A previously derived method for the determination of Gibbs free energies of transfer of alkali chlorides using cationic glass electrodes is applied to the transfer of HCI. and results for the transfer of HCI from water to a large number of water-organic solvent mixtures are reported. The accuracy of
Gibbs free energies of transfer (ΔG∘tr) for alkali metal ions and tl+
✍ Scribed by G. Gritzner
- Publisher
- Elsevier Science
- Year
- 1977
- Tongue
- English
- Weight
- 830 KB
- Volume
- 24
- Category
- Article
- ISSN
- 0020-1693
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✦ Synopsis
Employing bisbiphenylchromium(I)/bisbiphenyE chromium(O) as a reference redox system the polarographic behaviour of alkali metal ions and Tl' has been studied in butyrolactone, N-methylpyrrolidinone(2), N-methylthiopyrrolidinone(2), ethanol and acetonitrile. Based on the half wave potentials versus the above mentioned reference redox system, Gibbs free energies of transfer have been calculated for these solvents as well as for fourteen other solvents for which half wave potentials have been already published. Acetonitrile was chosen as a reference solvent. The difference in half wave potentials between ferrocene and bisbiphenylchromium(I) is reported for fourteen solvents. The half wave potential of the bisbiphenylchromium(I) reduction has also been measured in acetonitrile versus the AgfO.O1 molar AgClO, electrode in molar tetraethylammonium perchlorate solutions in acetonitrile. Gibbs free energies of transfer based on the bisbiphenylchromium assumption are compared with data obtained from the tetraphenylarsonium tetraphenylborate assumption in those solvents for which such data are available. The bisbiphenylchromium assumption and the effect of solvent parameters on the Gibbs free energy of transfer of alkali metal ions and Tl' are discussed.
📜 SIMILAR VOLUMES
Solvent free energies for electron transfer reactions at the water/Pt interface are calculated using molecular dynamics umbrella sampling for different ion charges and external electric fields. In all cases, the free energy curves as a function of solvent coordinate are in reasonable agreement with