Thesis
The effect of counter ions on lanthanide solvation
Washington State University
Master of Science (MS), Washington State University
2013
Handle:
https://hdl.handle.net/2376/105393
Abstract
Understanding the behavior of fission products in solution is important to separations. Because separations take place in ionic solutions, the counterion can have an effect on extraction. This work looks at the effect of chloride on the solvation structure of different members of the lanthanide series. The effect of chloride on the solvation properties of lanthanides was explored using computational methods. Density Functional Theory (DFT) calculations were used to determine the thermodynamics of lanthanide chloride complexes in solution. Calculations determined the favorability of the formation of first shell chloride complexes and solvent separated ion pairs as well as the favorability of the mechanism (addition vs replacement) of chloride ligation. Molecular dynamics was used to determine the structure of the lanthanide clusters and their behavior in increasingly concentrated chloride solutions. The DFT calculations show that a replacement reaction is the most thermodynamically favorable. Also, chloride complexation becomes less favorable as you move across the lathanide series. Molecular dynamics showed that the lanthanides become under coordinated when chloride is in the second solvation iv shell, and this allows chloride to enter the first solvation shell through an addition mechanism.
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Details
- Title
- The effect of counter ions on lanthanide solvation
- Creators
- Daniel Thomas Sullivan
- Contributors
- Aurora E. Clark (Degree Supervisor)
- Awarding Institution
- Washington State University
- Academic Unit
- Chemistry, Department of
- Theses and Dissertations
- Master of Science (MS), Washington State University
- Publisher
- Washington State University; [Pullman, Washington] :
- Identifiers
- 99900525105301842
- Language
- English
- Resource Type
- Thesis