skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems

Abstract

The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism and acid dependence of the redox reaction.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1414529
Report Number(s):
PNNL-SA-127756
Journal ID: ISSN 1040-0397; AF5805010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Electroanalysis
Additional Journal Information:
Journal Volume: 29; Journal Issue: 12; Journal ID: ISSN 1040-0397
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Lines, Amanda M., Adami, Susan R., Casella, Amanda J., Sinkov, Sergey I., Lumetta, Gregg J., and Bryan, Samuel A. Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems. United States: N. p., 2017. Web. doi:10.1002/elan.201700465.
Lines, Amanda M., Adami, Susan R., Casella, Amanda J., Sinkov, Sergey I., Lumetta, Gregg J., & Bryan, Samuel A. Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems. United States. doi:10.1002/elan.201700465.
Lines, Amanda M., Adami, Susan R., Casella, Amanda J., Sinkov, Sergey I., Lumetta, Gregg J., and Bryan, Samuel A. Wed . "Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems". United States. doi:10.1002/elan.201700465.
@article{osti_1414529,
title = {Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems},
author = {Lines, Amanda M. and Adami, Susan R. and Casella, Amanda J. and Sinkov, Sergey I. and Lumetta, Gregg J. and Bryan, Samuel A.},
abstractNote = {The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism and acid dependence of the redox reaction.},
doi = {10.1002/elan.201700465},
journal = {Electroanalysis},
issn = {1040-0397},
number = 12,
volume = 29,
place = {United States},
year = {2017},
month = {9}
}

Works referenced in this record:

Electrochemical and spectroscopic studies of Pu(IV) and Pu(III) in nitric acid solutions
journal, May 2012

  • Kim, S. -Y.; Asakura, T.; Morita, Y.
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 295, Issue 2
  • DOI: 10.1007/s10967-012-1858-z

Bestimmung von Stabilitätskonstanten einiger Aktinidenkomplexe
journal, January 1970


Stability constants of nitrate complexes of trivalent plutonium in aqueous and tributyl phosphate solutions
journal, November 1960

  • Shevchenko, V. B.; Timoshev, V. G.; Volkova, A. A.
  • The Soviet Journal of Atomic Energy, Vol. 6, Issue 4
  • DOI: 10.1007/BF01479734

The measurement of the diffusion coefficients of Pu(III) in hydrochloric acid by use of an analytical ultracentrifuge
journal, May 1985


Spectroscopic monitoring of spent nuclear fuel reprocessing streams: an evaluation of spent fuel solutions via Raman, visible, and near-infrared spectroscopy
journal, September 2011

  • Bryan, S. A.; Levitskaia, Tatiana G.; Johnsen, A. M.
  • Radiochimica Acta, Vol. 99, Issue 9
  • DOI: 10.1524/ract.2011.1865

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes
journal, May 2016

  • Lines, Amanda M.; Wang, Zheming; Clark, Sue B.
  • Electroanalysis, Vol. 28, Issue 9
  • DOI: 10.1002/elan.201600034

The absorption spectra of plutonium ions in perchloric acid solutions
journal, March 1961


Analytical electrochemistry: methodology and applications of dynamic techniques
journal, April 1978

  • Heineman, William R.; Kissinger, Peter T.
  • Analytical Chemistry, Vol. 50, Issue 5
  • DOI: 10.1021/ac50028a020

Luminescence-Based Spectroelectrochemical Sensor for [Tc(dmpe) 3 ] 2+/+ (dmpe = 1,2- bis (dimethylphosphino)ethane) within a Charge-Selective Polymer Film
journal, March 2011

  • Chatterjee, Sayandev; Del Negro, Andrew S.; Edwards, Matthew K.
  • Analytical Chemistry, Vol. 83, Issue 5
  • DOI: 10.1021/ac1030368

Multivariate Analysis for Quantification of Plutonium(IV) in Nitric Acid Based on Absorption Spectra
journal, August 2017


Optically Transparent Thin-Film Electrode Chip for Spectroelectrochemical Sensing
journal, July 2017


Cyclic voltammetry of Pu and Np in nitric acid media
journal, November 1971

  • Casadio, Sergio; Orlandini, Franco
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 33, Issue 1
  • DOI: 10.1016/S0022-0728(71)80224-3

Chloride, nitrate and sulphate complexes of europium (III) and americium (III)
journal, June 1964

  • Bansal, B. M. L.; Patil, S. K.; Sharma, H. D.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 6
  • DOI: 10.1016/0022-1902(64)80261-X

Study of the plutonium (IV) electrochemical behavior in nitric acid at a platinum electrode. Application to the cathodic reduction of Pu(IV) in a plate electrolyzer
journal, August 2014


An electrochemical experiment using an optically transparent thin layer electrode
journal, September 1976

  • DeAngelis, Thomas P.; Heineman, William R.
  • Journal of Chemical Education, Vol. 53, Issue 9
  • DOI: 10.1021/ed053p594

Redox and environmentally relevant aspects of actinide(IV) coordination chemistry
journal, May 2014

  • Natrajan, Louise S.; Swinburne, Adam N.; Andrews, Michael B.
  • Coordination Chemistry Reviews, Vol. 266-267
  • DOI: 10.1016/j.ccr.2013.12.021

Electrochemical studies of plutonium ions in perchloric acid solution
journal, March 1961


Standard Electrode Potentials and Temperature Coefficients in Water at 298.15 K
journal, January 1989

  • Bratsch, Steven G.
  • Journal of Physical and Chemical Reference Data, Vol. 18, Issue 1
  • DOI: 10.1063/1.555839

An investigation of the mechanism of the Eu(III)/Eu(II) electrode reaction in the presence of edta
journal, November 1972

  • Kisova, L.; Sluyters-Rehbach, M.; Sluyters, J. H.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 40, Issue 1
  • DOI: 10.1016/S0022-0728(72)80123-2

Mechanism of the Disproportionation of Plutonium (V)
journal, May 1949

  • Connick, Robert E.
  • Journal of the American Chemical Society, Vol. 71, Issue 5
  • DOI: 10.1021/ja01173a002