Double potential distribution

Figure 23. Electric potential distribution in electric double layer. HL, Helmholtz layer DL, diffuse layer.

When an electrode is in contact with an electrolyte, the interphase as a whole is electroneutral. However, electric double layers (EDLs) with a characteristic potential distribution are formed in the interphase because of a nonuniform distribution of the charged particles. 

This result was taken as an experimental eonfirmation of the model developed by Sehmiekler [7]. However, it appeared somehow eontradictory with other results obtained with SECM. It was also suggested that eoneentration polarization phenomena occurring at the aqueous side are negligible as the whole potential drop is presumably developed in the benzene phase. This assumption can be qualitatively verified by evaluating a simplified expression for the potential distribution based on a back-to-back diffuse double layer [40,113],... 

Fig. 4.1 Structure of the electric double layer and electric potential distribution at (A) a metal-electrolyte solution interface, (B) a semiconductor-electrolyte solution interface and (C) an interface of two immiscible electrolyte solutions (ITIES) in the absence of specific adsorption. The region between the electrode and the outer Helmholtz plane (OHP, at the distance jc2 from the electrode) contains a layer of oriented solvent molecules while in the Verwey and Niessen model of ITIES (C) this layer is absent...

To minimize absorption from the solution, optical thin layer cells have been designed. The working electrode has the shape of a disc, and is mounted closely behind an IR-transparent window. For experiments in aqueous solutions the intervening layer is about 0.2 to 2 ftm thick. Since the solution layer in front of the working electrode is thin, its resistance is high this increases the time required for double-layer charging - time constants of the order of a few milliseconds or longer are common - and may create problems with a nonuniform potential distribution. 

One additional word of caution has to be added in this regard. In the above derivation, it was tacitly assumed that the change of concentration of the species whose reaction order was determined did not affect the potential distribution in the double layer, i.e., that Aty = MzlOHP<[> = constant (Section 7.3.1). This is true only if the concentration of ions in the double layer remains high and unchanged with varying concentrations of the ionic species investigated. This condition can be closely approxi-... 

The purpose of the present chapter is to introduce some of the basic concepts essential for understanding electrostatic and electrical double-layer pheneomena that are important in problems such as the protein/ion-exchange surface pictured above. The scope of the chapter is of course considerably limited, and we restrict it to concepts such as the nature of surface charges in simple systems, the structure of the resulting electrical double layer, the derivation of the Poisson-Boltzmann equation for electrostatic potential distribution in the double layer and some of its approximate solutions, and the electrostatic interaction forces for simple geometric situations. Nonetheless, these concepts lay the foundation on which the edifice needed for more complicated problems is built. 

For studying the stability of colloidal particles in suspension (Chapter 13) or for determining the potential at the surface of particles (Chapter 12), one often needs expressions for potential distributions around small particles that have curved surfaces. Solving the Poisson-Boltzmann equation for curved geometries is not a simple matter, and one often needs elaborate numerical methods. The linearized Poisson-Boltzmann equation (i.e., the Poisson-Boltzmann equation in the Debye-Hiickel approximation) can, however, be solved for spherical electrical double layers relatively easily (see Section 12.3a), and one obtains, in place of Equation (37),... 

In addition to all these, it is also important to keep in mind that the results depend also on what types of surface equilibrium conditions exist as the double layers interact. For example, when two charged surfaces approach each other, the overlap of the double layers will also affect the manner in which the charges on the surfaces adjust themselves to the changing local conditions. As the double layers overlap and get compressed, the local ionic equilibrium at the surface may change, and this will clearly have an impact on the potential distribution and on the potential energy of interaction. 

Solve the Poisson-Boltzmann equation for a spherically symmetric double layer surrounding a particle of radius Rs to obtain Equation (38) for the potential distribution in the double layer. Note that the required boundary conditions in this case are at r = Rs, and p - 0 as r -> oo. (Hint Transform p(r) to a new function y(r) = r J/(r) before solving the LPB equation.)... 

The electric field which actually affects the charge transfer kinetics is that between the electrode and the plane of closest approach of the solvated electroactive species ( outer Helmholtz plane ), as shown in Fig. 2.2. While the potential drop across this region generally corresponds to the major component of the polarization voltage, a further potential fall occurs in the diffuse double layer which extends from the outer Hemlholtz plane into the bulk of the solution. In addition, when ions are specifically absorbed at the electrode surface (Fig. 2.2c), the potential distribution in the inner part of the double layer is no longer a simple function of the polarization voltage. Under these circumstances, serious deviations from Tafel-like behaviour are common. 

The second term in eqn. (110) is the double layer correction to the observed reaction order due to the changes in the interfacial potential distribution with the bulk concentration of the ionic reactant. When 9A02/9 In [O] = 0, eqn. (110) becomes identical to eqn. (89) for concentrations instead of activities. This occurs in the presence of large excess of supporting electrolyte, since the concentration of the reacting ion 02o does not determine the interfacial potential distribution and the true reaction order is obtained in eqn. (110). 

