Effect of f-element complexation on the radiolysis of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])

Mezyk, Stephen P.; Baxter, Makayla; Celis-Barros, Cristian; Grimes, Travis S.; Zalupski, Peter R.; Rae, Cathy; Zarzana, Christopher A.; Cook, Andrew R.; Horne, Gregory P.

doi:10.1039/d4dt00424h

Title: Effect of f-element complexation on the radiolysis of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])

Journal Article · 25 February 2024 · Dalton Transactions

DOI: https://doi.org/10.1039/d4dt00424h · OSTI ID:2319168

^[1]; Baxter, Makayla ^[2];

^[3];

^[4];

^[4]; Rae, Cathy ^[4];

^[4];

^[5];

^[4]

California State Univ. (CalState), Long Beach, CA (United States)
Northwestern Univ., Evanston, IL (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

A systematic study of the impact on the chemical reactivity of the oxidising n-dodecane radical cation (RH˙⁺) with f-element complexed 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) has been undertaken utilizing time-resolved electron pulse radiolysis/transient absorption spectroscopy and high-level quantum mechanical calculations. Lanthanide ion complexed species, [Ln((HEH[EHP])₂)₃], exhibited vastly increased reactivity (over 10× faster) in comparison to the non-complexed ligand in n-dodecane solvent, whose rate coefficient was k = (4.66 ± 0.22) × 10⁹ M^-1 s^-1. Similar reactivity enhancement was also observed for the corresponding americium ion complex, k = (5.58 ± 0.30) × 10¹⁰ M^-1 s^-1. The vastly increased reactivity of these f-element complexes was not due to simple increased diffusion-control of these reactions; rather, enhanced hole transfer mechanisms for the complexes were calculated to become energetically more favourable. Interestingly, the observed reactivity trend with lanthanide ion size was not linear; instead, the rate coefficients showed an initial increase (Lu to Yb) followed by a decrease (Tm to Ho), followed by another increase (Dy to La). This behaviour was excellently predicted by the calculated reaction volumes of these complexes. In conclusion, complementary cobalt-60 gamma irradiations for select lanthanide complexes demonstrated that the measured kinetic differences translated to increased ligand degradation at steady-state timescales, affording ~38% increase in ligand loss of a 1:1 [La((HEH[EHP])₂)₃]: HEH[EHP] ratio system.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP)

