ArticleThe journal of physical chemistry. B2023
How Do Liquid-Junction Potentials and Medium Polarity at Electrode Surfaces Affect Electrochemical Analyses for Charge-Transfer Systems?
Article in The journal of physical chemistry. B, 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 6 papers.
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6 citing papers in PubMed.
- Kinetic and Interfacial Aspects of Bi(III) Ion Electroreduction in the Presence of Acetonitrile and 2-Thiouracil.Molecules (Basel, Switzerland) · 2026Article
- Article
- Dipoles affect conformational equilibrium.Journal of photochemistry and photobiology. A, Chemistry · 2025Article
- Twisting, Hydrogen Bonding, Exciplex Formation, and Charge Transfer. What Makes a Bright Fluorophore Not So Bright?The Journal of organic chemistry · 2025Article
- How Permanent Are the Permanent Macrodipoles of Anthranilamide Bioinspired Molecular Electrets?Journal of the American Chemical Society · 2024Article
- Optical Window to Polarity of Electrolyte Solutions.Molecules (Basel, Switzerland) · 2023Article
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Authors and funding
6 authors.
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Abstract
The importance of electrochemical analysis for charge-transfer science cannot be overstated. Interfaces in electrochemical cells present certain challenges in the interpretation and the utility of the analysis. This publication focuses on: (1) the medium polarity that redox species experience at the electrode surfaces that is smaller than the polarity in the bulk media and (2) the liquid-junction potentials from interfacing electrolyte solutions of different organic solvents, namely, dichloromethane, benzonitrile, and acetonitrile. Electron-donor-acceptor pairs of aromatics with similar structures (i.e., 1-naphthylamine and 1-nitronaphthalene, 10-methylphenothiazine and 9-nitroanthracene, and 1-aminopyrene and 1-nitropyrene) serve as redox analytes for this study. Using the difference between the reduction potentials of the oxidized donors and the acceptors eliminates the effects of the liquid junctions on the analysis of charge-transfer thermodynamics. This analysis also offers a means for evaluating the medium polarity that the redox species experience at the surface of the working electrode and the effects of the liquid junctions on the measured reduction potentials. While the liquid-junction potentials between the dichloromethane and acetonitrile solutions amount to about 90 mV, for the benzonitrile-acetonitrile junctions, the potentials are only about 30 mV. The presented methods for analyzing the measured electrochemical characteristics of donors and acceptors illustrate a means for improved evaluation of the thermodynamics of charge-transfer systems.
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