Interface ITIES

By positioning the tip close to the surface, SECM can be used to measure the flux of ions through the pores of a membrane (e.g., skin) driven by an electric current iontophoresis) (33). Similarly the rate of electron and ion transfer across the liquid/liquid interface (ITIES) can be studied (34). 

The transfer of ions across immiscible electrolyte interfaces (ITIES) can be described by a similar Butler-Volmer formalism and involves resolvation of the transferred ions. The flux of ions can be measured by the electronic current in the external circuit generated at symmetrical reference electrodes reversible to one of the ions. 

An interface between two immiscible electrolyte solutions (ITIES) is formed between two liqnid solvents of a low mutual miscibility (typically, <1% by weight), each containing an electrolyte. One of these solvents is usually water and the other one is a polar organic solvent of a moderate or high relative dielectric constant (permittivity). The latter requirement is a condition for at least partial dissociation of dissolved electrolyte(s) into ions, which thus can ensure the electric conductivity of the liquid phase. A list of the solvents commonly used in electrochemical measurements at ITIES is given in Table 32.1. 

ITIES interface between two immiscible electrolyte solutions... 

Liquid surfaces and liquid-liquid interfaces are very common and have tremendous significance in the real world. Especially important are the interfaces between two immiscible liquid electrolyte solutions (acronym ITIES), which occur in tissues and cells of all living organisms. The usual presence of aqueous electrolyte solution as one phase of ITIES is the main reason for the electrochemical nature of such interfaces. 

The specific adsorption, which in the case of ITIES is usually the adsorption of ionic pairs [8], contributes to the Galvani potential, as well as changes the zero charge of this interface. 

The electrochemisty of ITIES is developing mainly on the basis of the studies of the water-nitrobenzene and water-1,2-dichloroethane interfaces. The polarizability ranges of these interfaces in the presence of typical electrolytes (Scheme 13) are about 0.30 V. Extension of these ranges has been achieved using other organic ions or/and solvents [2,8]. For example, TBA ions may be substituted by tetraphenylarsonium crystal violet cations and TPhB ions by dicarbollyl cobaltate (III) anions [1,2]. 

Charge transfer reactions at ITIES include both ET reactions and ion transfer (IT) reactions. One question that may be addressed by nonlinear optics is the problem of the surface excess concentration during the IT reaction. Preliminary experiments have been reported for the IT reaction of sodium assisted by the crown ether ligand 4-nitro-benzo-15-crown-5 [104]. In the absence of sodium, the adsorption from the organic phase and the reorientation of the neutral crown ether at the interface has been observed. In the presence of the sodium ion, the problem is complicated by the complex formation between the crown ether and sodium. The SH response observed as a function of the applied potential clearly exhibited features related to the different steps in the mechanisms of the assisted ion transfer reaction although a clear relationship is difficult to establish as the ion transfer itself may be convoluted with monolayer rearrangements like reorientation. 

Similarly to charge-transfer processes at solid-electrolyte interfaces, the ET rate for heterogeneous reactions at ITIES is determined by the flux of reactants to the interface as well... 

Despite the fact that the electrodeposition of copper and silver at the water-DCE and the water-dichloromethane interfaces has been generally regarded as the first experimental evidence for heterogeneous ET at externally biased ITIES [171], a very limited amount of work has dealt with this type of process. This reaction has also theoretical interest because the molecular liquid-liquid interface can be seen as an ideal substrate for electrochemical nucleation studies due to the weak interactions between the interface and the newly formed phase and the lack of preferential nucleation sites always present at metallic electrodes. 

The final internal boundary condition applies to the interface between phase 1 and phase 2, and relates the flux of species Red] and Red2, at the ITIES, to the rate of the second-order redox reaction occurring at the interface. 

Since the first use of SECM to study ET kinetics at a liquid-liquid interface in 1995 [47], the methodology has been proven a powerful approach for investigating the dependence of ET rate constants on the Galvani potential drop across an ITIES. 

The ITIES with an adsorbed monolayer of surfactant has been studied as a model system of the interface between microphases in a bicontinuous microemulsion [39]. This latter system has important applications in electrochemical synthesis and catalysis [88-92]. Quantitative measurements of the kinetics of electrochemical processes in microemulsions are difficult to perform directly, due to uncertainties in the area over which the organic and aqueous reactants contact. The SECM feedback mode allowed the rate of catalytic reduction of tra 5-l,2-dibromocyclohexane in benzonitrile by the Co(I) form of vitamin B12, generated electrochemically in an aqueous phase to be measured as a function of interfacial potential drop and adsorbed surfactants [39]. It was found that the reaction at the ITIES could not be interpreted as a simple second-order process. In the absence of surfactant at the ITIES the overall rate of the interfacial reaction was virtually independent of the potential drop across the interface and a similar rate constant was obtained when a cationic surfactant (didodecyldimethylammonium bromide) was adsorbed at the ITIES. In contrast a threefold decrease in the rate constant was observed when an anionic surfactant (dihexadecyl phosphate) was used. 