Current and potential distributions are affected by the geometry of the system and by mass transfer, both of which have been discussed. They are also affected by the electrode kinetics, which will tend to make the current distribution uniform, if it is not so already. Finally, in solutions with a finite resistance, there is an ohmic potential drop (the iR drop) which we minimise by addition of an excess of inert electrolyte. The electrolyte also concentrates the potential difference between the electrode and the solution in the Helmholtz layer, which is important for electrode kinetic studies. Nevertheless, it is not always possible to increase the solution conductivity sufficiently, for example in corrosion studies. It is therefore useful to know how much electrolyte is necessary to be excess and how the double layer affects the electrode kinetics. Additionally, in non-steady-state techniques, the instantaneous current can be large, causing the iR term to be significant. An excellent overview of the problem may be found in Newman s monograph [87]. 

Thus, in practice, the potential distribution within the electrolyte is obtained by solving Laplace s equation subject to a time-dependent, Dirichlet-type boundary condition at the end of the double layer of the WE, a given value of (j> at the end of the double layer of the CE and zero-flux or periodic boundary conditions at all other domain boundaries. Knowing the potential distribution, the electric field at the WE can be calculated, and the temporal evolution of the double layer potential is obtained by integrating Eq. (11) in time, which results in changed boundary conditions (b.c.) at the WE. 

Let us consider the potential distribution for one such mixed boundary value problem in more detail. If a disk electrode of radius p0 embedded in an infinite insulating plane and with the counter electrode far away has a uniform double layer potential, DL, then the current distribution at the electrode normalized to the average current density, /avg, is given by [40]... 

Fig. 34. Illustration showing why nonlocal coupling leads to accelerated front motion. The arrows indicate the contribution of the migration coupling on the temporal evolution of the double layer at a certain distance from the interface (e.g. the inflection point) for different potential distributions.

The upper sign corresponds to a water-dielectric , and the lower one to a water-conductor type of interface. Equation (7) shows that a charge located next to a conductor will be attracted by its own image, and dielectrics in aqueous solutions will repel it. For a review of statistical-mechanical models of the double layer near a single interface we refer to [7], and here we would like only to illustrate how the image forces will alter the ion concentration and the electrostatic potential distribution next to a single wall. At a low electrolyte concentration the self-image forces will mostly dominate, and the ion-surface interaction will only be affected by the polarization due... 

Figure 1 The electrical double layer and the potential distribution at the surface 1, fixed surface charges 2, Stern layer of "fixed" charges 3, Gouy or diffuse charge layer 4, counterions 5, Helmholtz plane 6, plane of shear 7, potential distribution in the electrical double layer.

In the non-steady state, changes of stoichiometry in the bulk or at the oxide surface can be detected by comparison of transient total and partial ionic currents [32], Because of the stability of the surface charge at oxide electrodes at a given pH, oxidation of oxide surface cations under applied potential would produce simultaneous injection of protons into the solution or uptake of hydroxide ions by the surface, resulting in ionic transient currents [10]. It has also been observed that, after the applied potential is removed from the oxide electrode, the surface composition equilibrates slowly with the electrolyte, and proton (or hydroxide ion) fluxes across the Helmholtz layer can be detected with the rotating ring disk electrode in the potentiometric-pH mode [47]. This pseudo-capacitive process would also result in a drift of the electrode potential, but its interpretation may be difficult if the relative relaxation of the potential distribution in the oxide space charge and across the Helmholtz double layer is not known [48]. 

A reduction of the stability of the liquid crystalline phase means a reduced region where it is stable and a corresponding increase of the region for the inverse micellar solution. The present results agree with these predictions, and it is justifiable to relate the changes in stability areas mainly to modifications of the potential distribution within the electric double layers. 

The initial introduction of conditional probabilities is typically associated with the description of independent events, P A, B) = P A)P B) when A and B are independent. Our description of the potential distribution theorem will hinge on consideration of independent systems first, a specific distinguished molecule of the type of interest and, second, the solution of interest. We will use the notation ((... ))o to indicate the evaluation of a mean, average, or expectation of ... for this case of these two independent systems. The doubling of the brackets is a reminder that two systems are considered, and the subscript zero is a reminder that these two systems are independent. Then a simple example of a conditional expectation can be given that uses the notation explained above and in Fig. 1.8 ... 

In Chapter 1, we have discussed the potential and charge of hard particles, which colloidal particles play a fundamental role in their interfacial electric phenomena such as electrostatic interaction between them and their motion in an electric field [1 ]. In this chapter, we focus on the case where the particle core is covered by an ion-penetrable surface layer of polyelectrolytes, which we term a surface charge layer (or, simply, a surface layer). Polyelectrolyte-coated particles are often called soft particles [3-16]. It is shown that the Donnan potential plays an important role in determining the potential distribution across a surface charge layer. Soft particles serve as a model for biocolloids such as cells. In such cases, the electrical double layer is formed not only outside but also inside the surface charge layer Figure 4.1 shows schematic representation of ion and potential distributions around a hard surface (Fig. 4.1a) and a soft surface (Fig. 4.1b). 

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