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Title: Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR

Abstract

Electrophoretic NMR (eNMR) is emerging as a powerful technique for characterizing ion transport in electrolyte systems. We show that the standard approach for analyzing eNMR data is valid only for dilute electrolytes and provide a theoretical framework for interpreting eNMR results for all binary electrolyte systems with univalent salts. We derive relationships between the velocities of the ion species and the solvent in terms of the electrochemical Stefan-Maxwell diffusion coefficients and provide modified expressions for correctly calculating the transference number and conductivity from eNMR data in concentrated electrolytes. Our approach suggests that it is necessary to measure not just the displacement of ion species during the application of current in an eNMR experiment but also the displacement of the uncharged solvent in order to correctly calculate ion mobilities and the transference number.

Authors:
ORCiD logo; ; ORCiD logo
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1492480
Alternate Identifier(s):
OSTI ID: 1604662
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 166 Journal Issue: 2; Journal ID: ISSN 0013-4651
Publisher:
IOP Publishing - The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Timachova, Ksenia, Newman, John, and Balsara, Nitash P. Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR. United States: N. p., 2019. Web. https://doi.org/10.1149/2.0591902jes.
Timachova, Ksenia, Newman, John, & Balsara, Nitash P. Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR. United States. https://doi.org/10.1149/2.0591902jes
Timachova, Ksenia, Newman, John, and Balsara, Nitash P. Mon . "Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR". United States. https://doi.org/10.1149/2.0591902jes.
@article{osti_1492480,
title = {Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR},
author = {Timachova, Ksenia and Newman, John and Balsara, Nitash P.},
abstractNote = {Electrophoretic NMR (eNMR) is emerging as a powerful technique for characterizing ion transport in electrolyte systems. We show that the standard approach for analyzing eNMR data is valid only for dilute electrolytes and provide a theoretical framework for interpreting eNMR results for all binary electrolyte systems with univalent salts. We derive relationships between the velocities of the ion species and the solvent in terms of the electrochemical Stefan-Maxwell diffusion coefficients and provide modified expressions for correctly calculating the transference number and conductivity from eNMR data in concentrated electrolytes. Our approach suggests that it is necessary to measure not just the displacement of ion species during the application of current in an eNMR experiment but also the displacement of the uncharged solvent in order to correctly calculate ion mobilities and the transference number.},
doi = {10.1149/2.0591902jes},
journal = {Journal of the Electrochemical Society},
number = 2,
volume = 166,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1149/2.0591902jes

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Cited by: 1 work
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