FIG. 26 Typical DPSC data for the oxidation of DMFc to DMFc+ (forward step of 0.371 s duration, upper solid line) and the collection of DMFc" by reduction to DMFc (reverse step, lower solid line) at a tip in a DCE phase, positioned at a distance of 4.4 pm from the DCE-aqueous interface. The upper dashed line shows the theoretical characteristics for hindered diffusion of DMFc to the tip. The lower dashed line is the theoretical response when there is no DMFc+ transfer across the ITIES. (Reprinted from Ref. 86. Copyright Elsevier Science.)... 

In this chapter, we describe some of the more widely used and successful kinetic techniques involving controlled hydrodynamics. We briefly discuss the nature of mass transport associated with each method, and assess the attributes and drawbacks. While the application of hydrodynamic methods to liquid liquid interfaces has largely involved the study of spontaneous processes, several of these methods can be used to investigate electrochemical processes at polarized ITIES we consider these applications when appropriate. We aim to provide an historical overview of the field, but since some of the older techniques have been reviewed extensively [2,3,13], we emphasize the most recent developments and applications. 

The concentration of the transferred ion in organic solution inside the pore can become much higher than its concentration in the bulk aqueous phase [15]. (This is likely to happen if r <5c d.) In this case, the transferred ion may react with an oppositely charged ion from the supporting electrolyte to form a precipitate that can plug the microhole. This may be one of the reasons why steady-state measurements at the microhole-supported ITIES are typically not very accurate and reproducible [16]. Another problem with microhole voltammetry is that the exact location of the interface within the hole is unknown. The uncertainty of and 4, values affects the reliability of the evaluation of the formal transfer potential from Eq. (5). The latter value is essential for the quantitative analysis of IT kinetics [17]. Because of the above problems no quantitative kinetic measurements employing microhole ITIES have been reported to date and the theory for kinetically controlled CT reactions has yet to be developed. 

The use of micropipette electrodes for quantitative voltammetric measurements of ion transfer (IT) and electron transfer (ET) reactions at the ITIES requires knowledge of geometry of the liquid interface. For the micrometer-sized micropipettes, both the orifice radius and the thickness of the pipette wall can be measured microscopically. A typical error of the microscopic determination of a radius was estimated to be 0.5/am for a micropipette and 1 /am for a microhole [24]. 

Unlike solid electrodes, the shape of the ITIES can be varied by application of an external pressure to the pipette. The shape of the meniscus formed at the pipette tip was studied in situ by video microscopy under controlled pressure [19]. When a negative pressure was applied, the ITIES shape was concave. As expected from the theory [25a], the diffusion current to a recessed ITIES was lower than in absence of negative external pressure. When a positive pressure was applied to the pipette, the solution meniscus became convex, and the diffusion current increased. The diffusion-limiting current increased with increasing height of the spherical segment (up to the complete sphere), as the theory predicts [25b]. Importantly, with no external pressure applied to the pipette, the micro-ITIES was found to be essentially flat. This observation was corroborated by numerous experiments performed with different concentrations of dissolved species and different pipette radii [19]. The measured diffusion current to such an interface agrees quantitatively with Eq. (6) if the outer pipette wall is silanized (see next section). The effective radius of a pipette can be calculated from Eq. (6) and compared to the value found microscopically [19]. 

Quinn et al. studied ET at micro-ITIES supported by micropipettes or microholes [16]. The studied systems involved ferri/ferrocyanide redox couple in aqueous phase and ferrocene, dimethylferrocene, or TCNQ in either DCE or o-nitrophenyl octyl ether. Sigmoidal, steady-state voltammograms were obtained for ET at the water-DCE interface supported at a micropipette. The semilogarithmic plot of E versus log[(/(j — /)//] was... 

The voltammograms at the microhole-supported ITIES were analyzed using the Tomes criterion [34], which predicts ii3/4 — iii/4l = 56.4/n mV (where n is the number of electrons transferred and E- i and 1/4 refer to the three-quarter and one-quarter potentials, respectively) for a reversible ET reaction. An attempt was made to use the deviations from the reversible behavior to estimate kinetic parameters using the method previously developed for UMEs [21,27]. However, the shape of measured voltammograms was imperfect, and the slope of the semilogarithmic plot observed was much lower than expected from the theory. It was concluded that voltammetry at micro-ITIES is not suitable for ET kinetic measurements because of insufficient accuracy and repeatability [16]. Those experiments may have been affected by reactions involving the supporting electrolytes, ion transfers, and interfacial precipitation. It is also possible that the data was at variance with the Butler-Volmer model because the overall reaction rate was only weakly potential-dependent [35] and/or limited by the precursor complex formation at the interface [33b]. 

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