Double layer Coulombic potential

The DLVO model (named after its principal creators, Deqaguin, Landau, Verwey and Overbeek) is the most widely used to describe inter-particle surface force potential (1,2). It assumes that the total inter-particle potential is the sum of an attractive van der Waals force and a repulsive double-layer force. The repulsive force due to the double-layer coulombic interaction between equal spheres separated by a distance D generates a positive potential energy Vr. If the radius r of the spheres is large compared to the double-layer thickness 1/k (Kr l, with K the Debye-Hiickel parameter), Fr is described approximately by ... 

The first simulation studies of full double layers with molecular models of ions and solvent were performed by Philpott and coworkers [51,54,158] for the NaCl solution, using the fast multipole method for the calculation of Coulomb interactions. The authors studied the screening of a negative surface charge by free ions in several highly concentrated NaCl solutions. A combination of (9-3) LJ potential and image charges was used to describe the metal surface. 

Ionic compounds such as halides, carboxylates or polyoxoanions, dissolved in (generally aqueous) solution can generate electrostatic stabilization. The adsorption of these compounds and their related counter ions on the metallic surface will generate an electrical double-layer around the particles (Fig. 1). The result is a coulombic repulsion between the particles. If the electric potential associated with the double layer is high enough, then the electrostatic repulsion will prevent particle aggregation [27,30]. 

Certain negative ions such as Cl , Br, CNS , N03 and SO2 show an adsorption affinity to the mercury surface so in case (a), where the overall potential of the dme is zero, the anions transfer the electrons from the Hg surface towards the inside of the drop, so that the resulting positive charges along the surface will form an electric double layer with the anions adsorbed from the solution. Because according to Coulomb s law similar charges repel one another, a repulsive force results that counteracts the Hg surface tension, so that the apparent crHg value is lowered. 

Thus, it is interesting to note that high-purity aluminum rests at a potential at which corrosion is at its minimum and is, indeed, relatively very small. It is also largely independent of the anions present in the electrolyte.69 This may be attributed to the coulombic repulsion of anions away from the surface by the negative charge on the metal. The latter seems not to be completely compensated in a thin oxide film, as shown schematically in Fig. 9, so that the solution side of the double layer formed at the O/S interface contains excess cations, anions being repelled. The anions could approach the O/S interface either at thicker films or at potentials more positive than the OCP. 

The electrified interface is generally referred to as the electric double layer (EDL). This name originates from the simple parallel plate capacitor model of the interface attributed to Helmholtz.1,9 In this model, the charge on the surface of the electrode is balanced by a plane of charge (in the form of nonspecifically adsorbed ions) equal in magnitude, but opposite in sign, in the solution. These ions have only a coulombic interaction with the electrode surface, and the plane they form is called the outer Helmholtz plane (OHP). Helmholtz s model assumes a linear variation of potential from the electrode to the OHP. The bulk solution begins immediately beyond the OHP and is constant in potential (see Fig. 1). 

The extent to which ions, etc. adsorb or experience an electrostatic ( coulombic ) attraction with the surface of an electrode is determined by the material from which the electrode is made (the substrate), the chemical nature of the materials adsorbed (the adsorbate) and the potential of the electrode to which they adhere. Adsorption is not a static process, but is dynamic, and so ions etc. stick to the electrode (adsorb) and leave its surface (desorb) all the time. At equilibrium, the rate of adsorption is the same as the rate of desorption, thus ensuring that the fraction of the electrode surface covered with adsorbed material is constant. The double-layer is important because faradaic charge - the useful component of the overall charge - represents the passage of electrons through the double-layer to effect redox changes to the material in solution. 

One of the simplest equations is obtained using the Debye-Hiickel approximation (for low potentials) and the superposition principle. The latter assumes that the unperturbed potential near a charged surface can be simply added to that potential due to the other (unperturbed) surface. Thus, for the example shown in the Figure 6.12, it follows that /m = 2 /d/2- This is precisely valid for Coulomb-type interactions, where the potential at any point can be calculated from the potentials produced by each fixed charge, individually. However, the Poisson-Boltzmann equation is non-linear (this has to do with the fact that in the diffuse double-layer the ions are not fixed but move because of their kinetic energy) and so this is formally not correct although it still offers a useful approximation. 

Despite these strong assumptions, the Poisson-Boltzmann theory describes electric double layers surprisingly well. The reason is that errors lead to opposite effects and compensate each other. Including non-coulombic interactions leads to an increase of the ion concentration at the surface and a reduced surface potential. On the other hand, taking the finite size of the ions into account leads to a lower ion concentration at the surface and thus an increased surface potential. A reduction of the dielectric permittivity due to the electric field increases its range but at the same time reduces the surface potential because less ions dissociate or adsorb. 

