An integrated theoretical-experimental approach to understand facilitated proton transfer-electron transfer coupled reactions at thick-film modified electrodes

Abstract

The main purpose of the current work is to generalize the analytical model for the facilitated proton transfer-electron transfer coupled reactions at thick organic film-modified electrodes, including ion pairing in the organic phase and considering non-ideal electrolyte solutions in both phases. The main equations to calculate half-wave potentials developed in this model allow the simulation of different chemical systems, comprising hydrophilic and hydrophobic neutral weak bases, at different experimental conditions such as pH, organic phase to aqueous phase volume ratio, and concentration ratios between the redox probe and the transferring protonated species. The model was checked against experimental voltammetric responses measured with the transfer of Tylosin A at the water|1,2dichloroethene interface. Consequently, we present here an integrated theoretical

Ametryn detection by proton assisted transfer at a single micro-interface between two immiscible electrolyte solutions

“…Where n was the total number of moles initially present in the system, Vorg and Vaq were the volumes of the organic and aqueous phases, respectively. Previous studies have investigated the effect of the ratio of the volumes of the two phases on the transfer potential and current at either macroscopic ITIES [43,[49][50][51][52][53][54] and thick film modified electrodes [55,56]. By combining equations ( 2), ( 3) and ( 4…”

Facilitated Ion Transfer Reactions Across Liquid|Liquid Interfaces Assisted by a Neutral Weak Acid: A Theoretical Approach

“…A theoretical approach for modelling the facilitated proton transfer or protonatable species transfer across L|L interfaces was developed by several authors [9,14,23–30,15–22] . On the other hand, physical‐chemical properties of the ligand (partition constant, charge, acid‐base activity, etc.)…”

“…A theoretical approach for modelling the facilitated proton transfer or protonatable species transfer across L j L interfaces was developed by several authors. [9,14,[23][24][25][26][27][28][29][30][15][16][17][18][19][20][21][22] On the other hand, physical-chemical properties of the ligand (partition constant, charge, acid-base activity, etc.) as well as its chelating capacity for a given cation (complex formation constants in both phases, and stoichiometry of the formed complexes) determine the nature of the charge transfer process across the L j L interface.…”

Analytical Modelling of Electron‐coupled Ion Transfers with Immobilized vs Soluble Redox Transducer at Thick Film‐modified Electrodes

“…Liquid-liquid electrochemistry offers valuable tools for the detection of ionic or ionisable species and for the study of their uptake-release across lipophilic barriers [1][2][3]. Since the original four-electrode system [4,5], different set-ups have been proposed, including the use of filmmodified electrodes [6][7][8][9][10][11]. These enable the simplification of the set-up to the conventional three-electrode configuration, as well as broad polarization windows and the accurate, stable and reproducible control of the applied potential.…”