Grant/Contract Number:: SC0012704; AC07-05ID14517; NE0008406

OSTI ID:: 2319168

Alternate ID(s):: OSTI ID: 2311925

Report Number(s):: BNL--225369-2024-JAAM; {"Journal ID: ISSN 1477-9226",""}

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 16 Vol. 53; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P. Solvent Extraction and Ion Exchange, Vol. 27, Issue 1 https://doi.org/10.1080/07366290802544767	journal	January 2009
Does addition of 1-octanol as a phase modifier provide radical scavenging radioprotection for N , N , N ′, N ′-tetraoctyldiglycolamide (TODGA)? Horne, Gregory P.; Zarzana, Christopher A.; Rae, Cathy Physical Chemistry Chemical Physics, Vol. 22, Issue 43 https://doi.org/10.1039/D0CP04310A	journal	January 2020
Development of experimental irradiation strategies to evaluate the robustness of TODGA and water-soluble BTP extraction systems for advanced nuclear fuel recycling Sánchez-García, I.; Galán, H.; Perlado, J. M. Radiation Physics and Chemistry, Vol. 177 https://doi.org/10.1016/j.radphyschem.2020.109094	journal	December 2020
Impact of lanthanide ion complexation and temperature on the chemical reactivity of N,N,N′,N′-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation Horne, Gregory P.; Celis-Barros, Cristian; Conrad, Jacy K. Physical Chemistry Chemical Physics, Vol. 25, Issue 24 https://doi.org/10.1039/D3CP01119D	journal	January 2023
Optical Absorption Characteristics For 7F0'→5L6' and 7F0'→ 7F6' Transitions of Trivalent Americium Ion in Aqueous Electrolyte Mixtures Zalupski, Peter R.; Grimes, Travis S.; Heathman, Colt R. Applied Spectroscopy, Vol. 71, Issue 12 https://doi.org/10.1177/0003702817721528	journal	July 2017
Dimerization of 2-Ethylhexylphosphonic Acid Mono-2-ethylhexyl Ester (HEH[EHP]) as Determined by NMR Spectrometry Kimberlin, Ashleigh; Nash, Kenneth L. Solvent Extraction and Ion Exchange, Vol. 39, Issue 1 https://doi.org/10.1080/07366299.2020.1816610	journal	September 2020
Actinide Lanthanide Separation Process—ALSEP Gelis, Artem V.; Lumetta, Gregg J. Industrial & Engineering Chemistry Research, Vol. 53, Issue 4 https://doi.org/10.1021/ie403569e	journal	January 2014
Speciation of Select f -Elements with Lipophilic Phosphorus Acids and Diglycol Amides in the ALSEP Backward-Extraction Regime Gullekson, Brian J.; Brown, M. Alex; Paulenova, Alena Industrial & Engineering Chemistry Research, Vol. 56, Issue 42 https://doi.org/10.1021/acs.iecr.7b02379	journal	October 2017
Behaviour of the extractant Me-TODGA upon gamma irradiation: quantification of degradation compounds and individual influences on complexation and extraction Hubscher-Bruder, V.; Mogilireddy, V.; Michel, S. New Journal of Chemistry, Vol. 41, Issue 22 https://doi.org/10.1039/C7NJ02136D	journal	January 2017
Considerations for choice of a kinetic fig. of merit in process radiation chemistry for waste treatment Mincher, Bruce J.; Curry, Randy D. Applied Radiation and Isotopes, Vol. 52, Issue 2 https://doi.org/10.1016/S0969-8043(99)00161-X	journal	February 2000
Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex Picayo, Gabriela A.; Etz, Brian D.; Vyas, Shubham ACS Omega, Vol. 5, Issue 14 https://doi.org/10.1021/acsomega.0c00209	journal	March 2020
Diffusion in Liquid Hydrocarbon Mixtures Geet, Anthony L. Van; Adamson, Arthur W. The Journal of Physical Chemistry, Vol. 68, Issue 2 https://doi.org/10.1021/j100784a004	journal	February 1964
Radiolysis of aqueous solutions of ethylenediaminetetraacetatocerium(III) Hafez, M. B.; Rouhdy, H.; Hafez, N. Journal of Radioanalytical Chemistry, Vol. 43, Issue 1 https://doi.org/10.1007/BF02519447	journal	March 1978
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp063552y	journal	August 2006
Radiolytic Stability of TODGA: Characterization of Degraded Samples under Different Experimental Conditions Galán, Hitos; Núñez, Ana; Espartero, Amparo G. Procedia Chemistry, Vol. 7 https://doi.org/10.1016/j.proche.2012.10.033	journal	January 2012
Covalency in Actinide Compounds Pace, Kristen A.; Klepov, Vladislav V.; Berseneva, Anna A. Chemistry – A European Journal, Vol. 27, Issue 19 https://doi.org/10.1002/chem.202004632	journal	January 2021