The arrows above and the symbols below the interfaces indicate the transfer of the charge at each interface when the concentration of NaF in the sample is abruptly increased. It is possible to estimate the actual number of ions that are required to establish the potential difference at the interfaces. A typical value for the doublelayer capacitor is 10 5 F cm 2. If a potential difference of n = 100 mV is established at this interface, the double-layer capacitor must be charged by the charge Q = nCdi = 10 6 coulombs. From Faraday s law (6.3), we see that it corresponds to approximately 10 11 mol cm 2 or 1012 ions cm 2 of the electrode surface area. Thus, a finite amount of the potential determining ions is removed from the sample but this charge is replenished through the liquid junction, in order to maintain electroneutrality. 

Recently, Forsman developed a correlation-corrected PB model by introducing an effective potential between like-charge ions (Forsman, 2007). The effective potential at large ion-ion separation approaches the classical Coulomb potential and becomes a reduced effective repulsive Coulomb potential for small ion-ion separation. Such an effective potential represents liquid-like correlation behavior between the ions. For electric double layer with multivalent ions, the model makes improved predictions for the ion distribution and predicts an attractive force between two planes in the presence of multivalent ions (Forsman, 2007). However, for realistic nucleic acid structures, the model is computationally expensive. In addition, the ad hoc effective potential lacks validation for realistic nucleic acid structures. 

Several repulsive and attractive forces operate between colloidal species and determine their stability [12,13,15,26,152,194], In the simplest example of colloid stability, dispersed species would be stabilized entirely by the repulsive forces created when two charged surfaces approach each other and their electric double layers overlap. The overlap causes a coulombic repulsive force acting against each surface, which will act in opposition to any attempt to decrease the separation distance (see Figure 5.2). One can express the coulombic repulsive force between plates as a potential energy of repulsion. There is another important repulsive force causing a strong repulsion at very small separation distances where the atomic electron clouds overlap, called Born repulsion. 

The DLVO theory [1,2], which describes the interaction in colloidal dispersions, is widely used now when studying behavior of colloidal systems. According to the theory, the pair interaction potential of a couple of macroscopic particles is calculated on the basis of additivity of the repulsive and attractive components. For truly electrostatic systems, a repulsive part is due to the electrostatic interaction of likely charged macroscopic objects. If colloidal particles are immersed into an electrolyte solution, this repulsive, Coulombic interaction is shielded by counterions, which are forming the diffuse layer around particles. A significant interaction occurs only when two double layers are sufficiently overlapping during approach of those particles. 

Method (a), the use of the position of the coulombic attraction theory minimum with the Od = 0 value for g, leads to the same mathematical formula for s as that expressing the Donnan equilibrium. However, we cannot say that this constitutes a derivation of the Donnan equilibrium from the coulombic attraction theory because it does not correspond to a physical limit. If Od = 0 really were the case, there would be no reason for the macroions to remain at the minimum position of the interaction potential. Nevertheless, the identity of the two expressions is an interesting result. Because Equation 4.20 is derived in the case in which there is no double layer overlap and Equation 4.1 (the Donnan equilibrium) is likewise derived without reference to the overlap of the double layers, it is precisely in this limit that the calculation should reproduce the Donnan equilibrium. The fact that it does gives us some confidence that our approximations are not too drastic and should lead to physically significant results when applied to overlapping double layers. 

Isolated sphere with charge Q and a surface potential Identified as which obeys Coulomb s law (0= Anae ell). Using Stokes law, v=QE/Qnr)a, eq. 14.3.5] Is then Immediately obtained. This oversimplified situation applies only when the double layer contains very few Ions, as In media of extremely low dielectric permittivity. In sec. 3.11 It was verified that under those conditions screening Is negligible so that the Gouy-Chapman relations between charges and potentials reduce to that of Coulomb. Hence, the result Is as expected. 

Murray has demonstrated that soluble metallic clusters exhibit coulomb staircase-type behaviour [102]. The ionic space charge formed around the dissolved MFCs is reported to contribute to its capacitance, upon charging of the metal core. It is well known that small metal particles exhibit double layer charging (capacitive charging) properties in liquid electrolytes [104]. The sub-attofarad capacitance associated with the MFCs leads to charging of the tiny capacitor by single electron processes in potential intervals of A V that surpass ke T where is the Boltzmann constant and T is the temperature [102, 105]. 

Though the theory of Derjaguin-Landau-Verwey-Overbeek (DLVO) [17, 18] was essentially designed for hydrophobic colloids, it is often applied to the analysis of the stability of polyelectrolyte solutions. According to this approach an overlap of the electrical double-layers of two charge-like colloidal spheres in an electrolyte solution always yields a repulsive screened Coulomb interaction, and the van der Waals forces are responsible for the attraction. A number of experiments in the recent decades, however, provide evidence that the effective interparticle potential shows a long-range attraction which cannot be ascribed to the van der Waals forces [15, 88-93], In spite of numerous theoretical attempts to explain this phenomena (for a review see [7, 8, 10, 94,... 

---