Ideally Polarizable ITIES

According to Eq. (32.10), the distribution potential corresponding to the equilibrium partition of the electrolyte RX is independent of the electrolyte concentration. On the other hand, when more than two ions are involved in the partition equilibrium, there always exists a thermodynamic relationship between the potential difference and the concentrations of ions present. More specifically, let us consider an ITIES with a different electrolyte in each phase. 

Koryta et al. (1977) have shown that the distribution potential for such an ITIES fulfills the inequality cp s+ 9 ix- 9 )r+ provided that RX consists of 

0-X-/0.X- 1- In this case, the potential difference can be controlled by externally 

---

Thermodynamic analysis of the ideally polarizable ITIES in the absence of the ion association yields the electrocapillary equation (for T,p = const) (Kakiuchi and Senda, 1983)... 

Under these circumstances [12, 13], the ITIES behaves as an ideally polarizable interface, i.e. within a certain range of electrical potential values between water and the organic phase, attains the value applied from an external source. 

The general thermodynamic approach yields the - Gibbs-Lippmann equation (- electrocapillary) for the nonpolarizable [v] and ideally polarizable [ix] ITIES. For the interface between the electrolyte solutions of RX in w and SY in o, see also - interface between two immiscible electrolyte solutions, this equation has the form [x]... 

Most of the events in electrochemistry take place at an interface, and that is why interfacial electrochemistry constitutes the major part of electrochemical science. Relevant interfaces here are the metal-liquid electrolyte (LE), metal-solid electrolyte (SE), semiconductor-electrolyte, and the interface between two immiscible electrolyte solutions (ITIES). These interfaces are chargeable, that is, when the external potential is applied, charge separation of positive and negative charges on the two sides of the contact occurs. Such an interface can accumulate energy and be characterized by electric capacitance, within the range of ideal polarizability beyond which Faraday processes turn on. 

---