Show simple item record

dc.contributor.advisorNash, Kenneth L
dc.creatorTokheim, Benjamin George
dc.date.accessioned2017-06-19T17:44:28Z
dc.date.available2017-06-19T17:44:28Z
dc.date.issued2016
dc.identifier.urihttp://hdl.handle.net/2376/12073
dc.descriptionThesis (Ph.D.), Chemistry, Washington State Universityen_US
dc.description.abstractTwelve new unsymmetrical diglycolamide (UDGA) ligands have been synthesized as solvent extraction reagents for trivalent lanthanide ions from highly acidic nitrate media. The asymmetry in the extractant design arises from attaching nonpolar alkyl chains (hexyl, octyl, 2-ethylhexyl, 3,7-dimethyloctyl) to one amide group and smaller, more compact, cyclic alkyl groups (pyrrolidinyl, piperidinyl, morpholino) to the other amide moiety. This structural variant of a well-known cation receptor reduces the interfacial footprint of the extractant and is designed to increase the rate of phase transfer of the target cations. The partitioning of 152,154Eu(III) between aqueous phases of varying nitric acid concentrations (0.01-3 M) and a 0.05 M UDGA in 5% v/v 1-octanol/n-dodecane organic phase was measured radiometrically and compared to the symmetrical diglycolamide, N,N,N′,N′-tetraoctyldiglycolamide (TODGA). All twelve UDGA ligands quantitatively extracted trivalent Eu(III) cations from 1 M nitric acid. Separate solvent extraction slope analysis experiments were used to determine the stoichiometry and conditional extraction equilibrium constant (K'ex) of the extracted Eu-UDGA complex in 5% v/v 1-octanol/n-dodecane. The metal-ligand complex stoichiometry in the extracted species was found to be approximately 1:3 for the UDGA ligands and TODGA while the conditional extraction equilibrium constants (K'ex) decreased with increasing ligand size and alkyl chain branching. Luminescence spectroscopy investigations established the relative stability and stoichiometry of the complexes in acetonitrile. The overall trends in the conditional extraction equilibrium constant (K'ex) and the 1:3 conditional stability constant (β103) followed a similar pattern, indicating a correlation between complex stability and ligand structural features.en_US
dc.description.sponsorshipWashington State University, Chemistryen_US
dc.language.isoEnglish
dc.rightsIn copyright
dc.rightsPublicly accessible
dc.rightsopenAccess
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0
dc.rights.urihttp://www.ndltd.org/standards/metadata
dc.rights.urihttp://purl.org/eprint/accessRights/OpenAccess
dc.subjectChemistryen_US
dc.subjectdiglycolamideen_US
dc.subjectlanthanideen_US
dc.subjectligand synthesisen_US
dc.subjectnuclear fuel reprocessingen_US
dc.subjectsolvent extractionen_US
dc.subjectunsymmetricalen_US
dc.titleSynthesis and Characterization of New Unsymmetrical Diglycolamides for Trivalent Lanthanide Metal Extraction
dc.typeText
dc.typeElectronic Thesis or Dissertation


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record