Studying the thermodynamics and kinetics of ion tranfers across water-2-nitrophenyloctyl ether interface by means of organic solution modified electrodes

Francois Quentel (1) , Valentin Mirceski (2) , Catherine Elleouet (1) , Maurice L'Her (1)

1 CEMCA - Chimie, Electrochimie Moléculaires et Chimie Analytique
2 Institute of chemistry

Transfer reactions across water-2-nitrophenyloctyl ether (W|NPOE) interface for a series of monovalent inorganic ions and tetraalkylammonium cations are studied by means of square-wave (SWV) and cyclic voltammetry at thin organic-film-modified (TFE) and three-phase electrodes (TPE). Both electrode configurations are assembled using lutetium bis(tetra-tert-butylphthalocyaninato) as a redox probe, whose redox properties enable assessment of both anion and cation transfer reactions in a single voltammetric experiment. It is demonstrated that TFE can be effectively applied to measure the Gibbs energy of ion transfer reactions when the transferring ion is a common ion for both liquid phases, controlling the Galvani potential difference at the W|NPOE interface. A comparative study of the thermodynamics of ion transfer reactions performed with TFE and TPE reveals that both electrode configurations provide a consistent set of data. Kinetic measurements referring to the transfers of ClO4-, and a series of tetraalkylammonium cations have been conducted by combining TFE and SWV according to the method known as “quasireversible maximum” in thin-film voltammetry (Mirčeski, V. J. Phys. Chem. B 2004, 108, 13719).

Domaines: Chimie analytique

Francois Quentel, Valentin Mirceski, Catherine Elleouet, Maurice L'Her. Studying the thermodynamics and kinetics of ion tranfers across water-2-nitrophenyloctyl ether interface by means of organic solution modified electrodes. Journal of Physical Chemistry C, 2008, 112, pp.15553-15561. ⟨10.1021/jp804893g⟩. ⟨hal-00456915⟩