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

Research output: Contribution to journalArticle

1 Citation (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

Fingerprint

dubnium
Niobium
Tantalum
thermochemical properties
tantalum
niobium
Enthalpy
volatility
Gases
enthalpy
Sublimation
vapor phases
sublimation
tantalum isotopes
niobium isotopes
Adsorption
Quartz
adsorption
relativistic effects
Isotopes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Formation and thermochemical properties of oxychlorides of niobium (Nb) and tantalum (Ta) : Towards the gas-phase investigation of dubnium (Db) oxychloride. / Chiera, Nadine M.; Sato, Tetsuya K.; Tomitsuka, Tomohiro; Asai, Masato; Suzuki, Hayato; Tokoi, Katsuyuki; Toyoshima, Atsushi; Tsukada, Kazuaki; Nagame, Yuichiro.

In: Inorganica Chimica Acta, Vol. 486, 24.02.2019, p. 361-366.

Research output: Contribution to journalArticle

Chiera, Nadine M. ; Sato, Tetsuya K. ; Tomitsuka, Tomohiro ; Asai, Masato ; Suzuki, Hayato ; Tokoi, Katsuyuki ; Toyoshima, Atsushi ; Tsukada, Kazuaki ; Nagame, Yuichiro. / Formation and thermochemical properties of oxychlorides of niobium (Nb) and tantalum (Ta) : Towards the gas-phase investigation of dubnium (Db) oxychloride. In: Inorganica Chimica Acta. 2019 ; Vol. 486. pp. 361-366.
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