Reliability of organic phase reference electrodes in polarization measurements at liquid/liquid interfaces

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00638094" target="_blank" >RIV/61388955:_____/25:00638094 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S1572665725004552?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S1572665725004552?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jelechem.2025.119381" target="_blank" >10.1016/j.jelechem.2025.119381</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reliability of organic phase reference electrodes in polarization measurements at liquid/liquid interfaces

Popis výsledku v původním jazyce

Ion transfer voltammetry and solubility measurements are used to examine the reliability of the organic phase reference electrode commonly used in polarization measurements at the water (w)/organic solvent (o) interface. According to the thermodynamic treatment developed by Hung (1980), the reference potential can be controlled by the equilibrium partition of a highly hydrophobic cation between the organic (o) and the reference aqueous (w′) phase, provided that the difference between the standard ion transfer potentials of the hydrophobic cation and the counter anion present in the phase (w′) is sufficiently large and positive. This assumption is tested for the commonly investigated water/1,2-dichloroethane (1,2-DCE) and water/α,α,α-trifluorotoluene (TFT) two-phase liquid systems, where the reference cation and counter anion are represented by bis(triphenylphosphoranylidene)ammonium (BA+) and chloride, respectively. For this purpose, the standard Gibbs energies of transfer of the BA+ ion from water to TFT and 1,2-DCE were evaluated from the solubility data. It is concluded that only the potential of the organic phase reference electrode for the water/TFT system is controlled by the partition of the BA+ cation at the w′/o interface, while the potential of the organic phase reference electrode for the water/1,2-DCE interface is of a non-thermodynamic origin. Long-term stability of the reference potential is demonstrated, which is observed even in the absence of the BA+ cation in the aqueous phase (w′). The reported observations can be of practical relevance.

Název v anglickém jazyce

Reliability of organic phase reference electrodes in polarization measurements at liquid/liquid interfaces

Popis výsledku anglicky

Ion transfer voltammetry and solubility measurements are used to examine the reliability of the organic phase reference electrode commonly used in polarization measurements at the water (w)/organic solvent (o) interface. According to the thermodynamic treatment developed by Hung (1980), the reference potential can be controlled by the equilibrium partition of a highly hydrophobic cation between the organic (o) and the reference aqueous (w′) phase, provided that the difference between the standard ion transfer potentials of the hydrophobic cation and the counter anion present in the phase (w′) is sufficiently large and positive. This assumption is tested for the commonly investigated water/1,2-dichloroethane (1,2-DCE) and water/α,α,α-trifluorotoluene (TFT) two-phase liquid systems, where the reference cation and counter anion are represented by bis(triphenylphosphoranylidene)ammonium (BA+) and chloride, respectively. For this purpose, the standard Gibbs energies of transfer of the BA+ ion from water to TFT and 1,2-DCE were evaluated from the solubility data. It is concluded that only the potential of the organic phase reference electrode for the water/TFT system is controlled by the partition of the BA+ cation at the w′/o interface, while the potential of the organic phase reference electrode for the water/1,2-DCE interface is of a non-thermodynamic origin. Long-term stability of the reference potential is demonstrated, which is observed even in the absence of the BA+ cation in the aqueous phase (w′). The reported observations can be of practical relevance.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GA22-32631S" target="_blank" >GA22-32631S: Anomální extrakce solí z vody do organického rozpouštědla: Nový mechanismus spontánní emulzifikace a praktická aplikace</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Electroanalytical Chemistry

ISSN

1572-6657

e-ISSN

1873-2569

Svazek periodika

996

Číslo periodika v rámci svazku

NOV 2025

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

5

Strana od-do

119381

Kód UT WoS článku

001547372600001

EID výsledku v databázi Scopus

2-s2.0-105012534094