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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
Resource Relation:
Journal Name: Electroanalysis; Journal Volume: 29; Journal Issue: 12
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},
number = 12,
volume = 29,
place = {United States},
year = {Wed Sep 20 00:00:00 EDT 2017},
month = {Wed Sep 20 00:00:00 EDT 2017}
}