Radiolytic behaviour of a TODGA based solvent under alpha irradiation Malmbeck, R.; Banik, N. L. Journal of Radioanalytical and Nuclear Chemistry, Vol. 326, Issue 3 https://doi.org/10.1007/s10967-020-07444-7	journal	October 2020
Radiolysis study of actinide complexing agent by irradiation with helium ion beam Sugo, Yumi; Taguchi, Mitsumasa; Sasaki, Yuji Radiation Physics and Chemistry, Vol. 78, Issue 12 https://doi.org/10.1016/j.radphyschem.2009.06.031	journal	December 2009
Evolution of Acid-Dependent Am ³⁺ and Eu ³⁺ Organic Coordination Environment: Effects on the Extraction Efficiency Hall, Gabriel B.; Holfeltz, Vanessa E.; Campbell, Emily L. Inorganic Chemistry, Vol. 59, Issue 7 https://doi.org/10.1021/acs.inorgchem.9b03612	journal	March 2020
Review Article: The Effects of Radiation Chemistry on Solvent Extraction 3: A Review of Actinide and Lanthanide Extraction Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P. Solvent Extraction and Ion Exchange, Vol. 27, Issue 5-6 https://doi.org/10.1080/07366290903114098	journal	December 2009
The Oxidation of Fe ⁺⁺ to Fe ⁺⁺⁺ by the Irradiation with X‐Rays of Solutions of Ferrous Sulfate in Sulfuric Acid Fricke, Hugo; Hart, Edwin J. The Journal of Chemical Physics, Vol. 3, Issue 1 https://doi.org/10.1063/1.1749558	journal	January 1935
Radiation-induced effects on the extraction properties of hexa- n -octylnitrilo-triacetamide (HONTA) complexes of americium and europium Toigawa, Tomohiro; Peterman, Dean R.; Meeker, David S. Physical Chemistry Chemical Physics, Vol. 23, Issue 2 https://doi.org/10.1039/D0CP05720G	journal	January 2021
Evaluation of the impacts of gamma radiolysis on an ALSEP process solvent Peterman, Dean R.; Zarzana, Christopher A.; Tillotson, Richard D. Journal of Radioanalytical and Nuclear Chemistry, Vol. 316, Issue 2 https://doi.org/10.1007/s10967-018-5737-0	journal	February 2018
Complexation and Separation of Trivalent Actinides and Lanthanides by a Novel DGA Derived from Macrocyclic Crown Ether: Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies Fan, Yu; Li, Youzhen; Shu, Xi ACS Omega, Vol. 6, Issue 3 https://doi.org/10.1021/acsomega.0c05317	journal	January 2021
Chemistry with ADF te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J. Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967 https://doi.org/10.1002/jcc.1056	journal	January 2001
Oxidation state and covalency in f-element metallocenes (M = Ce, Th, Pu): a combined CASSCF and topological study Kerridge, Andrew Dalton Transactions, Vol. 42, Issue 46 https://doi.org/10.1039/c3dt52279b	journal	January 2013
The Radiation Chemistry of CMPO: Part 1. Gamma Radiolysis Mincher, Bruce J.; Mezyk, Stephen P.; Elias, Gracy Solvent Extraction and Ion Exchange, Vol. 31, Issue 7 https://doi.org/10.1080/07366299.2013.815491	journal	September 2013
The Chemistry of Separations Ligand Degradation by Organic Radical Cations Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J. Procedia Chemistry, Vol. 21 https://doi.org/10.1016/j.proche.2016.10.009	journal	January 2016
Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide Drader, J.; Saint-Louis, G.; Muller, J. M. Solvent Extraction and Ion Exchange, Vol. 35, Issue 7 https://doi.org/10.1080/07366299.2017.1379713	journal	September 2017
A Comparison of the γ -Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J. Solvent Extraction and Ion Exchange, Vol. 33, Issue 5 https://doi.org/10.1080/07366299.2015.1012885	journal	March 2015
The reaction of superoxide radical with iron complexes of EDTA studied by pulse radiolysis Ilan, Y. A.; Czapski, G. Biochimica et Biophysica Acta (BBA) - General Subjects, Vol. 498, Issue 2 https://doi.org/10.1016/0304-4165(77)90277-X	journal	July 1977
A Study of the γ-Radiolysis of N,N -Didodecyl- N′,N′ -Dioctyldiglycolamide Using UHPLC-ESI-MS Analysis Roscioli-Johnson, Kristyn M.; Zarzana, Christopher A.; Groenewold, Gary S. Solvent Extraction and Ion Exchange, Vol. 34, Issue 5 https://doi.org/10.1080/07366299.2016.1212540	journal	June 2016
