A Nuclear Magnetic Resonance Study on Ligand Exchange Reactions in U(VI) Nitrato Complexes with Ligands Containing Phosphoryl Group in Non-aqueous Solvents.
-
- HATAKEYAMA Koh
- Research Laboratory for Nuclear Reactors Tokyo Institute of Technology Naka Energy Research Center Mitsubishi Materials Corp.,
-
- PARK Yoon-Yul
- Research Laboratory for Nuclear Reactors Tokyo Institute of Technology Pusan Junior College
-
- TOMIYASU Hiroshi
- Research Laboratory for Nuclear Reactors Tokyo Institute of Technology
-
- IKEDA Yasuhisa
- Kashiwa Laboratory Institute of Research and Innovation
Bibliographic Information
- Other Title
-
- Nuclear Magnetic Resonance Study on Lig
Search this article
Abstract
The exchange reactions of tributyl phosphate (TBP) and dihexyl-N, N-diethylcarbamoylmethylphosphonate (CMP) in U(VI) nitrato complexes with TBP or CMP (abbreviated as U(VI)-TBP or U(VI)-CMP) have been studied by means of 31P NMR method in CD3COCD3 or CD2Cl2. The number of TBP coordinated to uranyl nitrate was directly determined to be 1 in CD3COCD3 and 2 in CD2Cl2 by the area integrations of 31P NMR signals of free and coordinated TBP. Similarly, the number of coordinated CMP was evaluated as 1 in CD3COCD3. The exchange rate constants of TBP and CMP in U(VI)-TBP and U(VI)-CMP complexes were calculated by the two-site exchange model. The exchange rate of TBP in U(VI)-TBP is independent of the free TBP concentrations ([TBP]f ), while that in U(VI)-CMP is dependent on [CMP]f. From these results, the dissociative (D) and interchange (I) mechanisms were proposed for the exchange reactions of TBP in U(VI)-TBP and CMP in U(VI)-CMP, respectively. Kinetic parameters are as follows: rate constant (25°C), ΔH≠(kJ-mol-1), ΔS≠(J•K-1•mol-1); 9.9×103s-1, 33.7, -55.4 (U(VI)-TBP system), 2.3×104 m-1•s-1 (apparent second-order), 25.2, -75.9 (U(VI)-CMP system).
Journal
-
- Journal of Nuclear Science and Technology
-
Journal of Nuclear Science and Technology 34 (3), 298-303, 1997
Atomic Energy Society of Japan
- Tweet
Keywords
Details 詳細情報について
-
- CRID
- 1390001204096034176
-
- NII Article ID
- 10002076743
-
- NII Book ID
- AA00703720
-
- COI
- 1:CAS:528:DyaK2sXivFWlu7c%3D
-
- ISSN
- 18811248
- 00223131
-
- NDL BIB ID
- 4176283
-
- Text Lang
- en
-
- Data Source
-
- JaLC
- NDL
- Crossref
- CiNii Articles
-
- Abstract License Flag
- Disallowed