In an effort to meet the growing demand for more rapid separation methods, this work reports the development and thermodynamic characterizations of organometallic species as a vehicle for the rapid separation of volatile nuclear fission products.  Volatile organometallic complexes can be rapidly separated from each other via gas phase chromatographic separations due to differences in adsorption enthalpy. Because adsorption and sublimation thermodynamics are linearly correlated, there is considerable motivation to determine sublimation enthalpies to improve the ability to predict separations effectiveness. A method of using thermogravimetric analysis (TGA) is employed in this study on complexes of fourteen lanthanides, and up to four different chelating ligands. 1,1,1,5,5,5-hexafluoroacetylacetone (hfac), 1,1,1-trifluoro-2,4-pentanedione (tfac), 2,2,6,6-tetramethyl-3,5-heptanedione (dpm or thd), and 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (fod) are all used to synthesize homoleptic complexes of the lanthanides. These 56 complexes are characterized with melting point, ICP-MS, FT-IR and elemental analysis. Sublimation enthalpies are determined using the Langmuir method involving isothermal jump heating. An empirical correlation is used to estimate adsorption enthalpies of lanthanide complexes on a quartz column from the sublimation data. TGA-MS and melting point are also used to confirm sublimation and the stability of the chelate through the sublimation region.<br/>

Thermal analysis of lanthanide chelates for nuclear forensics

255th National Meeting (2018)

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