The discoveries of uranium 237 and symmetric fission - from the archival papers of Nishina and Kimura

Shortly before the Second World War time, Nishina reported on a series of prominent nuclear physical and radiochemical studies in collaboration with Kimura. They artificially produced (231)Th, a member of the natural actinium series of nuclides, by bombarding thorium with fast neutrons. This resulted in the discovery of (237)U, a new isotope of uranium, by bombarding uranium with fast neutrons, and confirmed that (237)U disintegrates into element 93 with a mass number of 237. They also identified the isotopes of several middle-weighted elements produced by the symmetric fission of uranium. In this review article, the highlights of their work are briefly summarized along with some explanatory commentaries.     

氟离子选择性电极法测定钍氟各级稳定常数

硫酸体系钍氟各级稳定常数对稀土冶炼生产实践具有重要的指导作用.采用溶解度法测定了室温(25 ℃)下不同酸度的钍氟共存区,采用氟离子选择电极测定不同浓度氟化氢溶液中的游离氟浓度,得到氢氟各级稳定常数.然后根据钍氟共存区图,配制一系列硫酸钍、氢氟酸和硫酸的混合液,测定各溶液中的游离氟浓度,从而得到钍氟各级稳定常数.结果表明,H与F的第1,2级稳定常数分别为k1=664.4,k2=47.9,Th和F的第1,2,3级稳定常数分别为k16.27×105,k2=9.68×104,k3=5.36×104.     

ChemInform Abstract: Thorium Fluorides ThF,ThF2, ThF3, ThF4, ThF3(F2), and ThF5‐ Characterized by Infrared Spectra in Solid Argon and Electronic Structure and Vibrational Frequency Calculations.

Laser‐ablated Th atoms are reacted with different F₂ concentrations to produce ThF_x (x = 1, 2, 3, 4), ThF₃(F₂) and ThF₅^‐.     

钍俘获反应率离线伽马测量方法

为了测定聚变-裂变反应堆模型钍包层中的钍俘获率以及钍-铀转化率, 探索了一种新的钍活化离线γ测量法. 利用测量²³²Th俘获反应产物²³³Th衰变链中²³³Pa衰变放出的311.98 keV 特征γ射线, 来反推计算并最终确定²³²Th(n,γ)²³³Th的反应率, 测试实验中不确定度约6% (²³³Th/²³²Th量级为10^-17情况下). 详细介绍了此方法的背景和原理方法, 并进行简单的校验实验, 证明其能够较好地得到模拟装置中的俘获率. 与瞬发γ测量法以及质谱分析法进行对比, 本方法更适合用于聚变-裂变反应堆模型钍包层中的钍俘获率以及钍-铀转化率测量, 并有望进一步测量其他相关参数.     

An EDXRF method for determination of uranium and thorium in AHWR fuel after dissolution

A fast energy dispersive x‐ray fluorescence (EDXRF) method requiring only microgram amounts of analytes, i.e. uranium (U) and thorium (Th), in their mixtures in solution form is described. Calibration solutions and samples covering the fuel composition range (0–5% of U in U + Th) of advanced heavy water reactor (AHWR) were prepared by mixing uranium and thorium solutions. A known fixed amount of internal standard yttrium (Y) was added to these solutions. EDXRF spectra of calibration solutions and samples were measured by taking 20 µl aliquots on 30 mm diameter filter papers, after drying, using a Rh target tube operated at 40 kV and 500 µA. Calibration plots were made by plotting U/Y, U/Th and Th/Y amount ratios against the respective intensity ratios of Th Lα, U Lα and Y Kα. In the first set, U was determined using Y as an internal standard, and for Th determination, U, thus determined, was used as an internal standard since the amounts of Th and Y were kept constant in the calibration solutions and samples. In the second set, both U and Th were varied and determined using Y as internal standard. The results of U and Th determinations showed a precision of about 3% (1s) and the results deviated from the expected values by <3% in most of the cases. This approach has an advantage that it requires only microgram amounts of sample, thus mitigating radiation hazards associated with radioactive samples as well as the amount of radioactive analytical waste generated is quite less. Copyright © 2009 John Wiley & Sons, Ltd.     

