Synthesis, thermogravimetric analysis and enthalpy determination of lanthanide β-diketonates

Shahbazi, Shayan; Oldham, C. J.; Mullen, Austin D.; Auxier II, John D.; Hall, Howard L.

doi:10.1515/ract-2018-3085

Synthesis, thermogravimetric analysis and enthalpy determination of lanthanide β-diketonates

Journal Article · Sat Apr 13 04:00:00 EDT 2019 · Radiochimica Acta

DOI:https://doi.org/10.1515/ract-2018-3085· OSTI ID:1801054

Shahbazi, Shayan ^[1]; Oldham, C. J. ^[2]; Mullen, Austin D. ^[2]; Auxier II, John D. ^[3]; Hall, Howard L. ^[3]

Department of Nuclear Engineering, 301 Middle Dr., Pasqua Nuclear Engineering Building , University of Tennessee , Knoxville, TN 37996 , USA; OSTI
Department of Nuclear Engineering, 301 Middle Dr., Pasqua Nuclear Engineering Building , University of Tennessee , Knoxville, TN 37996 , USA
Department of Nuclear Engineering, 301 Middle Dr., Pasqua Nuclear Engineering Building , University of Tennessee , Knoxville, TN 37996 , USA; Radiochemistry Center of Excellence, 1508 Middle Dr., Ferris Hall, University of Tennessee , Knoxville, TN 37996 , USA; Institute for Nuclear Security, 1640 Cumberland Ave. Howard Baker Jr. Center for Public Policy, University of Tennessee , Knoxville, TN 37996 , USA

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.

Research Organization:: Univ. of Tennessee, Knoxville, TN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

DOE Contract Number:: NA0001983

OSTI ID:: 1801054

Journal Information:: Radiochimica Acta, Journal Name: Radiochimica Acta Journal Issue: 12 Vol. 107; ISSN 0033-8230

Publisher:: de Gruyter

Country of Publication:: United States

Language:: English

References (30)