A Pulse Radiolysis Investigation of the Reactions of Tributyl Phosphate with the Radical Products of Aqueous Nitric Acid Irradiation Mincher, Bruce J.; Mezyk, Stephen P.; Martin, Leigh R. The Journal of Physical Chemistry A, Vol. 112, Issue 28 https://doi.org/10.1021/jp802169v	journal	July 2008
The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis Mincher, Bruce J.; Mezyk, Stephen P.; Elias, Gracy Solvent Extraction and Ion Exchange, Vol. 32, Issue 2 https://doi.org/10.1080/07366299.2013.850300	journal	January 2014
Optical Spectroscopy Study of Organic-Phase Lanthanide Complexes in the TALSPEAK Separations Process Grimes, Travis S.; Tian, Guoxin; Rao, Linfeng Inorganic Chemistry, Vol. 51, Issue 11 https://doi.org/10.1021/ic300503p	journal	May 2012
The role of organic solvent radical cations in separations ligand degradation Mezyk, Stephen P.; Mincher, Bruce J.; Dhiman, Surajdevprakash B. Journal of Radioanalytical and Nuclear Chemistry, Vol. 307, Issue 3 https://doi.org/10.1007/s10967-015-4582-7	journal	November 2015
Investigation of the Impacts of Gamma Radiolysis on an Advanced TALSPEAK Separation Zarzana, Christopher A.; Peterman, Dean R.; Groenewold, Gary S. Separation Science and Technology, Vol. 50, Issue 18 https://doi.org/10.1080/01496395.2015.1085419	journal	December 2015
Curium( iii ) radiation-induced reaction kinetics in aqueous media Horne, Gregory P.; Grimes, Travis S.; Zalupski, Peter R. Dalton Transactions, Vol. 50, Issue 31 https://doi.org/10.1039/D1DT01268A	journal	January 2021
Determination of CMPO using HPLC–UV Elias, Gracy; Groenewold, Gary S.; Mincher, Bruce J. Journal of Chromatography A, Vol. 1243 https://doi.org/10.1016/j.chroma.2012.04.047	journal	June 2012
α-Radiation effect on solvent extraction of minor actinide Sugo, Yumi; Sasaki, Yuji; Taguchi, Mitsumasa Journal of Radioanalytical and Nuclear Chemistry, Vol. 303, Issue 2 https://doi.org/10.1007/s10967-014-3494-2	journal	September 2014
Stability studies of GANEX system under different irradiation conditions Sánchez-García, Iván; Galán, Hitos; Perlado, Jose Manuel EPJ Nuclear Sciences & Technologies, Vol. 5 https://doi.org/10.1051/epjn/2019049	journal	January 2019
Separation of actinides from spent nuclear fuel: A review Veliscek-Carolan, Jessica Journal of Hazardous Materials, Vol. 318 https://doi.org/10.1016/j.jhazmat.2016.07.027	journal	November 2016
Dynamic and Solvation Behaviors of ALSEP Organic Ligands Ta, An T.; Jensen, Mark P.; Vyas, Shubham The Journal of Physical Chemistry B, Vol. 123, Issue 40 https://doi.org/10.1021/acs.jpcb.9b06224	journal	August 2019
Atoms in Molecules Bader, Richard F. W. https://doi.org/10.1093/oso/9780198551683.001.0001	book	December 1990
Effect of metal complexation on diglycolamide radiolysis: a comparison between ex situ gamma and in situ alpha irradiation Kimberlin, Ashleigh; Saint-Louis, Georges; Guillaumont, Dominique Physical Chemistry Chemical Physics, Vol. 24, Issue 16 https://doi.org/10.1039/D1CP05731F	journal	January 2022
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning Kaltsoyannis, Nikolas Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3006025	journal	June 2012
A review of the alpha radiolysis of extractants for actinide lanthanide separation in spent nuclear fuel reprocessing Wang, Ying; Wan, Yaoshuang; Cai, Yimin Radiochimica Acta, Vol. 109, Issue 8 https://doi.org/10.1515/ract-2021-1009	journal	July 2021
Covalency in f-element bonds Choppin, Gregory R. Journal of Alloys and Compounds, Vol. 344, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)00305-5	journal	October 2002
Re-evaluation of the thiocyanate dosimeter for pulse radiolysis Buxton, George V.; Stuart, Craig R. Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 2 https://doi.org/10.1039/ft9959100279	journal	January 1995
The radiation chemistry of aqueous solutions of ferric ethylenediamine tetraacetate Bhattacharyya, S. N.; Kundu, K. P. International Journal for Radiation Physics and Chemistry, Vol. 3, Issue 1 https://doi.org/10.1016/0020-7055(71)90003-9	journal	June 1971
