DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

Abstract

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in the organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.

Authors:
 [1];  [2];  [2]
  1. Univ. of Iowa, Iowa City, IA (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1389552
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Solvent Extraction and Ion Exchange
Additional Journal Information:
Journal Volume: 35; Journal Issue: 4; Journal ID: ISSN 0736-6299
Publisher:
Taylor and Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Aliquat-336; americium; europium; separations; solvent extraction; thiocyanate

Citation Formats

Knight, Andrew W., Chiarizia, Renato, and Soderholm, L. Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?. United States: N. p., 2017. Web. doi:10.1080/07366299.2017.1326770.
Knight, Andrew W., Chiarizia, Renato, & Soderholm, L. Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?. United States. https://doi.org/10.1080/07366299.2017.1326770
Knight, Andrew W., Chiarizia, Renato, and Soderholm, L. Wed . "Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?". United States. https://doi.org/10.1080/07366299.2017.1326770. https://www.osti.gov/servlets/purl/1389552.
@article{osti_1389552,
title = {Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?},
author = {Knight, Andrew W. and Chiarizia, Renato and Soderholm, L.},
abstractNote = {In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in the organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.},
doi = {10.1080/07366299.2017.1326770},
journal = {Solvent Extraction and Ion Exchange},
number = 4,
volume = 35,
place = {United States},
year = {2017},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The liquid-liquid extraction of certain tripositive transplutonium ions from salted nitrate solutions with a tertiary and quaternary amine
journal, October 1966

  • Horwitz, E. P.; Bloomquist, C. A. A.; Sauro, L. J.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 28, Issue 10
  • DOI: 10.1016/0022-1902(66)80122-7

Extraction of Am(III) and Eu(III) from Nitrate Solution with Purified Cyanex 301
journal, January 1996

  • Zhu, Yongjun; Chen, Jing; Jiao, Rongzhou
  • Solvent Extraction and Ion Exchange, Vol. 14, Issue 1
  • DOI: 10.1080/07366299608918326

Actinide Lanthanide Separation Process—ALSEP
journal, January 2014

  • Gelis, Artem V.; Lumetta, Gregg J.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 4
  • DOI: 10.1021/ie403569e

Recycling metals by controlled transfer of ionic species between complex fluids: en route to “ienaics”
journal, November 2014

  • Zemb, Thomas; Bauer, Caroline; Bauduin, Pierre
  • Colloid and Polymer Science, Vol. 293, Issue 1
  • DOI: 10.1007/s00396-014-3447-x

Liquid-Liquid Equilibrium Analysis in Perspective.Part 1. Slope Analysis of the Extraction of Uranyl Nitrate from Nitric acid by Di-2-Ethylhexylsulfoxide
journal, December 1991

  • Moyer, Bruce A.; McDowell, W. J.; Baes, C. F.
  • Solvent Extraction and Ion Exchange, Vol. 9, Issue 5
  • DOI: 10.1080/07366299108918086

Comparison of the solution chemistry of the actinides and lanthanides
journal, September 1983


Adaptation of the Mohr Volumetric Method to General Determinations of Chlorine.
journal, August 1919

  • Yoder, Lester
  • Journal of Industrial & Engineering Chemistry, Vol. 11, Issue 8
  • DOI: 10.1021/ie50116a013

Crown ether complexes of UO2(NCS)2 and Th(NCS)4: clues to solution behavior or just interesting supramolecular structures?
journal, June 1998


Extraction of some trivalent lanthanides and americium(III) by neutral organophosphorous extractants from thiocyanate solutions
journal, August 1972


Extraction of Zinc(Ii) ion by Didodecylnaphthalenesulfonic acid (Hddns) in Carbon Tetrachloride: the role of Aggregation
journal, February 1991

  • Lumetta, Gregg J.; Moyer*, Bruce A.; Johnson, Paula A.
  • Solvent Extraction and Ion Exchange, Vol. 9, Issue 1
  • DOI: 10.1080/07366299108918048

Trends in separation factors for the lanthanum series as obtained in solvent extraction from an aqueous thiocyanate solution
journal, January 1981


Separation of Americium (III) from Lanthanides by Quaternary Ammonium Salt Extraction
journal, January 1965


Two‐Phase Calorimetry. I. Studies on the Thermodynamics of Lanthanide Extraction by Bis(2‐EthylHexyl) Phosphoric Acid
journal, September 2008


Application of the Baxter Model for Hard Spheres with Surface Adhesion to SANS Data for the U(VI)−HNO 3 , TBP− n -Dodecane System
journal, November 2003

