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Title: Coordination Modes in the Formation of Ternary Complexes of Am(III), Cm(III) and Eu(III) with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and Thermodynamics of the complexation.

Abstract

The formation and the structure of the ternary complexes of trivalent Am, Cm, and Eu with mixtures of EDTA+NTA (ethylenediamine tetraacetate and nitrilotriacetate) have been studied by time-resolved laser fluorescence spectroscopy, {sup 13}C NMR, extended X-ray absorption fine structure, and two-phase metal ion equilibrium distribution at 6.60 m (NaClO{sub 4}) and a hydrogen ion concentration value (pcH) between 3.60 and 11.50. In the ternary complexes, EDTA binds via four carboxylates and two nitrogens, while the binding of the NTA varies with the hydrogen ion concentration, pcH, and the concentration ratios of the metal ion and the ligand. When the concentration ratios of the metal to ligand is low (1:1:1-1:1:2), two ternary complexes, M(EDTA)(NTAH){sup 3-} and M(EDTA)(NTA){sup 4-}, are formed at pcH ca. 9.00 in which NTA binds via three carboxylates, via two carboxylates and one nitrogen, or via two carboxylates and a H{sub 2}O. At higher ratios (1:1:20 and 1:10:10) and pcH's of ca. 9.00 and 11.50, one ternary complex, M(EDTA)(NTA){sup 4-}, is formed in which NTA binds via three carboxylates and not via nitrogen. The two-phase equilibrium distribution studies at tracer concentrations of Am, Cm, and Eu have also confirmed the formation of the ternary complex M(EDTA)(NTA){sup 4-} atmore » temperatures between 0 and 60 {sup o}C. The stability constants (log{beta}{sub 111}) for these metal ions increase with increasing temperature. The endothermic enthalpy and positive entropy indicated a significant effect of cation dehydration in the formation of the ternary complexes at high ionic strength.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930244
Report Number(s):
BNL-80932-2008-JA
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US0806720
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 45
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ABSORPTION; AUGMENTATION; CATIONS; COMPLEXES; CONCENTRATION RATIO; DEHYDRATION; DISTRIBUTION; EDTA; ENTHALPY; ENTROPY; EQUILIBRIUM; FINE STRUCTURE; FLUORESCENCE SPECTROSCOPY; HYDROGEN IONS; IONS; LASERS; LIGANDS; METALS; MIXTURES; NITROGEN; NTA; NUCLEAR MAGNETIC RESONANCE; STABILITY; THERMODYNAMICS; national synchrotron light source

Citation Formats

Mathur,J., Thakur, P., Dodge, C., Francis, A., and Choppin, G. Coordination Modes in the Formation of Ternary Complexes of Am(III), Cm(III) and Eu(III) with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and Thermodynamics of the complexation.. United States: N. p., 2006. Web. doi:10.1021/ic052166c.
Mathur,J., Thakur, P., Dodge, C., Francis, A., & Choppin, G. Coordination Modes in the Formation of Ternary Complexes of Am(III), Cm(III) and Eu(III) with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and Thermodynamics of the complexation.. United States. doi:10.1021/ic052166c.
Mathur,J., Thakur, P., Dodge, C., Francis, A., and Choppin, G. Sun . "Coordination Modes in the Formation of Ternary Complexes of Am(III), Cm(III) and Eu(III) with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and Thermodynamics of the complexation.". United States. doi:10.1021/ic052166c.
@article{osti_930244,
title = {Coordination Modes in the Formation of Ternary Complexes of Am(III), Cm(III) and Eu(III) with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and Thermodynamics of the complexation.},
author = {Mathur,J. and Thakur, P. and Dodge, C. and Francis, A. and Choppin, G.},
abstractNote = {The formation and the structure of the ternary complexes of trivalent Am, Cm, and Eu with mixtures of EDTA+NTA (ethylenediamine tetraacetate and nitrilotriacetate) have been studied by time-resolved laser fluorescence spectroscopy, {sup 13}C NMR, extended X-ray absorption fine structure, and two-phase metal ion equilibrium distribution at 6.60 m (NaClO{sub 4}) and a hydrogen ion concentration value (pcH) between 3.60 and 11.50. In the ternary complexes, EDTA binds via four carboxylates and two nitrogens, while the binding of the NTA varies with the hydrogen ion concentration, pcH, and the concentration ratios of the metal ion and the ligand. When the concentration ratios of the metal to ligand is low (1:1:1-1:1:2), two ternary complexes, M(EDTA)(NTAH){sup 3-} and M(EDTA)(NTA){sup 4-}, are formed at pcH ca. 9.00 in which NTA binds via three carboxylates, via two carboxylates and one nitrogen, or via two carboxylates and a H{sub 2}O. At higher ratios (1:1:20 and 1:10:10) and pcH's of ca. 9.00 and 11.50, one ternary complex, M(EDTA)(NTA){sup 4-}, is formed in which NTA binds via three carboxylates and not via nitrogen. The two-phase equilibrium distribution studies at tracer concentrations of Am, Cm, and Eu have also confirmed the formation of the ternary complex M(EDTA)(NTA){sup 4-} at temperatures between 0 and 60 {sup o}C. The stability constants (log{beta}{sub 111}) for these metal ions increase with increasing temperature. The endothermic enthalpy and positive entropy indicated a significant effect of cation dehydration in the formation of the ternary complexes at high ionic strength.},
doi = {10.1021/ic052166c},
journal = {Inorganic Chemistry},
number = ,
volume = 45,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}