Debye-Hiickel layer

A charged particle in suspension with its inner immobile Stern layer and outer diffuse Gouy (or Debye-Hiickel) layer presents a different problem than a smooth and small non-polar sphere. Such particles when moving experience electroviscous effects which have two sources (i) the resistance of the ion cloud to deformation (ii) the repulsion between particles in close contact. When particles interact, for example, to form pairs in the system the new particle will have a different shape from the original and will have different flow properties. The coefficient 2.5 in Einstein s equation (9.11) applies only to spheres asymmetric particles will produce coefficients greater than 2.5. 

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. 

However, it is interesting to note that the theory of the diffuse double layer was presented independently by Gouy and Chapman (1910) 13 years before the Debye-Hiickel theory of ion ion interactions (1923). The Debye-Hiickel theory was immediately discussed and applied to the diffuse charge around an ion, doubtless owing to the preoccupation of the majority of scientists in the 1920s with bulk properties rather than those at surfaces. 

This same relationship is the starting point of the Debye-Hiickel theory of electrolyte nonideality, except that the Debye-Hiickel theory uses the value of V2 p required for spherical symmetry. It is interesting to note that Gouy (in 1910) and Chapman (in 1913) applied this relationship to the diffuse double layer a decade before the Debye-Hiickel theory appeared. 

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),... 

FIG. 11.5 Fraction of double-layer potential versus distance from a surface according to the Debye-Hiickel approximation, Equation (37) (a) curves drawn for 1 1 electrolyte at three concentrations and (b) curves drawn for 0.001 M symmetrical electrolytes of three different valence types. 

Even allowing for the fact that the Debye-Hiickel approximation applies only for low potentials, the above analysis reveals some features of the electrical double layer that are general and of great importance as far as stability with respect to coagulation of dispersions and electrokinetic phenomena are concerned. In summary, three specific items might be noted ... 

The Debye-Hiickel approximation to the diffuse double-layer problem produces a number of relatively simple equations that introduce a variety of double-layer topics as well as a number of qualitative generalizations. In order to extend the range of the quantitative relationships, however, it is necessary to return to the Poisson-Boltzmann equation and the unrestricted Gouy-Chapman theory, which we do in Section 11.6. 

Equation (62) describes the variation in potential with distance from the surface for a diffuse double layer without the simplifying assumption of low potentials. It is obviously far less easy to gain a feeling for this relationship than for the low-potential case. Anticipation of this fact is why so much attention was devoted to the Debye-Hiickel approximation in the first place. Note that Equation (62) may be written... 

The Derjaguin approximation illustrated in the above example is suitable when kR > 10, that is, when the radius of curvature of the surface, denoted by the radius R, is much larger than the thickness of the double layer, denoted by k 1. (Note that for a spherical particle R = Rs, the radius of the particle.) Other approaches are required for thick double layers, and Verwey and Overbeek (1948) have tabulated results for this case. The results can be approximated by the following expression when the Debye-Hiickel approximation holds ... 

Equation (1.35) is known as the Debye-Hiickel or Gui-Chapman equation for the equilibrium double layer potential. In terms of the original variable x (1.34), (1.35) suggest e1/2(r(j) is the correct scale of ip variation, that is, the correct scale for the thickness of the electric double layer. At the same time, it is observed from (1.32) that for N 1 the appropriate scale depends on N, shrinking to zero when N — oo (ipm — — oo). This illustrates the previously made statement concerning the meaningfulness of the presented interpretation of relectric potential

(—oo) — 0, < (oo) — —oo). 

Equations (6.4.43a-c) yield the central result of this section—the following expression for the electro-osmotic slip velocity ua under an applied potential and concentration gradient, in the Debye-Hiickel approximation for a thin double layer... 

The diffuse layer is described by the Gouy—Chapman theory of 1913 [21, 22], which is based on the same equations as the Debye—Hiickel theory of 1923 for electrolytes, which describes the electrostatic potential around an ion in a given ionic atmosphere [23]. 

The characteristic thickness of the double layer is given by Debye-Hiickel theory as A 1, where h is... 

When Di > i>2, the effective Debye—Hiickel length X (which now depends on ip(x)) is larger than that obtained for the Poisson—Boltzmann equation. Consequently, the diffuse double layer is larger in the vicinity of a charged surface, as predicted earlier.4 7 9 However, when V2 > Vi (small counterions), X < X and the diffuse double layer is compressed. The effect is proportional to the ionic strength and is, in general, small for typical electrolyte concentrations, since n(v — v[Pg.337]

When the electrolyte concentration is increased, the range of the double layer decreases dramatically (the Debye-Hiickel length decreases) and the magnitude of the surface potential also decreases. In the linear approximation, ]f(x) = iJj(c E)cxp( — (x-dB)/X) (for x>dB) and the second right-hand-side term of Eq. (48) becomes ... 

For the sake of simplicity, in what follows it will be considered that the double layer potential is sufficiently small to allow the linearization of the Poisson—Boltzmann equation (the Debye—Hiickel approximation). The extension to the nonlinear cases is (relatively) straightforward however, it will turn out that the differences from the DLVO theory are particularly important at high electrolyte concentrations, when the potentials are small. In this approximation, the distribution of charge inside the double layer is given by... 

Debye-Hiickel parameter, estimated here as k = y/ c/3 A. 1 (assuming the dielectric constant of the solvent medium inside the double layer is 80). valence of charges (= 1) electronic charge... 

Equation (1.9) is the linearized Poisson-Boltzmann equation and k in Eq. (1.10) is the Debye-Htickel parameter. This linearization is called the Debye-Hiickel approximation and Eq. (1.9) is called the Debye-Hiickel equation. The reciprocal of k (i.e., 1/k), which is called the Debye length, corresponds to the thickness of the double layer. Note that nf in Eqs. (1.5) and (1.10) is given in units of m . If one uses the units of M (mol/L), then must be replaced by IQQQNAn, Na being Avogadro s number. 

Figure 1.4 shows y(x) for several values of yo calculated from Eq. (1.37) in comparison with the Debye-Hlickel linearized solution (Eq. (1.25)). It is seen that the Debye-Hiickel approximation is good for low potentials (lyol< 1). As seen from Eqs. (1.25) and (1.37), the potential i//(x) across the electrical double layer varies nearly... 

Debye-Hiickel parameter k (the Debye length), which has the dimension of length, serves as a measure for the thickness of the electrical double layer. Figure 1.5 plots the... 

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