  • Chiarizia, Renato; Nash, Ken L.; Jensen, Mark P.
  • Langmuir, Vol. 19, Issue 23
  • DOI: 10.1021/la030152i

Acidic esters of orthophosphoric acid as selective extractants for metallic cations—tracer studies
journal, October 1958

  • Peppard, D. F.; Mason, G. W.; Driscoll, W. J.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 7, Issue 3
  • DOI: 10.1016/0022-1902(58)80078-0

Extraction of selected metallic cations by di-acidic phosphorus-based extractants, XPO(OH)2, in a ketone diluent
journal, March 1966


Reverse-Micelle Formation in the Partitioning of Trivalent f-Element Cations by Biphasic Systems Containing a Tetraalkyldiglycolamide
journal, April 2007

  • Jensen, Mark P.; Yaita, Tsuyoshi; Chiarizia, Renato
  • Langmuir, Vol. 23, Issue 9
  • DOI: 10.1021/la0631926

Differentiating between Trivalent Lanthanides and Actinides
journal, June 2012

  • Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao
  • Journal of the American Chemical Society, Vol. 134, Issue 25
  • DOI: 10.1021/ja303804r

Liquid anion exchange of thiocyanate-nitrate actinide and lanthanide complexes
journal, October 1973


Activity coefficients of strong electrolytes in multicomponent aqueous solutions
journal, March 1972


Equilibria of extraction of chromium(III) from alkaline solutions with trioctylmethylammonium chloride (Aliquat 336)
journal, July 2005


Separation of actinides from spent nuclear fuel: A review
journal, November 2016


Liquid ion exchange selectivity of dinonylnaphthalenesulfonic acid (HD) with respect to some lanthanide and actinide ions
journal, June 1975


Determination of the aggregation number of dinonyl naphthalene sulfonic acid by metal ion extraction
journal, July 1974

  • Van Dalen, A.; Gerritsma, K. W.; Wijkstra, J.
  • Journal of Colloid and Interface Science, Vol. 48, Issue 1
  • DOI: 10.1016/0021-9797(74)90334-8

Thermodynamics of thiocyanate complexes of trivalent actinides and lanthanides
journal, April 1980


Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes
journal, September 2015

  • Carter, Tyler J.; Wilson, Richard E.
  • Chemistry - A European Journal, Vol. 21, Issue 44
  • DOI: 10.1002/chem.201502770

Liquid-liquid extraction with long-chain quaternary Ammonium Halides
journal, January 1964


Lanthanide(III) complexes with bidentate biheterocyclic ligands
journal, January 1997


Tetraalkylammonium Uranyl Isothiocyanates
journal, October 2012

  • Rowland, Clare E.; Kanatzidis, Mercouri G.; Soderholm, L.
  • Inorganic Chemistry, Vol. 51, Issue 21
  • DOI: 10.1021/ic301741u

Structures and Energetics of Erbium Chloride Complexes in Aqueous Solution
journal, June 2009

  • Soderholm, L.; Skanthakumar, S.; Wilson, Richard E.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 22
  • DOI: 10.1021/jp9012366

Am(III) AND Eu(III) EXTRACTION BY ALIQUAT-336 AND BENZYL SUBSTITUTED QUATERNARY AMMONIUM SALTS FROM NITRATE AND THIOCYANATE SOLUTIONS*
journal, July 1995

  • Chiarizia, R.; Gatrone, R. C.; Horwitz, E. P.
  • Solvent Extraction and Ion Exchange, Vol. 13, Issue 4
  • DOI: 10.1080/07366299508918295

Critical survey of stability constants of complexes of thiocyanate ion (Technical Report)
journal, January 1997

  • Bahta, Abraha; Parker, G. A.; Tuck, D. G.
  • Pure and Applied Chemistry, Vol. 69, Issue 7
  • DOI: 10.1351/pac199769071489

Extraction of Trivalent Lanthanides and Americium by Tri- n -octylphosphine Oxide from Ammonium Thiocyanate Media
journal, March 2011


The Lanthanide Contraction beyond Coordination Chemistry
journal, April 2016

  • Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.
  • Chemistry - A European Journal, Vol. 22, Issue 20
  • DOI: 10.1002/chem.201601032

Structural Studies Coupling X-ray Diffraction and High-Energy X-ray Scattering in the UO 2 2+ –HBr aq System
journal, November 2011

  • Wilson, Richard E.; Skanthakumar, S.; Cahill, C. L.
  • Inorganic Chemistry, Vol. 50, Issue 21
  • DOI: 10.1021/ic201265s

Thiocyanate complexes of some trivalent lanthanide and actinide elements
journal, June 1965