Gamma-radiolysis of ferric ethylene diamine tetra-acetate in neutral aqueous solution Kundu, K. P.; Matsuura, N. International Journal for Radiation Physics and Chemistry, Vol. 7, Issue 4 https://doi.org/10.1016/0020-7055(75)90021-2	journal	August 1975
Review: The Effects of Radiation Chemistry on Solvent Extraction 4: Separation of the Trivalent Actinides and Considerations for Radiation-Resistant Solvent Systems Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P. Solvent Extraction and Ion Exchange, Vol. 28, Issue 4 https://doi.org/10.1080/07366299.2010.485548	journal	June 2010
³¹ P NMR study of the activated radioprotection mechanism of octylphenyl- N , N -diisobutylcarbamoylmethyl phosphine oxide (CMPO) and analogues Horne, Gregory P.; Kiddle, James J.; Zarzana, Christopher A. Dalton Transactions, Vol. 48, Issue 30 https://doi.org/10.1039/C9DT01950B	journal	January 2019
Radiation chemical effects on radiochemistry: A review of examples important to nuclear power Mincher, Bruce J.; Mezyk, Stephen P. Radiochimica Acta, Vol. 97, Issue 9 https://doi.org/10.1524/ract.2009.1646	journal	January 2009
Effect of chemical environment on the radiation chemistry of N , N -di-(2-ethylhexyl)butyramide (DEHBA) and plutonium retention Horne, Gregory P.; Zarzana, Christopher A.; Grimes, Travis S. Dalton Transactions, Vol. 48, Issue 38 https://doi.org/10.1039/C9DT02383F	journal	January 2019
Influence of uranyl complexation on the reaction kinetics of the dodecane radical cation with used nuclear fuel extraction ligands (TBP, DEHBA, and DEHiBA) Celis Barros, Cristian; Pilgrim, Corey D.; Cook, Andrew R. Physical Chemistry Chemical Physics, Vol. 23, Issue 43 https://doi.org/10.1039/D1CP03797H	journal	January 2021
The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory Wishart, James F.; Cook, Andrew R.; Miller, John R. Review of Scientific Instruments, Vol. 75, Issue 11 https://doi.org/10.1063/1.1807004	journal	November 2004
Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling Galán, Hitos; Zarzana, Christopher A.; Wilden, Andreas Dalton Transactions, Vol. 44, Issue 41 https://doi.org/10.1039/C5DT02484F	journal	January 2015
Radiolysis of NTA complexes with U(VI), Fe(III) and Ni(II) Khater, M. M.; Kenawi, I. M.; Atwa, A. M. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 111, Issue 1 https://doi.org/10.1007/BF02060517	journal	April 1987
THE DIFFUSION COEFFlCIENT OF HEHEHP IN HEPTANE MEASURED BY THE MODIFIED STOKES CELL TECHNIQUE AT TEMPERATURES BETWEEN 25 AND 55^°C. Dreisinger, D. B.; Cooper, W. Charles Solvent Extraction and Ion Exchange, Vol. 8, Issue 6 https://doi.org/10.1080/07366299008918037	journal	June 1990
Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 111, Issue 2 https://doi.org/10.1021/jp065403l	journal	January 2007
On the gamma-radiolysis of aqueous solutions of cerium(III) - ethylmediamine tetra-acetate Sharma, B. K.; Gupta, R. Radiation Effects, Vol. 57, Issue 5 https://doi.org/10.1080/01422448008228594	journal	January 1981
Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 2. A Review of Fission‐Product Extraction Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P. Solvent Extraction and Ion Exchange, Vol. 27, Issue 3 https://doi.org/10.1080/07366290902821263	journal	May 2009

Similar Records

Combining CMPO and HEH[EHP] for Separating Trivalent Lanthanides from the Transuranic Elements

Journal Article · 2013 · Solvent Extraction and Ion Exchange, 31(6):567-577 · OSTI ID:1092636

Braley, Jenifer C.; Lumetta, Gregg J.; Carter, Jennifer C.

An Advanced TALSPEAK Concept Using 2-Ethylhexylphosphonic Acid Mono-2-Ethylhexyl Ester as the Extractant

Journal Article · 2014 · Solvent Extraction and Ion Exchange, 33(3):211-223 · OSTI ID:1188888

Lumetta, Gregg J.; Casella, Amanda J.; Rapko, Brian M.; +5 more

Impact of f-element complexation on the radiolytic robustness of separations ligands

Conference · 2022 · OSTI ID:1968317

Horne, Gregory P

Title: Effect of f-element complexation on the radiolysis of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])

Citation Formats

References (63)

Similar Records

Related Subjects