Electrochemistry at the interface between two immiscible electrolyte solutions

Senda, Mitsugi; Kakiuchi, Takashi; Osaka, Toshiyuki

doi:10.1016/0013-4686(91)85246-4

Cited by 236 publications

(154 citation statements)

References 109 publications

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“…( 1 1 (19) However, it would appear71 that the faradaic time constant at a liquid-liquid interface is often greater than that for diffusion, and VanderNoot concluded that any ac impedance, ac polarographic, or for that matter any transient technique is not really suitable for the determination of kinetic parameters unless a linear regression method is used to entangle the kinetics from the diffusion process.…”

Section: Rtmentioning

confidence: 99%

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Charge Transfer across Liquid—Liquid Interfaces

Girault¹

1993

Modern Aspects of Electrochemistry

108

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Section: Rtmentioning

confidence: 99%

“…The elementary thermodynamics of the polarized liquid-liquid interface have been largely covered in previous reviews [12][13][14][15][16][17][18][19] and will therefore not be repeated.…”

mentioning

confidence: 99%

Charge Transfer across Liquid—Liquid Interfaces

Girault¹

1993

Modern Aspects of Electrochemistry

108

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“…where LEref is defined by the combination of RE1 and RE2.1,[6][7][8] In the following, we assume that only a single ion (MZ) can transfer across the interface in the ideal-polarized…”

Section: Theoreticalmentioning

confidence: 99%

“…The left-hand half-cell, RE1 I Bs+, As-, MZ(0) I, represents a potentiometric ISE which is immersed in an external (or test) solution containing an analyte ion MZ, I MZ, B2+, A2 (W) I, with a reference electrode (RE2). The interface, indicated by an asterisk, is the polarizable 0/W interface and the potential difference across the 0/W interface (z4) is related to the potential difference between the terminals of RE1 and RE2 (E) by E =40 4 +DEref,where LEref is defined by the combination of RE1 and RE2.1,[6][7][8] In the following, we assume that only a single ion (MZ) can transfer across the interface in the ideal-polarized …”

mentioning

confidence: 99%

Theory of the Transient Potential Response of Ion-Selective Electrodes Based on the Polarizable Oil/ Water Interface

1996

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The theory of the transient potential response of potentiometric ion-selective electrodes (J. Electroanal. Chem. Interfacial Electrochem., 378, 215 (1994)) is further elucidated. General solutions of the transient potential vs. time curves for a stepwise change in the activity (concentration) of a potential-determining ion in an external solution were numerically obtained for different cases concerning their ion-transfer kinetics. Also, the response time, defined as the time which is taken by the potential of an ion-selective electrode to change from its initial value to within a given limit of the final value, was numerically obtained, and is discussed in terms of the ion concentrations, the kinetic parameters of the ion-transfer reaction, and the electrical double layer capacity of the ion-selective electrode interface. Furthermore, the theory is extended so as to include the transient potential response of neutral-carrier-based ion-selective electrodes. The theory predicts the effect of the concentration of a neutral-carrier, which depends on the reaction mechanism of the carrierassisted ion transfer across the interface. In a previous papers, a theory of the transient potential response of ion-selective electrodes for a stepwise change in the activity (or concentration) of potential-determining ions in an external solution was presented. This theory is based on the phase-boundary potential model of the mechanism of the potential response.2-5 Recent electrochemical studies concerning ion-transfer processes across a liquid/liquid interface have enabled a more exact model of the phase-boundary potential mechanism to be presentedl,6-8, and, hence, to study the problem in more detail. Thus, a solution of the theoretical equation was derived for a specified case when the transfer coefficient of the ion transfer kinetics is equal to 0.5 and the transient potential vs. time (E(t)-t) curves were discussed in terms of the kinetic parameter (rate constant) of the ion-transfer reaction at the interface and the differential capacity of the interface as well as the potential-determining ion concentrations. In this paper, a discussion of the general solutions of the theoretical equation is given as well as that for cases different in their ion-transfer kinetics. Furthermore, the response time, which is defined in this study as the time taken by the potential to attain, for example, 95% of the entire change from its initial value to the final equilibrium value discussed (as well as its numerical solution) as a function of such parameters as the ratio of initial to final concentration of the potential-determining ion, the kinetic parameters of the ion-transfer reaction, and the electric double-layer capacity of the ion-selective electrode interface. Also, the theory is extended so as to include the transient potential response of neutral-carrier-based ion-selective electrodes. TheoreticalThe experimental setup of a potentiometric MZ ionselective electrode based on the polarizable interface between two immiscible electrolyte...

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“…From pulsed or cyclic measurements on ion-selective PVC membranes, the current signals were claimed to be proportional to the logarithm of ion activity or concentration [8,9,[20][21][22][23][24]. In contrast, from studies on ITIES using organic phases containing ionophores, the voltammetric or amperometric responses were apparently found to depend linearly on the ion concentration [26][27][28]30]. Similarly, membranes without or with only a very low PVC content also showed a linear dependence of the signal on the sample ion activity [16,18,19].…”

Section: Introductionmentioning

confidence: 99%

Current response of ion-selective solvent polymeric membranes at controlled potential

Sutter

Morf

Rooij

et al. 2004

Journal of Electroanalytical Chemistry

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From electrochemical measurements at the interface of two immiscible electrolytes, the current at controlled potential is usually a linear function of the ion concentration in the aqueous phase. Surprisingly, a linear relationship between the current and the logarithm of the sample ion activity is found for corresponding measurements on ion-selective electrode membranes. Here, a theoretical explanation for the apparent contradiction between the behavior of the two kinds of system is given. Experimental results obtained with conventional ion-selective PVC membranes as well as with membranes based on PVC free membrane matrices are presented.

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Electrochemistry at the interface between two immiscible electrolyte solutions

Cited by 236 publications

References 109 publications

Charge Transfer across Liquid—Liquid Interfaces

Charge Transfer across Liquid—Liquid Interfaces

Theory of the Transient Potential Response of Ion-Selective Electrodes Based on the Polarizable Oil/ Water Interface

Current response of ion-selective solvent polymeric membranes at controlled potential

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