Bicyclic and Acyclic Diamides: Comparison of Their Aqueous Phase Binding Constants with Nd(III), Am(III), Pu(IV), Np(V), Pu(VI) and U(VI)

Journal Article · Mon Dec 27 04:00:00 EST 2004 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic049377m· OSTI ID:15020728

Sinkov, Sergei I; Rapko, Brian M; Lumetta, Gregg J; Hay, Benjamin P; Hutchison, James E; Parks, Bevin W

This report describes affinity measurements for two, water-soluble, methyl-alkylated diamides incorporating the malonamide functionality, N,N,N?,N? tetramethylmalonamide (TMMA) and a bicyclic diamide (1a), towards actinide metal cations (An) in acidic nitrate solutions. Ligand complexation to actinides possessing oxidation states ranging from +3 to +6 was monitored through optical absorbance spectroscopy, and formation constants were obtained from the refinement of the spectrophotometric titration data sets. Species analysis gives evidence for the formation of 1, 4, 1, and 2 spectrophotometrically observable complexes by TMMA to An(III, IV, V, and VI), respectively, while for 1a, the respective numbers are 3, 4, 2, and 2. Consistent with the preorganization of 1a towards actinide binding, a significant difference is found in the magnitudes of their respective formation constants at each complexation step. It has been found that the binding affinity for TMMA follows the well established order: An(V)<An(III)<An(VI)<An(IV). However, with 1a, Np(V) forms stronger complexes than Am(III). The complexation of 1a with Np(V) and Pu(VI) at an acidity of 1.0 M is followed by reduction to Np(IV) and Pu(IV), whereas TMMA does not perturb the initial oxidation state for these dioxocations. These measurements of diamide binding affinity mark the first time single-component optical absorbance spectra have been reported for a span of actinide-diamide complexes covering all common oxidation states in aqueous solution.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 15020728
• Report Number(s): PNNL-SA-41622; KP1301020
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 26 Vol. 43
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
AFFINITY
AMERICIUM COMPLEXES
AMIDES
AQUEOUS SOLUTIONS
CHELATING AGENTS
NEODYMIUM COMPLEXES
NEPTUNIUM COMPLEXES
PLUTONIUM COMPLEXES
TITRATION
URANIUM COMPLEXES
VALENCE