Effects of electrolytes on redox potentials through ion pairing

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas; Bakalis, Jin; Ledbetter, Abram J.; Miller, John R.

doi:10.1016/j.jelechem.2017.09.030

Title: Effects of electrolytes on redox potentials through ion pairing

Journal Article · Thu Sep 21 00:00:00 EDT 2017 · Journal of Electroanalytical Chemistry

DOI:https://doi.org/10.1016/j.jelechem.2017.09.030· OSTI ID:1405940

Bird, Matthew J. ^[1]; Iyoda, Tomokazu ^[2]; Bonura, Nicholas ^[1]; Bakalis, Jin ^[1]; Ledbetter, Abram J. ^[1];

^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Doshisha Univ., Nara (Japan)

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, ΔG_d°, of ion pairing. Values of ΔG_d° 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.

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

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1405940

Alternate ID(s):: OSTI ID: 1549324

Report Number(s):: BNL-114474-2017-JA; R&D Project: CO037; KC0304030

Journal Information:: Journal of Electroanalytical Chemistry, Vol. 804, Issue C; ISSN 1572-6657

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Redox potentials
Ion pair
Electrolyte
Voltammetry

Title: Effects of electrolytes on redox potentials through ion pairing

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