ChemInform Abstract: Single Crystal Growth and Structural Characterization of Ternary Transition‐metal Uranium Oxides: MnUO4, FeUO4, and NiU2O6.

Single crystals of MnUO₄ (I) are prepared from U₃O₈ and MnCl₂ in a molten CsCl flux (alumina crucible, 900 °C, 12 h).     

铀尾矿酸浸过程中的矿物学性质变化研究

脉石含量高和矿物学性质复杂是导致低品位铀尾矿中的铀难以进一步回收的主要原因,而破坏复杂的脉石矿物结构是提高铀解离的有效途径.本文在详细分析了铀尾矿工艺矿物学性质的基础上,通过研究五种氧化剂(H_2O_2、MnO_2、Fe_2(SO_4)_3、HF、HClO_4)对铀尾矿粒径分布、形貌特征和物相组成的影响,揭示了酸浸过程中氧化剂与脉石矿物之间的作用规律.研究结果表明,H_2O_2可将硅酸铁盐矿物分解而使铀尾矿粒径变小,MnO_2可将硅酸铁盐转化为硅酸锰盐并伴随着硅酸锰盐物相的结晶长大,Fe_2(SO_4)_3对脉石矿物无破坏作用,反而能使脉石颗粒发生絮凝,HClO_4与HF可在脉石矿物表面或内部造成强烈的腐蚀而形成细小的孔洞.     

Synthesis and Insertion Chemistry of Mixed Tether Uranium Metallocene Complexes

The synthesis of mixed tethered alkyl uranium metallocenes has been investigated by examining the reactivity of the bis(tethered alkyl) metallocene [(η⁵‐C₅Me₄SiMe₂CH₂‐κC)₂U] ( 1 ) with substrates that react with only one of the U? C linkages. The effect of these mixed tether coordination environments on the reactivity of the remaining U? C bond has been studied by using CO insertion chemistry. One equivalent of azidoadamantane (AdN₃) reacts with 1 to yield the mixed tethered alkyl triazenido complex [(η⁵‐C₅Me₄SiMe₂CH₂‐κC)U(η⁵‐C₅Me₄SiMe₂‐CH₂NNN‐Ad‐κ²N^1,3)]. Similarly, a single equivalent of CS₂ reacts with 1 to form the mixed tethered alkyl dithiocarboxylate complex [(η⁵‐C₅Me₄SiMe₂CH₂‐κC)U(η⁵‐C₅Me₄SiMe₂‐ CH₂C(S)₂‐κ²S,S′)], a reaction that constitutes the first example of CS₂ insertion into a U⁴⁺? C bond. Complex 1 reacts with one equivalent of pyridine N‐oxide by C? H bond activation of the pyridine ring to form a mixed tethered alkyl cyclometalated pyridine N‐oxide complex [(η⁵‐C₅Me₄SiMe₂CH₂‐κC)(η⁵‐C₅Me₄SiMe₃)U(C₆H₄NO‐κ²C,O)]. The remaining (η⁵‐C₅Me₄SiMe₂CH₂‐κC)^2? ligand in each of these mixed tethered species show reactivity towards CO and tethered enolate ligands form by insertion. Subsequent rearrangement have been identified in [(η⁵‐C₅Me₄SiMe₃)U(C₅H₄NO‐κ²C,O)(η⁵‐C₅Me₄SiMe₂C(?CH₂)O‐κO)] and [(η⁵‐C₅Me₄SiMe₂CH₂NNN‐Ad‐κ²N^1,3)U(η⁵‐C₅Me₄SiMe₂C(?CH₂)O‐κO)].     

