Colloid dispersion forces

Electroacoustics — Ultrasound passing through a colloidal dispersion forces the colloidal particles to move back and forth, which leads to a displacement of the double layer around the particles with respect to their centers, and thus induces small electric dipoles. The sum of these dipoles creates a macroscopic AC voltage with the frequency of the sound waves. The latter is called the Colloid Vibration Potential (CVP) [i]. The reverse effect is called Electrokinetic Sonic Amplitude (ESA) effect [ii]. See also Debye effect. 

To first order, the dispersion (a-a) interaction is independent of the structure in a condensed medium and should be approximately pairwise additive. Qualitatively, this is because the dispersion interaction results from a small perturbation of electronic motions so that many such perturbations can add without serious mutual interaction. Because of this simplification and its ubiquity in colloid and surface science, dispersion forces have received the most significant attention in the past half-century. The way dispersion forces lead to long-range interactions is discussed in Section VI-3 below. Before we present this discussion, it is useful to recast the key equations in cgs/esu units and SI units in Tables VI-2 and VI-3. 

Determine the net DLVO interaction (electrostatic plus dispersion forces) for two large colloidal spheres having a surface potential 0 = 51.4 mV and a Hamaker constant of 3 x 10 erg in a 0.002Af solution of 1 1 electrolyte at 25°C. Plot U(x) as a function of x for the individual electrostatic and dispersion interactions as well as the net interaction. 

FIG. 1 The mean force potential acting between colloidal species, /3fV (r), in adsorbed colloidal dispersion. In parts (a) and (b) the matrix density is taken as negligibly small, = 10 and = 0.193, respectively. In both parts, the evolution of the mean force potential with solvent density is shown p = 0.2, 0.3 and 0.4 (solid, dashed, and dotted lines, respectively). In part (c) the evolution of the PMF on matrix density is presented. The solvent density is held constant, p =0.3 the matrix density is Pmcr = 0.193, 0.386, and 0.772 (dotted, dashed, and solid lines, respectively). The diameter of the matrix species is = 7.055. The density of colloids is Pcg] = 10 , with Uc = 5, in all the cases in question. 

This method is used particularly for colloids. A colloidal dispersion is forced through a long column packed with nonporous beads with an approximate radius of 10pm. Particles of different particle size travel with different speeds around the beads and are thus collected in size fractions. 

KEY TERMS intermolecular forces proteins colloidal dispersion... 

The pair potential of colloidal particles, i.e. the potential energy of interaction between a pair of colloidal particles as a function of separation distance, is calculated from the linear superposition of the individual energy curves. When this was done using the attractive potential calculated from London dispersion forces, Fa, and electrostatic repulsion, Ve, the theory was called the DLVO Theory (from Derjaguin, Landau, Verwey and Overbeek). Here we will use the term to include other potentials, such as those arising from depletion interactions, Kd, and steric repulsion, Vs, and so we may write the total potential energy of interaction as... 

When two similarly charged colloid particles, under the influence of the EDL, come close to each other, they will begin to interact. The potentials will detect one another, and this will lead to various consequences. The charged molecules or particles will be under both van der Waals and electrostatic interaction forces. The van der Waals forces, which operate at a short distance between particles, will give rise to strong attraction forces. The potential of the mean force between colloid particle in an electrolyte solution plays a central role in the phase behavior and the kinetics of agglomeration in colloidal dispersions. This kind of investigation is important in these various industries ... 

It should be realized, at the outset, that colloidal solutions (unlike true solutions) will almost always be in a metastable state. That is, an electrostatic repulsion prevents the particles from combining into their most thermodynamically stable state, of aggregation into the macroscopic form, from which the colloidal dispersion was (artificially) created in the first place. On drying, colloidal particles will often remain separated by these repulsive forces, as illustrated by Figure 1.1, which shows a scanning electron microscope picture of mono-disperse silica colloids. 

Preparation of Emulsions. An emulsion is a system in which one liquid is colloidally dispersed in another (see Emulsions). The general method for preparing an oil-in-water emulsion is to combine the oil with a compatible fatty acid, such as an oleic, stearic, or rosin acid, and separately mix a proportionate quantity of an alkali, such as potassium hydroxide, with the water. The alkali solution should then be rapidly stirred to develop as much shear as possible while the oil phase is added. Use of a homogenizer to force the resulting emulsion through a fine orifice under pressure further reduces its oil particle size. Liquid oleic acid is a convenient fatty acid to use in emulsions, as it is readily miscible with most oils. 

Coagulation of colloidal dispersions (Fig. 1.26h) as a function of salt concentration, pH, or temperature of the suspending liquid medium can also be used to obtain information on the interplay of repulsive and attractive forces between particles in pure liquids as well as in surfactant and polymer solutions. 

In Section 3.4a we examine a model for the second virial coefficient that is based on the concept of the excluded volume of the solute particles. A solute-solute interaction arising from the spatial extension of particles is the premise of this model. Therefore the potential exists for learning something about this extension (i.e., particle dimension) for systems for which the model is applicable. In Section 3.4b we consider a model that considers the second virial coefficient in terms of solute-solvent interaction. This approach offers a quantitative measure of such interactions through B. In both instances we only outline the pertinent statistical thermodynamics a somewhat fuller development of these ideas is given in Flory (1953). Finally, we should note that some of the ideas of this section are going to reappear in Chapter 13 in our discussions of polymer-induced forces in colloidal dispersions and of coagulation or steric stabilization (Sections 13.6 and 13.7). 

The London force is also often called the dispersion force. The word dispersion here has nothing to do with the role of the London force in colloidal dispersions, but is the result of the role this type of interaction force plays in the dispersion of light in the visible and ultraviolet wavelengths. 

Sato, T., and Ruch, R., Stabilization of Colloidal Dispersions by Polymer Adsorption, Marcel Dekker, New York, 1980. (Research monograph. An advanced treatment of polymer-induced forces.)... 

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