The electronic structure of thorium monoxide: Ligand field assignment of states in the range 0–5 eV

Configuration interaction ligand field theory (CI LFT) calculations of the electronic energy levels of ThO were performed by treating the molecular electronic states as Th ^{2 +} free-ion levels perturbed by the ligand field of O²⁻. Twenty nine experimentally characterized ThO v = 0 energy levels, together with the energy difference between the v = 0 levels of the Y and W states were fitted using a CI LFT model that included Th ^{2 +} 7s ² , 6d7s, 6d², 7s7p, 6d7p, 5f7s, and 7p² configurations. Predictions from these calculations were used to provide tentative assignments for 171 out of 250 ThO band heads listed by Gatterer et al. [“Molecular Spectra of Metallic Oxides”, Specola Vaticana (1957)]. Term energies for 30 electronic states have been determined based on these assignments. Subsequently, the CI LFT model was refined by fitting to a set of 59 electronic term energies. The inclusion of CI effects together with integer valence, atomic-in-molecule, ionic bonding ideas reveals atomic energy level patterns that are multiply replicated in the molecular energy level patterns of six Th ^{2 +} O²⁻ atomic ion configurations (6d7s, 6d², 7s7p, 6d7p, 5f7s, and 7p²) revealing the underlying atomic ion structure that gives rise to the complex and seemingly erratic unassigned bands reported in the Vatican Atlas. © 2018 Wiley Periodicals, Inc.     

在L-缬氨酸介质中应用聚二苯并-18-冠醚-6-分离铈（III)

 A column chromatographic method has been developed for the separation and determination of cerium(Ⅲ) using poly［dibenzo-18-crown-6］. The separation was carried out in L-valine medium. The adsorption of cerium(Ⅲ) was quantitative from 1×10-1 to 1×10-4 mol/L L-valine. Amongst the various eluents, 1.0-8.0 mol/L hydrochloric acid, 1.0-8.0 mol/L hydrobromic acid, 1.0-8.0 mol/L perchloric acid, 1.0-2.0 mol/L sulfuric acid and 4.0-5.0 mol/L acetic acid, were found to be the efficient eluents for cerium(Ⅲ). The capacity of poly［dibenzo-18-crown-6］ for cerium(Ⅲ) was （0.428±0.01） mmol/g. The method was applied to the separation of cerium(Ⅲ) from associated elements link uranium(Ⅵ) and thorium(Ⅳ). It was also applied for the determination of cerium(Ⅲ) in geological samples. The method is simple, rapid and selective with good reproducibility (approximately±2%).     

Biosorption of actinides from dilute waste actinide solution by egg-shell membrane

Removal of radioactive elements from the effluent and waste aqueous solutions is an important problem. In previous laboratory batch experiments, hen egg-shell membrane (ESM) was stable as an insoluble protein and was very capable of binding heavy metal ions from aqueous solution. Batch laboratory pH profile, time dependency, and capacity experiments were performed to determine the binding of uranium (U) and thorium (Th) to ESM. Batch pH profile experiments indicated that the optimum pH for binding these actinides was approx 6.0 (U) or 3.0 (Th). The adsorption isotherms were developed at pH 5.0 (U) or 3.0 (Th) at 25°C, and the adsorption equilibrium data fitted both Langmuir and Freundlich models. The maximum uptakes by the Langmuir model were about 240 mg U/g and 60 mg Th/g dry weight ESM. In addition, their adsorption capacities increased as salt concentration increased. ESM could also accumulate uranium from dilute aqueous solution by adjusting to the optimum pH. These results showed that ESM was effective for removing actinides from solution and would be useful in filtration technology to remove actinides from aqueous solution. S.-I. Ishikawa is a research fellow at the Japan Society for the Promotion of Science.     

A high pressure raman study of ThO2 to 40 GPa and pressure-induced phase transition from fluorite structure

The pressure dependence of the first-order Raman peak and two second-order Raman features of ThO₂ crystallizing in the fluorite-type structure is investigated using a diamond anvil cell, up to 40GPa. A phase transition from the fluorite phase is observed near 30 GPa as evidenced by the appearance of seven new Raman peaks. The high pressure phases of ThO₂ and CeO₂ exhibit similar Raman features and from this it is believed that the two structures are the same, and have the PbCl₂-type structure. The pressure dependence dω/dP of the observed phonons and their mode Grüneisen parameters are similar to the isostructural CeO₂. The observed second-order Raman features are also identified from the calculated phonon dispersion curves for ThO₂.