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

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/C6DT04305D· OSTI ID:1341582
 [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)
+ Show Author Affiliations

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. 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.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
OSTI ID:
1341582
Alternate ID(s):
OSTI ID: 1369054
Journal Information:
Dalton Transactions, Vol. 46, Issue 4; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (4)

Coordination chemistry of lanthanides in a AOT–CMPO solvent extraction system: UV-Vis and XAFS studies journal January 2018
Synergism and Aggregation in Multi-Extractant Solvent Extraction Systems journal June 2019
Synergism and Aggregation in Multi-Extractant Solvent Extraction Systems text January 2019
Synergism and Aggregation in Multi-Extractant Solvent Extraction Systems text January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
EXAFS
HDBP
Lanthanides
Solvent extraction
TBP
XANES