The role of organic solvent radical cations in separations ligand degradation

Mezyk, Stephen P.; Mincher, Bruce J.; Dhiman, Surajdevprakash B.; Layne, Bobby; Wishart, James F.

doi:10.1007/s10967-015-4582-7

Title: The role of organic solvent radical cations in separations ligand degradation

Abstract

The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M^-1 s^-1 in dodecane/0.10 M CH₂Cl₂ solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO•HNO₃ complex formed in the acid contacted solvent.

Authors:

Mezyk, Stephen P. ^[1]; Mincher, Bruce J. ^[2]; Dhiman, Surajdevprakash B. ^[3]; Layne, Bobby ^[3]; Wishart, James F. ^[3]

California State Univ. (CalState), Long Beach, CA (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: Wed Nov 04 00:00:00 EST 2015

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1329809

Report Number(s):: BNL-112756-2016-JA
Journal ID: ISSN 0236-5731; R&D Project: CO031; KC0304030

Grant/Contract Number:: SC00112704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Radioanalytical and Nuclear Chemistry

Additional Journal Information:: Journal Volume: 307; Journal Issue: 3; Journal ID: ISSN 0236-5731

Publisher:: Springer

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dodecane radical cation; ps pulse radiolysis; CMPO; TODGA; Acid contact

Citation Formats


                    Mezyk, Stephen P., Mincher, Bruce J., Dhiman, Surajdevprakash B., Layne, Bobby, and Wishart, James F. The role of organic solvent radical cations in separations ligand degradation.  United States: N. p., 2015. 
Web.  doi:10.1007/s10967-015-4582-7.

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                    Mezyk, Stephen P., Mincher, Bruce J., Dhiman, Surajdevprakash B., Layne, Bobby, & Wishart, James F. The role of organic solvent radical cations in separations ligand degradation.  United States.  https://doi.org/10.1007/s10967-015-4582-7

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                    Mezyk, Stephen P., Mincher, Bruce J., Dhiman, Surajdevprakash B., Layne, Bobby, and Wishart, James F. Wed .  
"The role of organic solvent radical cations in separations ligand degradation".  United States.  https://doi.org/10.1007/s10967-015-4582-7.  https://www.osti.gov/servlets/purl/1329809.

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@article{osti_1329809,

  title        = {The role of organic solvent radical cations in separations ligand degradation},

  author       = {Mezyk, Stephen P. and Mincher, Bruce J. and Dhiman, Surajdevprakash B. and Layne, Bobby and Wishart, James F.},

  abstractNote = {The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M-1 s-1 in dodecane/0.10 M CH2Cl2 solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO•HNO3 complex formed in the acid contacted solvent.},

  doi          = {10.1007/s10967-015-4582-7},

  journal      = {Journal of Radioanalytical and Nuclear Chemistry},

  number       = 3,

  volume       = 307,

  place        = {United States},

  year         = {Wed Nov 04 00:00:00 EST 2015},

  month        = {Wed Nov 04 00:00:00 EST 2015}

}

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Works referenced in this record:

THE TRUEX PROCESS - A PROCESS FOR THE EXTRACTION OF THE TKANSURANIC ELEMENTS EROM NITRIC AC In WASTES UTILIZING MODIFIED PUREX SOLVENT*
journal, February 1985

Philip Horwitz, E.; Kalina, Dale C.; Diamond, Herbert
Solvent Extraction and Ion Exchange, Vol. 3, Issue 1-2
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Hydrolytic and Radiolytic Degradation of Octyl(Phenyl)-N,N-Diiso-Butylcarbamoylmethylphosphine Oxide and Related Compounds
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Chiarizla, Renato; Horwltz, E. Philip
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Hydrolytic and Radiolytic Degradation of Oφd(iB)Cmpo: Continuing Studies
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Degradation of Truex-Dodecane Process Solvent
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Nash, K. L.; Rickert, P. G.; Horwitz, E. P.
Solvent Extraction and Ion Exchange, Vol. 7, Issue 4
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Degradation, Cleanup, and Reusability of Octylphenyl- N, N′ -diisobutylcarbamoylmethyl Phosphine Oxide (CMPO) during Partitioning of Minor Actinides from High Level Waste (HLW) Solutions
journal, January 1998

Mathur, J. N.; Murali, M. S.; Ruikar, P. B.
Separation Science and Technology, Vol. 33, Issue 14
DOI: 10.1080/01496399808545722

The Radiation Chemistry of CMPO: Part 1. Gamma Radiolysis
journal, September 2013

Mincher, Bruce J.; Mezyk, Stephen P.; Elias, Gracy
Solvent Extraction and Ion Exchange, Vol. 31, Issue 7
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Effect of α-Radioiysis on TRUEX-NPH Solvent
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Separation Science and Technology, Vol. 31, Issue 16
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The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis
journal, January 2014

Mincher, Bruce J.; Mezyk, Stephen P.; Elias, Gracy
Solvent Extraction and Ion Exchange, Vol. 32, Issue 2
DOI: 10.1080/07366299.2013.850300

Alpha and gamma radiolysis of nuclear solvent extraction ligands used for An(III) and Ln(III) separations
journal, August 2012

Mezyk, Stephen P.; Mincher, Bruce J.; Ekberg, Christian
Journal of Radioanalytical and Nuclear Chemistry, Vol. 296, Issue 2
DOI: 10.1007/s10967-012-2036-z

Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution
journal, April 1988

Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips
Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2
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Jiang, Pei-Yun; Nagaishi, Ryuji; Yotsuyanagi, Tadasu
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Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis
journal, January 2009

Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P.
Solvent Extraction and Ion Exchange, Vol. 27, Issue 1
DOI: 10.1080/07366290802544767

Studies on hydrolysis and radiolysis of N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide
journal, January 2002

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journal, May 2007

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A Comparison of the γ -Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis
journal, March 2015

Zarzana, Christopher A.; Groenewold, Gary S.; Mincher, Bruce J.
Solvent Extraction and Ion Exchange, Vol. 33, Issue 5
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Determination of CMPO using HPLC–UV
journal, June 2012

Elias, Gracy; Groenewold, Gary S.; Mincher, Bruce J.
Journal of Chromatography A, Vol. 1243
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Characterization of CMPO and its radiolysis products by direct infusion ESI-MS
journal, September 2012

Groenewold, G. S.; Elias, G.; Mincher, B. J.
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journal, November 2004

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Works referencing / citing this record:

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
journal, June 2018

Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
Solvent Extraction and Ion Exchange, Vol. 36, Issue 4
DOI: 10.1080/07366299.2018.1495384

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018

Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
Taylor & Francis
DOI: 10.6084/m9.figshare.6851141

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018

Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
Taylor & Francis
DOI: 10.6084/m9.figshare.6851141.v2

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018

Wilden, Andreas; Mincher, Bruce J.; Mezyk, Stephen P.
Taylor & Francis
DOI: 10.6084/m9.figshare.6851141.v1

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Title: The role of organic solvent radical cations in separations ligand degradation

Abstract

Citation Formats

THE TRUEX PROCESS - A PROCESS FOR THE EXTRACTION OF THE TKANSURANIC ELEMENTS EROM NITRIC AC In WASTES UTILIZING MODIFIED PUREX SOLVENT* journal, February 1985

Hydrolytic and Radiolytic Degradation of Octyl(Phenyl)-N,N-Diiso-Butylcarbamoylmethylphosphine Oxide and Related Compounds journal, January 1986

Hydrolytic and Radiolytic Degradation of Oφd(iB)Cmpo: Continuing Studies journal, October 1988

Degradation of Truex-Dodecane Process Solvent journal, January 1989

Degradation, Cleanup, and Reusability of Octylphenyl- N, N′ -diisobutylcarbamoylmethyl Phosphine Oxide (CMPO) during Partitioning of Minor Actinides from High Level Waste (HLW) Solutions journal, January 1998

The Radiation Chemistry of CMPO: Part 1. Gamma Radiolysis journal, September 2013

Effect of α-Radioiysis on TRUEX-NPH Solvent journal, September 1996

The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis journal, January 2014

Alpha and gamma radiolysis of nuclear solvent extraction ligands used for An(III) and Ln(III) separations journal, August 2012

Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O − in Aqueous Solution journal, April 1988

γ-Radiolysis study of concentrated nitric acid solutions journal, January 1994

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis journal, January 2009

Studies on hydrolysis and radiolysis of N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide journal, January 2002

Influence of diluent on radiolysis of amides in organic solution journal, May 2007

A Comparison of the γ -Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis journal, March 2015

Determination of CMPO using HPLC–UV journal, June 2012

Characterization of CMPO and its radiolysis products by direct infusion ESI-MS journal, September 2012

The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory journal, November 2004

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides journal, June 2018

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides text, January 2018

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides text, January 2018

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides text, January 2018

THE TRUEX PROCESS - A PROCESS FOR THE EXTRACTION OF THE TKANSURANIC ELEMENTS EROM NITRIC AC In WASTES UTILIZING MODIFIED PUREX SOLVENT*
journal, February 1985

Hydrolytic and Radiolytic Degradation of Octyl(Phenyl)-N,N-Diiso-Butylcarbamoylmethylphosphine Oxide and Related Compounds
journal, January 1986

Hydrolytic and Radiolytic Degradation of Oφd(iB)Cmpo: Continuing Studies
journal, October 1988

Degradation of Truex-Dodecane Process Solvent
journal, January 1989

Degradation, Cleanup, and Reusability of Octylphenyl- N, N′ -diisobutylcarbamoylmethyl Phosphine Oxide (CMPO) during Partitioning of Minor Actinides from High Level Waste (HLW) Solutions
journal, January 1998

The Radiation Chemistry of CMPO: Part 1. Gamma Radiolysis
journal, September 2013

Effect of α-Radioiysis on TRUEX-NPH Solvent
journal, September 1996

The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis
journal, January 2014

Alpha and gamma radiolysis of nuclear solvent extraction ligands used for An(III) and Ln(III) separations
journal, August 2012

Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution
journal, April 1988

γ-Radiolysis study of concentrated nitric acid solutions
journal, January 1994

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis
journal, January 2009

Studies on hydrolysis and radiolysis of N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide
journal, January 2002

Influence of diluent on radiolysis of amides in organic solution
journal, May 2007

A Comparison of the γ -Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis
journal, March 2015

Determination of CMPO using HPLC–UV
journal, June 2012

Characterization of CMPO and its radiolysis products by direct infusion ESI-MS
journal, September 2012

The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory
journal, November 2004

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
journal, June 2018

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018

Radiolytic and hydrolytic degradation of the hydrophilic diglycolamides
text, January 2018