Citation: Baihua Chen, Jun Liu, Hongyuan Wei, Yuchuan Yang, Xingliang Li, Shuming Peng, Yanqiu Yang. Complexation between uranyl(Ⅵ) and CMPO in a hydroxyl-functionalized ionic liquid: An extraction, spectrophotography, and calorimetry study[J]. Chinese Chemical Letters, ;2022, 33(7): 3451-3455. doi: 10.1016/j.cclet.2021.12.066 shu

Complexation between uranyl(Ⅵ) and CMPO in a hydroxyl-functionalized ionic liquid: An extraction, spectrophotography, and calorimetry study

Institute of Nuclear Physics and Chemistry, CAEP, Mianyang 621900, China

pengshuming@caep.cn

yan.qiu.yang@163.com

Received Date: 4 November 2021
Revised Date: 22 December 2021
Accepted Date: 24 December 2021
Available Online: 29 December 2021

Figures(5)

The extraction complexes of uranyl(Ⅵ) in HNO₃ to a hydroxyl-functionalized ionic liquid (IL) phase, HOEtmimNTf₂ bearing CMPO, were investigated. Three possibly successive extraction complexes, UO₂L²⁺ (L = CMPO), UO₂L₂²⁺ and UO₂L₃²⁺, were detected based on variable U/L ratios. Uranyl(Ⅵ) prefers to be extracted as complex UO₂L₃²⁺, combining with the ions from HOEtmimNTf₂ to construct a solid material through self-assembly. The thermodynamics of complexes, UO₂L²⁺ (j = 1-3), were studied by spectrophotometry and microcalorimetry. All the formation reactions are principally driven by entropy, although a small part of the driving force of complexes UO₂L₂²⁺ and UO₂L₃²⁺ comes from enthalpy. Based on the thermodynamic properties for complex UO₂L₃²⁺, we provide a possible coordination mode in HOEtmimNTf₂: the first CMPO molecule coordinates with UO₂²⁺ in a bidentate fashion while the others do in a monodentate fashion. The results offer a thermodynamic insight into the formation behaviors of the uranyl(Ⅵ)/CMPO complexes involving the special IL HOEtmimNTf₂, which is of significance to advance the novel IL extraction strategy.
- Uranyl(Ⅵ),
- CMPO,
- Ionic liquid,
- Solvent extraction,
- Complexation,
- Thermodynamics
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