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

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

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2 Citations (Scopus)

Abstract

The formation of NbOCl3 and TaOCl3 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 (ΔHads) at zero surface coverage of –ΔHads(NbOCl3) = 102 ± 4 kJ/mol and –ΔHads(TaOCl3) = 128 ± 5 kJ/mol were determined by analyzing the chromatographic behavior of the Nb and Ta complexes with a Monte-Carlo simulation method based on an adsorption–desorption kinetic model. By applying an empirical correlation, the experimental ΔHads values were successively related to the macroscopic standard sublimation enthalpy, ΔH°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 ΔHads and ΔH°subl for metal-oxychlorides was updated with the inclusion of the present data. According to the predicted ΔH°subl(DbOCl3), a ΔHads(DbOCl3) value of 135 ± 2 kJ/mol was extrapolated. The future accomplishment of comparative studies with DbOCl3 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.

Original languageEnglish
Pages (from-to)361-366
Number of pages6
JournalInorganica Chimica Acta
Volume486
DOIs
Publication statusPublished - Feb 24 2019
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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