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

Graphical abstract Highlights • Niobium. • Tantalum. • Dubnium. • Oxychlorides. • Adsorption enthalpy. Abstract 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 (Δ H ads) at zero surface coverage of –Δ H ads (NbOCl 3) = 102 ± 4 kJ/mol and –Δ H ads (TaOCl 3) = 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 Δ H ads values were successively related to the macroscopic standard sublimation enthalpy, Δ H° 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 Δ H ads and Δ H° subl for metal-oxychlorides was updated with the inclusion of the present data. According to the predicted Δ H° subl (DbOCl 3), a Δ H ads (DbOCl 3) value of 135 ± 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. [ABSTRACT FROM AUTHOR]