Uranyl-Bound Tetra-Dentate Non-Innocent Ligands: Prediction of Structure and Redox Behaviour Using Density Functional Theory.

Computational methods have been applied to understand the reduction potentials of [UO2 -salmnt-L] complexes (L=pyridine, DMSO, DMF and TPPO), and their redox behavior is compared with previous experiments in dichloromethane solution. Since the experimental results were inconclusive regarding the influence of the uranyl-bound tetra-dentate 'salmnt' ligand, here we will show that salmnt acts as a redox-active ligand and exhibits non-innocent behavior to interfere with the otherwise expected one-electron metal (U) reduction. We have employed two approaches to determine the uranyl (VI/V) reduction potentials, using a direct study of one-electron reduction processes and an estimation of the overall reduction using isodesmic reactions. Hybrid density functional theory (DFT) methods were combined with the Conductor-like Polarizable Continuum Model (CPCM) to account for solvation effects. The computationally predicted one-electron reduction potentials for the range of [UO2 -salmnt-L] complexes are in excellent agreement with shoulder peaks (∼1.4 eV) observed in the cyclic voltammetry experiments and clearly correlate with ligand reduction. Highly conjugated pi-bonds stabilize the ligand based delocalized orbital relative to the localized U f-orbitals, and as a consequence, the ligand traps the incoming electron. A second reduction step results in metal U(VI) to U(V) reduction, in good agreement with the experimentally assigned uranyl (VI/V) reduction potentials.

Determination of Trace Amounts of Hydrofluoric Acid in Non-Aqueous Solutions by the Coulometric Titration Method.

For monitoring of trace amounts of hydrofluoric acid in the organic fluorine chemical industry, a facile method for determination of the hydrofluoric acid in an ethanol solution of lithium chloride, by coulometric titration, was proposed. Relying on homemade acid⁻base coulometric autotitrator, the electrolyte was 0.50 mol·L-1 LiCl ethanol solution and the constant current intensity was 0.2⁻2 mA. As for the working electrode pair, a platinum plate was used as a working electrode, and a platinum wire was used as an auxiliary electrode. The indicating electrode was the pH composite glass electrode and the titration endpoint was pH 5.50. The results showed that the relative standard deviation was below 2.0%, as the content of the hydrofluoric acid was between 2 µg to 100 µg. The recovery rate was 99.0⁻102.0%. This proposed route has the advantages of simplicity, convenience, quickness, accuracy, and automation, which can be applied to the accurate determination of trace amounts of hydrofluoric acid, in non-aqueous solutions.

Morphology and Distribution of Primary Carbides in Forged Cr-Ni-Mo-V/Nb Steel.

This study aims to investigate in situ the three-dimensional (3D) morphology and distribution of primary carbides (PCs) in electro-slag remelting (ESR) forged 30Cr3Ni3Mo2V steel. A facile non-aqueous electrolytic etching method was applied to prepare 3D PCs on the matrix. The morphology, composition, and element concentrations of PCs were characterized using a combination of optical microscopy (OM), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), and electron back-scattered diffusion (EBSD). The precipitation, type, and composition of PCs in the same steel were also simulated using Thermo-Calc software Version 2015a. The results indicate that PC is rich in Nb, which is a potential heterogeneous nucleating agent. Both the size and number of PCs increase from the edge to the center of the ingot. The large-sized PCs present three dominant types of morphology, which vary in different regions, i.e., a bulky type dominates in the edge region, a lamellar type dominates in the middle region, and a stripy type dominates in the core region. The results of EBSD analysis show that the orientation of PCs with different morphologies is different and that more nanosized V-rich type carbides are precipitated on the matrix. The thermodynamic calculations show that MC precipitates from the liquid phase when the solid phase fraction is greater than 0.985 and that the MC-type carbides are rich in Nb, which agrees well with the experimental results.

Detection of Chlorine in a Non-aqueous Solution via Anodic Oxidation and a Photochemical Reaction.

In this study, we developed a new chlorine gas detection method using anodic oxidation and a photochemical reaction. Chlorine gas was temporarily solvated with an aprotic polar solvent having an extensive potential range in the positive direction, and the solvated chlorine molecule was detected by an anodic oxidation reaction. In addition, when combined with ultraviolet light irradiation, we could detect high sensitivity using the photochemical reaction.

Effect of Synthesis Method of La1 - xSr x MnO3 Manganite Nanoparticles on Their Properties.

Nanoparticles of lanthanum-strontium manganite were synthesized via different methods, namely, sol-gel method, precipitation from non-aqueous solution, and precipitation from reversal microemulsions. It was shown that the use of organic compounds and non-aqueous media allowed significantly decreasing of the crystallization temperature of nanoparticles, and the single-phased crystalline product was formed in one stage. Morphology and properties of nanoparticles depended on the method and conditions of the synthesis. The heating efficiency directly depended on the change in the magnetic parameters of nanoparticles, especially on the magnetization. Performed studies showed that each of these methods of synthesis can be used to obtain weakly agglomerated manganite nanoparticles; however, particles synthesized via sol-gel method are more promising for use as hyperthermia inducers.PACS: 61.46.Df 75.75.Cd 81.20. Fw.