Rb2[U(NH2)6], a Rubidium Hexaamidouranate(IV) obtained from the Reaction of UI3 with RbNH2 in Anhydrous Ammonia

The pyrophoric compound Rb₂[U(NH₂)₆] was obtained as a grey to black powder from the reaction of more than three equivalents of RbNH₂ with UI₃ in anhydrous liquid ammonia. During the process, U^III is oxidized to U^IV and ammonia is reduced under evolution of H₂. Rb₂[U(NH₂)₆] crystallizes in the cubic crystal system, space group Fm3 m, with the lattice parameter a = 9.7870(12) Å, V = 937.4(2) ų, Z = 4 at T = 293 K. It is isotypic to K₂PtCl₆. The compound contains the unprecedented hexaamidouranate(IV) anion [U(NH₂)₆]^2–.     

Preparation and Crystal Structure of a New Uranyl Sulfate Templated by a Bis-isothiouronium Cation

Crystals of a new uranyl sulfate (C₂N₄H₈S₂)[UO₂(SO₄)₂] · 0.3H₂O ( 1 ) templated by a relatively rare bis-isothiouronium cation, were formed upon evaporation of aqueous solutions containing uranyl acetate, thiourea, and excess sulfuric acid. The new compound is orthorhombic, P2₁2₁2₁, a = 6.928(2) Å, b = 13.398(3) Å, c = 15.225(3) Å, Z = 2. Its crystal structure is comprised of [UO₂(SO₄)₂] moieties linked by hydrogen bonds formed between the template cations and terminal oxygen atoms of the sulfate tetrahedra. The C₂N₄H₈S₂²⁺ template is most likely formed in situ during a redox reaction between uranyl cation and thiourea in a strongly acidic medium, with UO₂²⁺ partially reduced to U⁴⁺.     

Inhibition of hydrogen chemisorption on uranium surfaces by traces of water vapor

Traces of about 2% water vapor are sufficient to inhibit hydrogen dissociation and chemisorption on uranium surfaces, under low pressure exposures, at room temperature. The efficiency of the inhibition increases with temperature in the range of 200 - 400 K. The inhibition effect is also influenced by the extent of residual strain of the sample, with increasing inhibition efficiencies exhibited by a less strained surface. O₂, in contrast to H₂O, is not an inhibitor to surface adsorption and dissociation of hydrogen. Three types of mechanisms are discussed in order to account for the above inhibition effect of water. It is concluded that the most probable mechanism involves the reversible adsorption of water molecules on hydrogen dissociation sites causing their “blocking”.     

Synthesis and characterization of uranium (IV) complexes with various amino acids

Complexes of uranium in its IV oxidation state, using cysteine, glycine, serine and aspartic acid as ligands, have been synthesized. Semi-microanalysis of the complexes indicate 1:1 metal to ligand ratio for all the synthesized complexes. Infrared spectra of solid complexes have been employed to establish the groups, coordinated to the metal ion. Effective magnetic moment of the complexes were also estimated.     

Assessment of the Nd/U ratio for the quantification of neodymium in UO2

The secondary ion energy spectrum of uranium depends on the experimental conditions, which is a problem for the application of a relative sensitivity factor (RSF) procedure for the measurement of the Nd concentration in UO₂. This is interpreted as due to the dependence of the sputtering and ionisation yields of uranium on the oxidation state of the surface. Three experimental procedures are being tested to cope with this difficulty.     

Preparation of electrodeless discharge lamps for emission studies of uranium isotopes at trace level

A simplified method for preparation of electrodeless discharge lamp for uranium isotopes with specific concerns for ²³²U is described. Micro-gram quantities of solid uranium oxides and aqueous solution of uranium nitrate have been used as a starting material for in situ synthesis of uranium tetraiodide. High temperature iodination reaction is carried out in the presence of inert gas neon. By careful design, the preparation time and surface area of quartz reaction tubes have been reduced considerably. The latter decreases the level of contamination which has a direct bearing on the operational lifetime of the lamps. Incorporation of steps to purify the product from an unwanted material improved the stability of the lamps. The procedure provides a safe and convenient way of handling ²³²U in particular but can be extended in general to any actinides having radioactivity similar to that of freshly separated ²³²U. Characteristic emission of uranium isotopes have been recorded by Fourier Transform Spectrometer to show the satisfactory operation of the lamps as well as their usage for studying emission spectra of the specific isotope.     

Simultaneous Determination of Ultra Trace of Uranium and Cadmium by Adsorptive Cathodic Stripping Voltammetry Using H‐Point Standard Addition Method

A sensitive adsorptive cathodic stripping voltammetry with H‐point standard addition method for simultaneous determination of uranium and cadmium has been developed. The trace amounts of these metal ions can be simultaneously determined using the Levodpa as complexing agent. Optimal conditions were: accumulation time 50 s, accumulation potential 0.0 mV, scan rate 40 mV s^?1, supporting electrolyte 0.1 M ammonium buffer pH 9.6, and 1×10^?5 M of Levodopa. The results revealed that the cadmium and uranium could be simultaneously determined by H‐point standard addition method with different concentration ratios of uranium to cadmium. The method was successfully applied in a several of real samples.     

Elaboration and characterisation of a plasticized cellulose triacetate membrane containing trioctylphosphine oxyde (TOPO): Application to the transport of uranium and molybdenum ions

A cellulose triacetate (CTA) membrane containing trioctylphosphine oxyde (TOPO) as carrier and 2-nitrophenyloctyl ether (NPOE) as a plasticizer was prepared. The membrane CTA + NPOE + TOPO was characterised using chemical techniques as well as Fourier Transform InfraRed (FTIR) spectroscopy, X-ray diffraction and Scanning Electron Microscopy (SEM). The CTA membrane is characterised by well-defined pores; these pores are completely filled with the NPOE and carrier. Surfaces of membranes with TOPO are smooth. The systems constituted by the mixture of CTA + NPOE, CTA + NPOE + TOPO do not give any diffraction. This can be due to the absence of crystallization within the membrane. On the other hand, this result should be attributable to the amorphous state of the structure, which permits us to eliminate the mechanism of transfer of the ions by electron jump. A comparative study of transport across a polymer inclusion membrane (PIM) and a supported liquid membrane (SLM) containing the same carrier in chloroform has shown that uranium or molybdenum transport efficiency was increased using PIM instead of SLM. PIM showed higher stability than SLM, the flux of transport remain constant in the former case after 2 weeks.