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Title: Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid

Journal Article · · Inorganic Chemistry
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In this study, the coordination behavior and thermodynamic features of complexation of trivalent lanthanides and americium by ethylenediamine-N,N'-di(acetylglycine)-N,N'-diacetic acid (EDDAG-DA) (bisamide-substituted-EDTA) were investigated by potentiometric and spectroscopic techniques. Acid dissociation constants (Ka) and complexation constants (β) of lanthanides (except Pm) were determined by potentiometric analysis. Absorption spectroscopy was used to determine stability constants for the binding of trivalent americium and neodymium by EDDAG-DA under similar conditions. The potentiometry revealed 5 discernible protonation constants and 3 distinct metal–ligand complexes (identified as ML–, MHL, and MH2L+). Time-resolved fluorescence studies of Eu-(EDDAG-DA) solutions (at varying pH) identified a constant inner-sphere hydration number of 3, suggesting that glycine functionalities contained in the amide pendant arms are not involved in metal complexation and are protonated under more acidic conditions. The thermodynamic studies identified that f-element coordination by EDDAG-DA is similar to that observed for ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA). However, coordination via two amidic oxygens of EDDAG-DA lowers its trivalent f-element complex stability by roughly 3 orders of magnitude relative to EDTA.

Research Organization:
Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
AC07-05ID14517
OSTI ID:
1303373
Report Number(s):
INL/JOU-15-37469
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 6; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

References (32)

A REVIEW OF THE BASIC CHEMISTRY AND RECENT DEVELOPMENTS IN TRIVALENT f-ELEMENTS SEPARATIONS journal May 1993
Preferential extraction of lanthanides over trivalent actinides by monoacidic organophosphates from carboxylic acids and from mixtures of carboxylic and aminopolyacetic acids journal January 1968
The Synthesis and Screening of Nonionic Gadolinium (III) DTPA-Bisamide Complexes as Magnetic Resonance Imaging Contrast Agents journal January 1991
Trans‐Lanthanide Extraction Studies in the TALSPEAK System: Investigating the Effect of Acidity and Temperature journal April 2009
Stability, structure and dynamics of cationic lanthanide(iii) complexes of N,N′-bis(propylamide)ethylenediamine-N,N′-diacetic acid journal January 2003
Actinide Lanthanide Separation Process—ALSEP journal January 2014
Synthesis, stability and nuclear magnetic resonance studies for the complexation of trivalent lanthanides, Ca2, Cu2 and Zn2 by N,N′-bis (amide) derivatives of ethylenedinitrilotetraacetic acid journal December 1998
The Actinide-Lanthanide Separation Concept journal May 2014
Factors in Ln(III) complexation journal March 1997
Complexation kinetics of f-elements and polydentate ligands journal July 1995
Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs journal October 1996
Kinetics and Mechanism of the Interfacial Mass Transfer of Eu(III) in the System: Bis(2-ethylhexyl)phosphoric Acid, n -Dodecane-NaCl, Lactic Acid, Polyaminocarboxylic Acid, Water journal May 1982
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
Potentiometric titrations using Gran plots: A textbook omission journal July 1965
Gadolinium(III) Chelates as MRI Contrast Agents:  Structure, Dynamics, and Applications journal September 1999
Luminescence study on determination of the hydration number of Cm(III) journal October 1994
EDTA bis-(ethyl phenylalaninate): A novel transition metal-Ion chelating hydroxyl radical scavenger with a potential anti-inflammatory role journal October 2001
Purification of Organophosphorus acid Extractants journal August 1995
Luminescence study on determination of the inner-sphere hydration number of Am(III) and Nd(III) journal June 1998
Complexes of the rare earths—II journal December 1962
New multidentate ligands. X. Chelating tendencies of N,N'-diglycylethylenediamine-N'',N'',N''',N'''-tetraacetic acid and ethylenediamine-N-N'-di(acetylglycine)-N,N'-diacetic acid journal July 1970
Thermodynamic Properties of Rare Earth Complexes. XX. Free Energy, Enthalpy and Entropy Changes for the Formation of Rare Earth(III) Complexes with Dicarboxylates, -OCOCH2RCH2CH2RCH2COO-, R=S, O, or NH. journal January 1974
Kinetics and mechanism of the interfacial mass transfer of europium(3+) and americium(3+) in the system bis(2-ethylhexyl) phosphate-n-dodecane-sodium chloride-hydrochloric acid-water journal November 1981
Alternatives to HDEHP and DTPA for Simplified TALSPEAK Separations journal June 2011
Characterization of Lanthanide Complexes with a Series of Amide-Based Macrocycles, Potential MRI Contrast Agents, Using Eu3+ Luminescence Spectroscopy and Molecular Mechanics journal June 1994
Principles of Nuclear Power book January 2002
Lanthanide ion probes of structure in biology. Laser-induced luminescence decay constants provide a direct measure of the number of metal-coordinated water molecules journal January 1979
Acid Dissociation Constants and Rare Earth Stability Constants for DTPA journal February 2014
Development of a TODGA based Process for Partitioning of Actinides from a PUREX Raffinate Part I: Batch Extraction Optimization Studies and Stability Tests journal October 2007
Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations journal August 2002
Review Article: A Review of the Development and Operational Characteristics of the TALSPEAK Process journal October 2007
Development and demonstration of innovative partitioning processes (i-SANEX and 1-cycle SANEX) for actinide partitioning journal April 2014

Cited By (6)

Prediction of trivalent actinide amino(poly)carboxylate complex stability constants using linear free energy relationships with the lanthanide series journal November 2017
Pyridine Polyaminocarboxylate Ligands for Use as Actinide-selective Holdback Reagents in Simplified TALSPEAK-like Extraction Systems journal March 2020
Pyridine Polyaminocarboxylate Ligands for Use as Actinide-selective Holdback Reagents in Simplified TALSPEAK-like Extraction Systems text January 2020
Pyridine Polyaminocarboxylate Ligands for Use as Actinide-selective Holdback Reagents in Simplified TALSPEAK-like Extraction Systems text January 2020
Influence of a Pre‐organized N‐Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant journal January 2019
On the Antibacterial Activity of Azacarboxylate Ligands: Lowered Metal Ion Affinities for Bis-amide Derivatives of EDTA do not mean Reduced Activity journal March 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
coordination
actinide
lanthanide
TALSPEAK
ALSEP
separations
nuclear fuel cycle
f-elements
chelate
EDTA
thermodynamics
metal coordination
aminopolycarboxylatel aqueous complexants