Application of Adsorptive Stripping Voltammetry for Determination of Uranium in the Presence of 3-Hydroxy-2-Naphthoic Hydrazide

Abstract

A new method is presented for determination of uranium based on a cathodic adsorptive stripping of the complex of uranium with a 3-hydroxy-2-naphthoic hydrazide at a hanging mercury drop electrode (HMDE). The most suitable operating conditions and parameters, such as pH, deposition potential, deposition time, ligand concentration, and others, were selected and the determination of uranium from aqueous solutions using the standard addition method was possible. Under optimum conditions, the measured peak current is proportional to the concentration of uranium over the range of 1–500 nA with a detection limit of 0.75 nM.     

Preconcentration of Uranium in Seawater with Heterocyclic Azo Dyes Supported on Silica Gel

Abstract

The chelating adsorbents, heterocyclic azo dyes supported on silica gel, were prepared and their adsorption behaviors of metal ions were investigated. The 1-(2-pyridylazo)-2-naphthol(PAN)-SG and 2-(2-thiazolylazo)-p-cresol(TAC)-SG show greater affinity for UO₂(II) and ZrO(II), compared with the other metal ions like Cu, Cd, Fe and alkaline earths. Trace uranyl can be quantitatively retained on the column of the gels at neutral pH region and flow-rate 3–4 ml/min. The uranyl retained is easily eluted from the column bed with a mixture of acetone and nitric acid(9:1 v/v) and determined by spectrophotometry using Arsenazo-III. Matrix components in seawater do not interfere and the spiked recovery of uranyl in artificial seawater was found to be average 98.6 %, with the relative standard deviation of 1.08 %. Both gels were applied to the determination of uranium in seawater with satisfactory results.     

Use of micro‐Raman spectrometry coupled with scanning electron microscopy to determine the chemical form of uranium compounds in micrometer‐size particles

In the frame of nuclear safeguards, knowledge of the chemical form (stoichiometry) of the uranium compounds present in the micrometric particulate material sampled by wiping surfaces in an inspected nuclear facility may point out the industrial process implemented in the installation. Micro‐Raman spectroscopy (MRS) coupled with scanning electron microscopy (SEM) has been used for the first time to analyze micrometer‐size particles of various uranium oxides [UO₂, U₃O₈, UO₃, and UO₄ · 4(H₂O)] deposited on carbon disks. Uranium particles are detected by means of SEM, and Raman analysis is then directly carried out inside the SEM measurement chamber without moving the carbon disk from SEM to MRS. When particles are deposited on appropriate carbon disks (sticky carbon tapes), despite a loss of signal‐to‐noise ratio of about an order of magnitude with regard to the stand‐alone MRS, all uranium oxides are successfully identified in particles by in‐SEM Raman analysis, obtaining similar characteristic bands as the ones obtained with the stand‐alone MRS. Moreover, with the SEM–MRS coupling, particles as small as 1 µm can be analyzed, whereas, without the SEM–MRS coupling, only particles larger than ~5 µm are efficiently analyzed, after localization inside the SEM, transfer of the sample holder into the MRS, and relocation of the particles inside the MRS. Copyright © 2013 John Wiley & Sons, Ltd.     

贫铀球壳中D-T中子诱发的铀反应率的测量与分析

为校验次临界能源堆的概念设计,在R19.4/30.0 cm的贫铀球壳装置上采用活化法开展14 MeV中子学积分实验.布放6片贫铀活化片于球壳中与入射D离子束90°方向上的不同位置处活化,用HPGe探测器测量238U(n,γ)反应、238U(n,f)及235U(n,f)反应和238U(n,2n)各反应产物发射的特征γ射线,得到了相应的反应率.238U(n,γ)反应率的不确定度为3.6％-3.7％,238U(n,D和235U(n,f)反应率的不确定度为5.1％-5.9％,238U(n,2n)反应率的不确定为4.3％-4.7％.用MCNP5程序在ENDF66c数据库下进行模拟计算,238U(n,γ)反应率的计算值/实验值(C/E)为0.972-1.034,238U(n,f)和235U(n,f)反应率的C/E为0.983-1.058,238U(n,2n)反应率的C/E为0.979-1.019.