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Title: Effects of electrolytes on redox potentials through ion pairing

Abstract

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redox potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔGd°, of ion pairing. Values of ΔGd° for pairs with TBA+ give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [1]
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  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Doshisha Univ., Nara (Japan)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1405940
Alternate Identifier(s):
OSTI ID: 1549324
Report Number(s):
BNL-114474-2017-JA
Journal ID: ISSN 1572-6657; R&D Project: CO037; KC0304030
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Electroanalytical Chemistry
Additional Journal Information:
Journal Volume: 804; Journal Issue: C; Journal ID: ISSN 1572-6657
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox potentials; Ion pair; Electrolyte; Voltammetry

Citation Formats

Bird, Matthew J., Iyoda, Tomokazu, Bonura, Nicholas, Bakalis, Jin, Ledbetter, Abram J., and Miller, John R. Effects of electrolytes on redox potentials through ion pairing. United States: N. p., 2017. Web. doi:10.1016/j.jelechem.2017.09.030.
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Bird, Matthew J., Iyoda, Tomokazu, Bonura, Nicholas, Bakalis, Jin, Ledbetter, Abram J., & Miller, John R. Effects of electrolytes on redox potentials through ion pairing. United States. https://doi.org/10.1016/j.jelechem.2017.09.030
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Bird, Matthew J., Iyoda, Tomokazu, Bonura, Nicholas, Bakalis, Jin, Ledbetter, Abram J., and Miller, John R. Thu . "Effects of electrolytes on redox potentials through ion pairing". United States. https://doi.org/10.1016/j.jelechem.2017.09.030. https://www.osti.gov/servlets/purl/1405940.
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@article{osti_1405940,
title = {Effects of electrolytes on redox potentials through ion pairing},
author = {Bird, Matthew J. and Iyoda, Tomokazu and Bonura, Nicholas and Bakalis, Jin and Ledbetter, Abram J. and Miller, John R.},
abstractNote = {Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redox potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔGd°, of ion pairing. Values of ΔGd° for pairs with TBA+ give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.},
doi = {10.1016/j.jelechem.2017.09.030},
journal = {Journal of Electroanalytical Chemistry},
number = C,
volume = 804,
place = {United States},
year = {Thu Sep 21 00:00:00 EDT 2017},
month = {Thu Sep 21 00:00:00 EDT 2017}
}
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    Practical Aspects of Cyclic Voltammetry: How to Estimate Reduction Potentials When Irreversibility Prevails
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    • DOI: 10.1149/2.0241905jes
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