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- Title
Measurements and Utilization of Consistent Gibbs Energies of Transfer of Single Ions: Towards a Unified Redox Potential Scale for All Solvents.
- Authors
Radtke, Valentin; Gebel, Niklas; Priester, Denis; Ermantraut, Andreas; Bäuerle, Monika; Himmel, Daniel; Stroh, Regina; Koslowski, Thorsten; Leito, Ivo; Krossing, Ingo
- Abstract
Utilizing the "ideal" ionic liquid salt bridge to measure Gibbs energies of transfer of silver ions between the solvents water, acetonitrile, propylene carbonate and dimethylformamide results in a consistent data set with a precision of 0.6 kJ mol−1 over 87 measurements in 10 half‐cells. This forms the basis for a coherent experimental thermodynamic framework of ion solvation chemistry. In addition, we define the solvent independent peabsH2O ‐ and the EabsH2O values that account for the electronating potential of any redox system similar to the pHabsH2O value of a medium that accounts for its protonating potential. This EabsH2O scale is thermodynamically well‐defined enabling a straightforward comparison of the redox potentials (reducities) of all media with respect to the aqueous redox potential scale, hence unifying all conventional solvents′ redox potential scales. Thus, using the Gibbs energy of transfer of the silver ion published herein, one can convert and unify all hitherto published redox potentials measured, for example, against ferrocene, to the EabsH2O scale.
- Subjects
GIBBS' free energy; ENERGY transfer; IONS; SILVER ions; OXIDATION-reduction reaction; REDUCTION potential; SOLVENTS; CARBONATE minerals
- Publication
Chemistry - A European Journal, 2022, Vol 28, Issue 40, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202200509