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Title: Structural study of complexes formed by acidic and neutral organophosphorus reagents

Abstract

The coordination of the trivalent 4f ions, Ln = La 3+, Dy 3+, and Lu 3+, with neutral and acidic organophosphorus reagents, both individually and combined, was studied by use of X-ray absorption spectroscopy. These studies provide metrical information about the interatomic interactions between these cations and the ligands tri- n-butyl phosphate (TBP) and di- n-butyl phosphoric acid (HDBP), whose behavior are of practical importance to chemical separation processes that are currently used on an industrial scale. Previous studies have suggested the existence of complexes involving a mixture of ligands, accounting for extraction synergy. Through systematic variation of the aqueous phase acidity and extractant concentration and combination, we have found that complexes with Ln and TBP : HDBP at any mixture and HDBP alone involve direct Ln–O interactions involving 6 oxygen atoms and distant Ln–P interactions involving on average 3–5 phosphorus atoms per Ln ion. It was also found that Ln complexes formed by TBP alone seem to favor eight oxygen coordination, though we were unable to obtain metrical results regarding the distant Ln–P interactions due to the low signal attributed to a lower concentration of Ln ions in the organic phases. Our study does not support the existence ofmore » mixed Ln–TBP–HDBP complexes but, rather, indicates that the lanthanides are extracted as either Ln–HDBP complexes or Ln–TBP complexes and that these complexes exist in different ratios depending on the conditions of the extraction system. Furthermore, this fundamental structural information offers insight into the solvent extraction processes that are taking place and are of particular importance to issues arising from the separation and disposal of radioactive materials from used nuclear fuel.« less

Authors:
 [1];  [2];  [3]
  1. Univ. of California, Irvine, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of California, Irvine, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1341582
Alternate Identifier(s):
OSTI ID: 1369054
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 4; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; EXAFS; HDBP; Lanthanides; Solvent extraction; TBP; XANES

Citation Formats

Braatz, Alexander D., Antonio, Mark R., and Nilsson, Mikael. Structural study of complexes formed by acidic and neutral organophosphorus reagents. United States: N. p., 2016. Web. doi:10.1039/C6DT04305D.
Braatz, Alexander D., Antonio, Mark R., & Nilsson, Mikael. Structural study of complexes formed by acidic and neutral organophosphorus reagents. United States. doi:10.1039/C6DT04305D.
Braatz, Alexander D., Antonio, Mark R., and Nilsson, Mikael. Fri . "Structural study of complexes formed by acidic and neutral organophosphorus reagents". United States. doi:10.1039/C6DT04305D. https://www.osti.gov/servlets/purl/1341582.
@article{osti_1341582,
title = {Structural study of complexes formed by acidic and neutral organophosphorus reagents},
author = {Braatz, Alexander D. and Antonio, Mark R. and Nilsson, Mikael},
abstractNote = {The coordination of the trivalent 4f ions, Ln = La3+, Dy3+, and Lu3+, with neutral and acidic organophosphorus reagents, both individually and combined, was studied by use of X-ray absorption spectroscopy. These studies provide metrical information about the interatomic interactions between these cations and the ligands tri-n-butyl phosphate (TBP) and di-n-butyl phosphoric acid (HDBP), whose behavior are of practical importance to chemical separation processes that are currently used on an industrial scale. Previous studies have suggested the existence of complexes involving a mixture of ligands, accounting for extraction synergy. Through systematic variation of the aqueous phase acidity and extractant concentration and combination, we have found that complexes with Ln and TBP : HDBP at any mixture and HDBP alone involve direct Ln–O interactions involving 6 oxygen atoms and distant Ln–P interactions involving on average 3–5 phosphorus atoms per Ln ion. It was also found that Ln complexes formed by TBP alone seem to favor eight oxygen coordination, though we were unable to obtain metrical results regarding the distant Ln–P interactions due to the low signal attributed to a lower concentration of Ln ions in the organic phases. Our study does not support the existence of mixed Ln–TBP–HDBP complexes but, rather, indicates that the lanthanides are extracted as either Ln–HDBP complexes or Ln–TBP complexes and that these complexes exist in different ratios depending on the conditions of the extraction system. Furthermore, this fundamental structural information offers insight into the solvent extraction processes that are taking place and are of particular importance to issues arising from the separation and disposal of radioactive materials from used nuclear fuel.},
doi = {10.1039/C6DT04305D},
journal = {Dalton Transactions},
number = 4,
volume = 46,
place = {United States},
year = {Fri Dec 23 00:00:00 EST 2016},
month = {Fri Dec 23 00:00:00 EST 2016}
}

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Works referenced in this record:

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


WinXAS a Program for X-ray Absorption Spectroscopy Data Analysis under MS-Windows
journal, March 1998