), ρcal=5.83(1) g/cm3. A full-matrix least-squares refinement on the basis of F2 yielded R1=0.029 and wR2=0.064 for 2136 independent reflections with I>2σ(I) collected with a Bruker AXS diffractometer (MoKα radiation). The crystal structure of PbUO2(V2O7) consists of a tri-dimensional framework resulting from the association of V2O7 divanadate units formed by two VO4 tetrahedra sharing corner and UO7 uranyl pentagonal bipyramids and creating one-dimensional elliptic channels occupied by the Pb2+ ions. In PbUO2(V2O7), infinite ribbons of four pentagons wide are formed which can be deduced from the sheets with Uranophane type anion-topology that occurs, for example, in the uranyl divanadate (UO2)2(V2O7), by replacement of half-U atoms of the edge-shared UO7 pentagonal bipyramids by Pb atoms. Infrared spectroscopy was investigated at room temperature in the frequency range 400-4000 cm−1, showing some characteristic bands of uranyl ion and of VO4 tetrahedra.  相似文献   

14.
A silver(I) coordination polymer with mixed 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) and maleic acid, [Ag2(bpz)3(fum)]n (1, H2fum = fumaric acid), was synthesized under hydrothermal condition by in situ isomerization of maleic acid to fumaric acid and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, TGA, and single-crystal X-ray diffraction. The maleic acid in situ isomerizes to fumaric acid and participates in the formation of 1. Topologically, the structure of 1 features a rare 3-connected twofold interpenetrated dia-f net with a point symbol of {4.142}. Compound 1 exhibits photoluminescence in the solid state with an emission maximum at 470 nm upon excitation at 365 nm at room temperature, which is attributed to intraligand or/and interligand π → π* transition.  相似文献   

15.
16.
The syntheses and crystal structures of four new uranyl complexes with [O,N,O,N′]-type ligands are described. The reaction between uranyl nitrate hexahydrate and the phenolic ligand [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-N′,N′-dimethylethylenediamine)], H2L1 in a 1:2 molar ratio (M to L), yields a uranyl complex with the formula [UO2(HL1)(NO3)] · CH3CN (1). In the presence of a base (triethylamine, one mole per ligand mole) with the same molar ratio, the uranyl complex [UO2(HL1)2] (2) is formed. The reaction between uranyl nitrate hexahydrate and the ligand [(N,N-bis(2-hydroxy-3,5-di-t-butylbenzyl)-N′,N′-dimethylethylenediamine)], H2L2, yields a uranyl complex with the formula [UO2(HL2)(NO3)] · 2CH3CN (3) and the ligand [N-(2-pyridylmethyl)-N,N-bis(2-hydroxy-3,5-dimethylbenzyl)amine], H2L3, in the presence of a base yields a uranyl complex with the formula [UO2(HL3)2] · 2CH3CN (4). The molecular structures of 14 were verified by X-ray crystallography. The complexes 14 are zwitter ions with a neutral net charge. Compounds 1 and 3 are rare neutral mononuclear [UO2(HLn)(NO3)] complexes with the nitrate bonded in η2-fashion to the uranyl ion. Furthermore, the ability of the ligands H2L1–H2L4 to extract the uranyl ion from water to dichloromethane, and the selectivity of extraction with ligands H2L1, H3L5 (N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-3-amino-1-propanol), H2L6 · HCl (N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminobutane · HCl) and H3L7 · HCl (N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-6-amino-1-hexanol · HCl) under varied chemical conditions were studied. As a result, the most efficient and selective ligand for uranyl ion extraction proved to be H3L7 · HCl.  相似文献   

17.
Biosorption of uranyl ions from aqueous solution by Saccharomyces cerevisiae was studied in a batch system. The influence of contact time, initial pH, temperature and initial concentration was investigated. The optimal conditions were found to be 3.5?h of contact time and pH?=?4.5. Temperature had no significant effect on adsorption. The uptake of uranyl ions was relatively fast and 85?% of the sorption was completed within 10?min. The experimental data were well fitted with Langmuir isotherm model and pseudo-second order kinetic model. According to this kinetic model, the sorption capacity and the rate constant were 0.455?mmol UO2 2+/g dry biomass and 1.89?g?mmol?1?min?1, respectively. The Langmuir isotherm indicated high affinity and capacity of the adsorbent for uranyl biosorption with the maximum loading of 0.477?mmol UO2 2+/g dry weight.  相似文献   

18.
Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N2C6H14)[(UO2)(AsO4)]2(H2O)3, DabcoUAs, {NH(C2H5)3}[(UO2)2(AsO4)(AsO3OH)], TriethUAs, and (N2C4H12)(UO2)[(UO2)(PO4)]4(H2O)2, PiperUP. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (DabcoUAs, TriethUAs, PiperUP) wR2=5.6%, 8.3%, 7.2% for all data, and R1=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (|Fo|?4σF), respectively. DabcoUAs is monoclinic, space group C2/m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å3, Dcalc=3.50 g/cm3. TriethUAs is monoclinic, space group P21/n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å3, Dcalc=3.41 g/cm3. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å3, Dcalc=4.41 g/cm3. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H2O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H2O groups in the cavities of the structure.  相似文献   

19.
20.
Two new potassium uranyl molybdates K2(UO2)2(MoO4)O2 and K8(UO2)8(MoO5)3O6 have been obtained by solid state chemistry . The crystal structures were determined by single crystal X-ray diffraction data, collected with MoKα radiation and a charge coupled device (CCD) detector. Their structures were solved using direct methods and Fourier difference techniques and refined by a least square method on the basis of F2 for all unique reflections, with R1=0.046 for 136 parameters and 1412 reflections with I?2σ(I) for K2(UO2)2(MoO4)O2 and R1=0.055 for 257 parameters and 2585 reflections with I?2σ(I) for K8(UO2)8(MoO5)3O6. The first compound crystallizes in the monoclinic symmetry, space group P21/c with a=8.250(1) Å, b=15.337(2) Å, c=8.351(1) Å, β=104.75(1)°, ρmes=5.22(2) g/cm3, ρcal=5.27(2) g/cm3 and Z=4. The second material adopts a tetragonal unit cell with a=b=23.488(3) Å, c=6.7857(11) Å, ρmes=5.44(3) g/cm3, ρcal=5.49(2) g/cm3, Z=4 and space group P4/n.In both structures, the uranium atoms adopt a UO7 pentagonal bipyramid environment, molybdenum atoms are in a MoO4 tetrahedral environment for K2(UO2)2(MoO4)O2 and MoO5 square pyramid coordination in K8(UO2)8(MoO5)3O6. These compounds are characterized by layered structures. The association of uranyl ions (UO7) and molybdate oxoanions MoO4 or MoO5, give infinite layers [(UO2)2(MoO4)O2]2− and [(UO2)8(MoO5)3O6]8− in K2(UO2)2(MoO4)O2 and K8(UO2)8(MoO5)3O6, respectively. Conductivity properties of alkali metal within the interlayer spaces have been measured and show an Arrhenius type evolution.  相似文献   

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