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Journal Articles

Formation and thermochemical properties of oxychlorides of niobium (Nb) and tantalum (Ta); Towards the gas-phase investigation of dubnium (Db) oxychloride

Chiera, N. M.; Sato, Tetsuya; Tomitsuka, Tomohiro; Asai, Masato; Suzuki, Hayato*; Tokoi, Katsuyuki; Toyoshima, Atsushi; Tsukada, Kazuaki; Nagame, Yuichiro

Inorganica Chimica Acta, 486, p.361 - 366, 2019/02

 Times Cited Count:2 Percentile:24.66(Chemistry, Inorganic & Nuclear)

The formation of NbOCl$$_3$$ and TaOCl$$_3$$ and their adsorption behavior on quartz surfaces was explored by applying an isothermal gas-chromatographic method. Trace amounts of short-lived Nb and Ta isotopes were used. Adsorption enthalpy values ($$Delta H_{rm ads}$$) at zero surface coverage of -$$Delta H_{rm ads}$$(NbOCl$$_3$$) = 102 $$pm$$ 4 kJ/mol and -$$Delta H_{rm ads}$$(TaOCl$$_3$$) = 128 $$pm$$ 5 kJ/mol were determined by analyzing the chromatographic behavior of the Nb andTa complexes with a Monte-Carlo simulation method based on an adsorption-desorption kinetic model.By applying an empirical correlation, the experimental $$Delta H_{rm ads}$$ values were successively related to the macroscopic standard sublimation enthalpy, $$Delta H^circ _{rm subl}$$, as a measure of the volatility of each substance. The inferred sublimation enthalpies are in agreement with tabulated thermochemical values. Thus, the linear empirical correlation between $$Delta H_{rm ads}$$ and $$Delta H^circ _{rm subl}$$ for metal-oxychlorides was updated with the inclusion of the present data. According to the predicted $$Delta H^circ _{rm subl}$$(DbOCl$$_3$$), a $$Delta H_{rm ads}$$(DbOCl$$_3$$) value of 135 $$pm$$ 2 kJ/mol was extrapolated. The future accomplishment of comparative studies with DbOCl$$_3$$ under the same experimental conditions will provide valuable information on the volatility trend in Group-5 elements, together with an indication on the magnitude of relativistic effects on the electronic structure of dubnium.

Journal Articles

A Structural study on uranyl (VI) nitrate complexes with cyclic amides; ${it N-n}$-butyl-2-pyrrolidone, ${it N}$-cyclohexylmethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidone

Koshino, Nobuyoshi*; Harada, Masayuki*; Nogami, Masanobu*; Morita, Yasuji; Kikuchi, Toshiaki*; Ikeda, Yasuhisa*

Inorganica Chimica Acta, 358(6), p.1857 - 1864, 2005/03

 Times Cited Count:52 Percentile:89.02(Chemistry, Inorganic & Nuclear)

Structural analyses of UO$$_{2}$$(NO$$_{3}$$)$$_{2}$$L$$_{2}$$ [L=${it N-n}$-butyl-2-pyrrolidone, N-cyclohexylmethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidone] have been carried out using X-ray diffraction method. These uranyl complexes were found to have a hexagonal bipyramidal structure. The bond distances of U=O and U-O (ligand), and bond angles of U-O-C(carbonyl) are determined. In uranyl nitrate complexes with cyclic amides such as 2-pyrrolidone, urea, and caprolactam derivatives, a linear correlation was found to hold between U-O (ligand) bond distances and U-O-C(carbonyl) bond angles. Vibrational frequencies of UO$$_{2}$$(NO$$_{3}$$)$$_{2}$$L$$_{2}$$ have also been measured by IR and Raman spectrophotometers. Using relationships between vibrational frequencies of O=U=O bonds and donor numbers (DNs) of ligands, donicities of N-substituted-2-pyrrolidones were determined.

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