Skip to Main content Skip to Navigation
Journal articles

Comparative study of the thermodynamics and kinetics of the ion transfer across the liquid | liquid interface by means of three-phase electrodes

Abstract : A comparative study of the behavior of different sorts of three-phase electrodes applied for assessing the thermodynamics and kinetics of the ion transfer across the liquid |liquid (L|L) interface is presented. Two types of three-phase electrodes are compared, that is, a paraffin-impregnated graphite electrode at the surface of which a macroscopic droplet of an organic solvent is attached and an edge pyrolytic graphite electrode partly covered with a very thin film of the organic solvent. The organic solvent contains either decamethylferrocene or lutetium bis(tetra-tert-butylphthalocyaninato) as a redox probe. The role of the redox probe, the type of the electrode material, the mass transfer regime, and the effect of the uncompensated resistance are discussed. The overall electrochemical process at both three-phase electrodes proceeds as a coupled electron-ion transfer reaction. The ion transfer across the L|L interface, driven by the electrode reaction of the redox compound at the electrode|organic solvent interface, is independent of the type of redox probe. The ion transfer proceeds without involving any chemical coupling between the transferring ion and the redox probe. Both types of three-phase electrodes provide consistent results when applied for measuring the energy of the ion transfer. Under conditions of square-wave voltammetry, the coupled electron-ion transfer at the three-phase electrode is a quasireversible process, exhibiting the property known as "quasireversible maximum". The overall electron-ion transfer process at the three-phase electrode is controlled by the rate of the ion transfer. It is demonstrated for the first time that the three-phase electrode in combination with the quasireversible maximum is a new tool for assessing the kinetics of the ion transfer across the L|L interface. © 2005 American Chemical Society.
Document type :
Journal articles
Complete list of metadatas

https://hal.univ-brest.fr/hal-01763761
Contributor : Nicolas Renard <>
Submitted on : Wednesday, April 11, 2018 - 1:43:15 PM
Last modification on : Monday, August 5, 2019 - 4:14:07 PM

Links full text

Identifiers

Collections

Citation

François Quentel, V. Mirčeski, Maurice l'Her, M. Mladenov, F. Scholz, et al.. Comparative study of the thermodynamics and kinetics of the ion transfer across the liquid | liquid interface by means of three-phase electrodes. Journal of Physical Chemistry B, American Chemical Society, 2005, 109 (27), pp.13228-13236. ⟨10.1021/jp0519969⟩. ⟨hal-01763761⟩

Share

Metrics

Record views

133