The Application of Thermoanalytical Techniques to Reaction Kinetics: The Thermogravimetric Evaluation of the Kinetics of the Decomposition of Calcium Oxalate Monohydrate Freeman, Eli S.; Carroll, Benjamin The Journal of Physical Chemistry, Vol. 62, Issue 4 https://doi.org/10.1021/j150562a003	journal	April 1958
The Vapor Pressure of Metallic Tungsten Langmuir, Irving Physical Review, Vol. 2, Issue 5 https://doi.org/10.1103/PhysRev.2.329	journal	November 1913
Characterization and thermogravimetric analysis of lanthanide hexafluoroacetylacetone chelates Shahbazi, Shayan; Stratz, S. Adam; Auxier, John D. Journal of Radioanalytical and Nuclear Chemistry, Vol. 311, Issue 1 https://doi.org/10.1007/s10967-016-5005-0	journal	August 2016
Thermoanalytical and mass spectrometric studies on volatile β-diketone chelates Leskelä, M.; Niinistö, L.; Nykänen, E. Thermochimica Acta, Vol. 175, Issue 1 https://doi.org/10.1016/0040-6031(91)80250-M	journal	February 1991
On the Stability and Volatility of Group 8 Tetroxides, MO ₄ (M = Ruthenium, Osmium, and Hassium ( Z = 108)) Düllmann, Christoph E.; Eichler, Bernd; Eichler, Robert The Journal of Physical Chemistry B, Vol. 106, Issue 26 https://doi.org/10.1021/jp0257146	journal	July 2002
Gas-phase detection of solid-state fission product complexes for post-detonation nuclear forensic analysis Stratz, S. Adam; Jones, Steven A.; Oldham, Colton J. Journal of Radioanalytical and Nuclear Chemistry, Vol. 310, Issue 3 https://doi.org/10.1007/s10967-016-4920-4	journal	June 2016
Synthesis and characterization of alkaline-earth-metal .beta.-diketonate complexes used as precursors for chemical vapor deposition of thin film superconductors Turnipseed, S. B.; Barkley, R. M.; Sievers, R. E. Inorganic Chemistry, Vol. 30, Issue 6 https://doi.org/10.1021/ic00006a003	journal	March 1991
Synthesis, thermogravimetric analysis, infrared, electronic and mass spectra of Mn(II), Co(II) and Fe(III) norfloxacin complexes Sadeek, Sadeek A. Journal of Molecular Structure, Vol. 753, Issue 1-3 https://doi.org/10.1016/j.molstruc.2005.06.011	journal	October 2005
Fractional sublimation of the β-diketone chelates of the lanthanide and related elements Berg, Eugene W.; Jaime Chiang Acosta, J. Analytica Chimica Acta, Vol. 40 https://doi.org/10.1016/S0003-2670(00)86700-8	journal	January 1968
Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates Johnson, Aaron T.; Parker, T. Gannon; Dickens, Sara M. Inorganic Chemistry, Vol. 56, Issue 21 https://doi.org/10.1021/acs.inorgchem.7b02290	journal	October 2017
Volatile Rare Earth Chelates Eisentraut, Kent J.; Sievers, Robert E. Journal of the American Chemical Society, Vol. 87, Issue 22 https://doi.org/10.1021/ja00950a051	journal	November 1965
Gas Phase Chromatography of Metal Chelates of Acetylacetone, Trifluoroacetylacetone, and Hexafluoroacetylacetone Sievers, Robert E.; Ponder, B. W.; Morris, Melvin L. Inorganic Chemistry, Vol. 2, Issue 4 https://doi.org/10.1021/ic50008a006	journal	August 1963
Substituent effects on the volatility of metal ?-diketonates Fahlman, Bradley D.; Barron, Andrew R. Advanced Materials for Optics and Electronics, Vol. 10, Issue 3-5 https://doi.org/10.1002/1099-0712(200005/10)10:3/5<223::AID-AMO411>3.0.CO;2-M	journal	January 2000
The use of Ce(fod)4 as a precursor for the growth of ceria films by metal-organic chemical vapour deposition McAleese, John; Plakatouras, John C.; Steele, Brian C. H. Thin Solid Films, Vol. 280, Issue 1-2 https://doi.org/10.1016/0040-6090(95)08193-3	journal	July 1996
Rare earth chelates of 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione Springer, Charles S.; Meek, Devon W.; Sievers, Robert E. Inorganic Chemistry, Vol. 6, Issue 6 https://doi.org/10.1021/ic50052a009	journal	June 1967
Thermodynamic analysis of volatile organometallic fission products Auxier, John D.; Jordan, Jacob A.; Stratz, S. Adam Journal of Radioanalytical and Nuclear Chemistry, Vol. 307, Issue 3 https://doi.org/10.1007/s10967-015-4653-9	journal	December 2015
Improved Docking of Polypeptides with Glide Tubert-Brohman, Ivan; Sherman, Woody; Repasky, Matt Journal of Chemical Information and Modeling, Vol. 53, Issue 7 https://doi.org/10.1021/ci400128m	journal	July 2013
Assessing thermochromatography as a separation method for nuclear forensics: current capability vis-à-vis forensic requirements Hanson, D. E.; Garrison, J. R.; Hall, H. L. Journal of Radioanalytical and Nuclear Chemistry, Vol. 289, Issue 1 https://doi.org/10.1007/s10967-011-1063-5	journal	April 2011
Synthesis and detection of a seaborgium carbonyl complex Even, J.; Yakushev, A.; Dullmann, C. E. Science, Vol. 345, Issue 6203 https://doi.org/10.1126/science.1255720	journal	September 2014
Metal alkoxides and ?-diketonates as precursors for oxide and non-oxide thin films Hubert-Pfalzgraf, L. G. Applied Organometallic Chemistry, Vol. 6, Issue 8 https://doi.org/10.1002/aoc.590060805	journal	December 1992
Calorimetry of two disperse dyes using thermogravimetry Price, Duncan M.; Hawkins, Michael Thermochimica Acta, Vol. 315, Issue 1 https://doi.org/10.1016/S0040-6031(98)00272-X	journal	May 1998
The Role of Nuclear Forensics in Nuclear Security Fedchenko, Vitaly Strategic Analysis, Vol. 38, Issue 2 https://doi.org/10.1080/09700161.2014.884442	journal	March 2014
Ionization energies of metal chelates. Acetylacetonates, trifluoroacetylacetonates, and hexafluoroacetylacetonates of trivalent metals of the first transition series Westmore, John B.; Reimer, Mark L. J.; Reichert, Charles Canadian Journal of Chemistry, Vol. 59, Issue 12 https://doi.org/10.1139/v81-268	journal	June 1981
The measurement of enthalpies of sublimation by thermogravimetry Ashcroft, S. J. Thermochimica Acta, Vol. 2, Issue 6 https://doi.org/10.1016/0040-6031(71)80021-7	journal	September 1971
Thermochemical Characterization of Seaborgium Compounds in Gas Adsorption Chromatography Eichler, B.; Türler, A.; Gäggeler, H. W. The Journal of Physical Chemistry A, Vol. 103, Issue 46 https://doi.org/10.1021/jp9917751	journal	November 1999
Kinetic Parameters from Thermogravimetric Data Coats, A. W.; Redfern, J. P. Nature, Vol. 201, Issue 4914 https://doi.org/10.1038/201068a0	journal	January 1964
The Basicity Characteristics of Scandium, Yttrium, and the Rare Earth Elements. Moeller, Therald.; Kremers, Howard E. Chemical Reviews, Vol. 37, Issue 1 https://doi.org/10.1021/cr60116a003	journal	August 1945
Volatility Studies on Gallium Chalcogenide Cubanes: Thermal Analysis and Determination of Sublimation Enthalpies Gillan, Edward G.; Bott, Simon G.; Barron, Andrew R. Chemistry of Materials, Vol. 9, Issue 3 https://doi.org/10.1021/cm960485j	journal	March 1997
A New Analysis of Thermogravimetric Traces. Horowitz, H. H.; Metzger, Gershon. Analytical Chemistry, Vol. 35, Issue 10 https://doi.org/10.1021/ac60203a013	journal	September 1963
General treatment of the thermogravimetry of polymers Flynn, Joseph H.; Wall, Leo A. Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 70A, Issue 6 https://doi.org/10.6028/jres.070A.043	journal	November 1966

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