Award Date


Degree Type


Degree Name

Doctor of Philosophy (PhD)


Chemistry and Biochemistry

First Committee Member

Ralf Sudowe

Second Committee Member

Dawn A. Shaughnessy

Third Committee Member

Ken R. Czerwinski

Fourth Committee Member

Gary S. Cerefice

Fifth Committee Member

Steen Madsen

Number of Pages



Study of the chemistry of the heaviest elements, Z ≥ 104, poses a unique challenge due to their low production cross-sections and short half-lives. Chemistry also must be studied on the one-atom-at-a-time scale, requiring automated, fast, and very efficient chemical schemes. Recent studies of the chemical behavior of copernicium (Cn, element 112) and flerovium (Fl, element 114) together with the discovery of isotopes of these elements with half-lives suitable for chemical studies have spurred a renewed interest in the development of rapid systems designed to study the chemical properties of elements with Z ≥ 114. This dissertation explores both extraction chromatography and solvent extraction as methods for development of a rapid chemical separation scheme for the homologs of flerovium (Pb, Sn, Hg) and element 115 (Bi, Sb), with the goal of developing a chemical scheme that, in the future, can be applied to on-line chemistry of both Fl and element 115. Macrocyclic extractants, specifically crown ethers and their derivatives, were chosen for these studies.

Carrier-free radionuclides, used in these studies, of the homologs of Fl and element 115 were obtained by proton activation of high purity metal foils at the Lawrence Livermore National Laboratory (LLNL) Center for Accelerator Mass Spectrometry (CAMS): natIn(p,n)113Sn, natSn(p,n)124Sb, and Au(p,n)197m,gHg. The carrier-free activity was separated from the foils by novel separation schemes based on ion exchange and extraction chromatography techniques. Carrier-free Pb and Bi isotopes were obtained from development of a novel generator based on cation exchange chromatography using the 232U parent to generate 212Pb and 212Bi.

Crown ethers show high selectivity for metal ions based on their size compared to the negatively charged cavity of the ether. Extraction by crown ethers occur based on electrostatic ion-dipole interactions between the negatively charged ring atoms (oxygen, sulfur, etc.) and the positively charged metal cations. Extraction chromatography resins produced by Eichrom Technologies, specifically the Pb resin based on di-t-byutlcyclohexano-18-crown-6, were chosen as a starting point for these studies. Simple chemical systems based solely on HCl matrices were explored to determine the extent of extraction for Pb, Sn and Hg on the resin. The kinetics and mechanism of extraction were also explored to determine suitability for a Fl chemical experiment. Systems based on KI/HCl and KI/HNO3 were explored for Bi and Sb. In both cases suitable separations, with high separation factors, were performed with vacuum flow columns containing the Pb-resin. Unfortunately the kinetics of uptake for Hg are far too slow on the traditional crown-ether to perform a Fl experiment and obtain whether or not Fl has true Hg-like character or not. However, the kinetics of Pb and Sn are more than sufficient for a Fl experiment to differentiate between Pb- or Sn-like character. To assess this kinetic issue a novel macrocyclic extractant based on sulfur donors was synthesized.

Hexathia-18-crown-6, the sulfur analog of 18-crown-6, was synthesized based with by a template reaction using high dilution techniques. The replacement of oxygen ring atoms with sulfur should give the extractant a softer character, which should allow for far greater affinity toward soft metals such as Hg and Pb. From HCl matrices hexathia-18-crown-6 showed far greater kinetics and affinity for Hg than the Pb-resin; however, no affinity for Pb or Sn was seen. This presumably is due to the fact the charge density of sulfur crown ethers does not point to the center of the ring, and future synthesis of a substituted sulfur crown ether which forces the charge density to mimic that of the traditional crown ether should enable extraction of Pb and Sn to a greater extent than with the Pb-resin. Initial studies show promise for the separation of Bi and Sb from HCl matrices using hexathia-18-crown-6.

Other macrocyclic extractants, including 2,2,2-cryptand, calix[6]arene and tetrathia-12-crown-4, were also investigated for comparison to the crown ethers. It was noted that these extractants are inferior compared to the crown and thiacrown ethers for extraction of Fl and element 115 homologs. A potential chemical system for Fl was established based on the Eichrom Pb resin, and insight to an improved system based on thiacrown ethers is presented.


Element 115; Extraction (Chemistry); Extraction Chromatography; Flerovium; Heavy Element; Solvent Extraction; Transactinide





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