Potential-determining ions electrical double layer

Figure 2.1 illustrates the results of cumulative electrical charge versus cumulative volume of flow for various different clay and clay mixtures when the major contributing ion in the soil matrix was cadmium. In these experiments, the initial concentration of Cd" in each medium was determined after mixing clay slurry with a concentrated solution of cadmium salt, which was left to consolidate to a constant effective stress over a few weeks, and measuring the total cadmium retained in the compressed clay matrix. This procedure allowed uniform distribution of the ion in the clay, the time necessary for potential ion exchanges to take place, and more importantly, the full development of the electric double layer at the ion concentration retained within the clay bulk fluid. 

The most important quantity that determines the instability in pitting dissolution is the fluctuation of the electrochemical potential of dissolved metal ions in the electric double layer. In the presence of a large amount of supporting electrolyte, the fluctuation can be formulated with the fluctuations of the potential x, y, ff of the Helmholtz layer and the concentration cm (, y, Cfl.0a as follows,... 

The Nernst equation is of limited use at low absolute concentrations of the ions. At concentrations of 10 to 10 mol/L and the customary ratios between electrode surface area and electrolyte volume (SIV 10 cm ), the number of ions present in the electric double layer is comparable with that in the bulk electrolyte. Hence, EDL formation is associated with a change in bulk concentration, and the potential will no longer be the equilibrium potential with respect to the original concentration. Moreover, at these concentrations the exchange current densities are greatly reduced, and the potential is readily altered under the influence of extraneous effects. An absolute concentration of the potential-determining substances of 10 to 10 mol/L can be regarded as the limit of application of the Nernst equation. Such a limitation does not exist for low-equilibrium concentrations. 

Studies of the adsorption of surface active electrolytes at the oil-water interface provide a convenient method for testing electrical double layer theory and for determining the state of water and ions in the neighborhood of an interface. The change in the surface amount of the large ions modifies the surface charge density. For instance, the surface ionic area of 100 per ion corresponds to 16, /rC/cm. The measurement of the concentration dependence of the changes of surface potential were also applied to find the critical concentration of formation of the micellar solution [18]. 

What is next Several examples were given of modem experimental electrochemical techniques used to characterize electrode-electrolyte interactions. However, we did not mention theoretical methods used for the same purpose. Computer simulations of the dynamic processes occurring in the double layer are found abundantly in the literature of electrochemistry. Examples of topics explored in this area are investigation of lateral adsorbate-adsorbate interactions by the formulation of lattice-gas models and their solution by analytical and numerical techniques (Monte Carlo simulations) [Fig. 6.107(a)] determination of potential-energy curves for metal-ion and lateral-lateral interaction by quantum-chemical studies [Fig. 6.107(b)] and calculation of the electrostatic field and potential drop across an electric double layer by molecular dynamic simulations [Fig. 6.107(c)]. 

At the next level we also take specific adsorption of ions into account (Fig. 4.6). Specifically adsorbed ions bind tightly at a short distance. This distance characterizes the inner Helmholtz plane. In reality all models can only describe certain aspects of the electric double layer. A good model for the structure of many metallic surfaces in an aqueous medium is shown in Fig. 4.6. The metal itself is negatively charged. This can be due to an applied potential or due to the dissolution of metal cations. Often anions bind relatively strongly, and with a certain specificity, to metal surfaces. Water molecules show a distinct preferential orientation and thus a strongly reduced permittivity. They determine the inner Helmholtz plane. 

Figure 1. Potential variation through the electrical double layer for a higher concentration of potential-determining ion (a), a lower concentration of potential-determining ion (b), and in the presence of a specifically adsorbed counter ion with a potential-determining ion below the point-of-zero charge (c). Note that the potential in all three instances could be identical. (Reproduced, with permission, from Ref. 1. Copyright 1970, International Union of Pure and Applied Chemists.)...

Silver iodide particles in aqueous suspension are in equilibrium with a saturated solution of which the solubility product, aAg+ai, is about 10 16 at room temperature. With excess 1 ions, the silver iodide particles are negatively charged and with sufficient excess Ag+ ions, they are positively charged. The zero point of charge is not at pAg 8 but is displaced to pAg 5.5 (pi 10.5), because the smaller and more mobile Ag+ ions are held less strongly than-the 1 ions in the silver iodide crystal lattice. The silver and iodide ions are referred to as potential-determining ions, since their concentrations determine the electric potential at the particle surface. Silver iodide sols have been used extensively for testing electric double layer and colloid stability theories. 

The H-form latex was converted to Na-form latex by adding either an excess or an exact amount of NaOH as determined by conductometric titration in order to eliminate the possible effect of the ion-exchange between the H+ ion on the latex particle and Na+ ion in the solution. The results showed that the Na-form latex had the same em (3.2 y.cm/sec. volt) with H-form latex (3.1 y.cm/sec. volt) in deionized water and same increasing dependency of mobility with increasing NaCl concentration, Figure 1. A reasonable explanation for the increase in zeta potential is the adsorption of negative chloride ion from solution to the surface of latex particle. The decrease in em above 10 M NaCl is associated with compression of the electrical double layer. 

The potential in the diffuse layer decreases exponentially with the distance to zero (from the Stem plane). The potential changes are affected by the characteristics of the diffuse layer and particularly by the type and number of ions in the bulk solution. In many systems, the electrical double layer originates from the adsorption of potential-determining ions such as surface-active ions. The addition of an inert electrolyte decreases the thickness of the electrical double layer (i.e., compressing the double layer) and thus the potential decays to zero in a short distance. As the surface potential remains constant upon addition of an inert electrolyte, the zeta potential decreases. When two similarly charged particles approach each other, the two particles are repelled due to their electrostatic interactions. The increase in the electrolyte concentration in a bulk solution helps to lower this repulsive interaction. This principle is widely used to destabilize many colloidal systems. 

The electrical double layer at the metal oxide/electrolyte solution interface can be described by characteristic parameters such as surface charge and electrokinetic potential. Metal oxide surface charge is created by the adsorption of electrolyte ions and potential determining ions (H+ and OH-).9 This phenomenon is described by ionization and complexation reactions of surface hydroxyl groups, and each of these reactions can be characterized by suitable constants such as pKa , pKa2, pKAn and pKct. The values of the point of zero charge (pHpzc), the isoelectric point (pH ep), and all surface reaction constants for the measured oxides are collected in Table 1. 

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). 

If lattice ions or other potential-determining ions are adsorbed on a solid surface, they may be regarded as belonging to the solid and imparting an electrical charge to it. For the sake of overall electrical neutrality, an equivalent number of oppositely charged ions (counterions) exist in solution, drawn to the charged surface by electrical attraction. The counterions and the adsorbed lattice ions form an electrical double layer. The closest counterions cannot be nearer the surface than a finite distance (inner Helmholtz plane ) that depends on the ionic radius. 

The ion and electrical potential distributions in the electrical double layer can be determined by solving the Poisson-Boltzmann equation [2,3]. According to the theory of electrostatics, the relationship between the eleetrieal potential ij/ and the local net charge density per unit volume at any point in the solution is deseribed by the Poisson equation ... 

Two parameters were introduced into the description of double electrical layer. One of them is the point of zero charge (PZC) which according to lUPAC definition [101] can be expressed as concentration of potential-determining ions PDI at which the surface charge is equal to zero ( o = 0), as well as the surface potential (V>o = 0). Another parameter is isoelectric point (lEP) defined [101] as concentration of PDI at which the electrokinetic potential is equal to zero (( = 0). 

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