The role of solvation, complementary to electronic effects, in specific adsorption of ions at electrodes
✍ Scribed by B.E. Conway
- Publisher
- Elsevier Science
- Year
- 1997
- Tongue
- English
- Weight
- 634 KB
- Volume
- 94
- Category
- Article
- ISSN
- 0167-2738
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✦ Synopsis
Specific adsorption of non-hydrophobic ions, especially anions, takes place usually with significant electron chargetransfer related to the electrosorption valency. In order for such electronic effects to arise through metal-lone-pair electron interactions, it is necessary for accompanying changes of geometry of the inner-shell solvent coordination of the ions to take place with diminution of their local solvation energy so that lone-pair orbitals, e.g., on anions, can have access to surface orbitals of the metal electrode. Correspondingly, the importance of the ion solvation factor is demonstrated by adsorption at air-water interfaces where the ion-metal electronic interaction is absent, yet substantial ion-specific adsorption effects arise.