Structure and thermodynamic stability of UTa 3 O 10 , a U( v )-bearing compound

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Wu, Di; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

doi:10.1039/c6dt02843h

Structure and thermodynamic stability of UTa ₃ O ₁₀ , a U( v )-bearing compound

Journal Article · Fri Sep 09 04:00:00 EDT 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/c6dt02843h· OSTI ID:1340791

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Wu, Di; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

Heating a mixture of uranyl(VI) nitrate and tantalum(V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa₃O₁₀. The honey colored to yellow brown crystals of UTa₃O₁₀ crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO₆]^7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO₆]^7- octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO₂]⁺, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa₃O₁₀ from Ta₂O₅, β-U₃O₇, and U₃O₈ has been determined to be 13.1 ± 18.1 kJ mol^-1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa₃O₁₀ can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM₃O₁₀ compounds.

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1340791

Report Number(s):: PNNL-SA--123270; KP1704020

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 47 Vol. 45; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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