Synthesis, thermogravimetric analysis and enthalpy determination of lanthanide β-diketonates
-
Shayan Shahbazi
,
C. J. Oldham
Abstract
This work reports thermodynamic characterizations of lanthanide β-diketonates for use in nuclear fission product separation. Adsorption and sublimation enthalpies have been shown to be linearly correlated, therefore there is motivation to determine sublimation thermodynamics. An isothermal thermogravimetric analysis method is employed on fourteen lanthanide chelates for the ligands 2,2,6,6-tetramethyl-3,5-heptanedione and 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione to determine sublimation enthalpies. No linear trend is seen across the series; values show a cyclical nature, possibly indicating a greater influence of chemisorption for some complexes and less of a role of physisorption in dictating adsorption differences between lanthanides in the same series. This is in line with previous reports in terms of the chromatographic separation order of the lanthanides. The results reported here can be used to manipulate separations parameters and column characteristics to better separate these lanthanide chelates. Fourteen chelates of the ligand 1,1,1-trifluoro-2,4-pentanedione are also thermally characterized but found to not sublime and be undesirable for this method. Additionally, all chelates are characterized by constant heating thermogravimetric analysis coupled with mass spectrometry, melting point analysis, elemental analysis and FTIR.
Funding source: Office of Defense Programs
Award Identifier / Grant number: DE-NA0001983
Funding source: Science and Technology Directorate
Award Identifier / Grant number: 2012-DN- 130-NF0001
Funding statement: This work was performed under Office of Defense Programs, Funder Id: http://dx.doi.org/10.13039/100006127, grant number DE-NA0001983 from the Stewardship Science Academic Alliances (SSAA) Program of the National Nuclear Security Administration (NNSA). This material is also based upon work supported by the U.S. Department of Homeland Security under Science and Technology Directorate, Funder Id: http://dx.doi.org/10.13039/100008287, Grant Award Number, 2012-DN- 130-NF0001. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the U.S. Department of Homeland Security, Department of Energy or NNSA. The authors wish to thank Katrina Pangilinan in the Polymer Characterization Lab at the University of Tennessee at Knoxville, Dawn Riegner and Jordan Johnson at the U.S. Military Academy, and Dr. George Schweitzer in the Department of Chemistry at the University of Tennessee at Knoxville. Finally, the authors wish to thank Adam Stratz, Daniel Harding and Jeff Lux in the Department of Nuclear Engineering at the University of Tennessee at Knoxville.
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Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/ract-2018-3085).
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