Range Forces as a Factor in Emulsion Stability

Long-Range Forces as a Factor in Emulsion Stability 

There appear to be two stages in the collapse of emulsions flocculation, in which some clustering of emulsion droplets takes place, and coalescence, in which the number of distinct droplets decreases (see Refs. 31-33). Coalescence rates very likely depend primarily on the film-film surface chemical repulsion and on the degree of irreversibility of film desorption, as discussed. However, if emulsions are centrifuged, a compressed polyhedral structure similar to that of foams results [32-34]—see Section XIV-8—and coalescence may now take on mechanisms more related to those operative in the thinning of foams. 

The manner in which potential should vary across an oil-water interface is shown in Fig. XIV-5, after van den Tempel [35]. Here AV denotes the surface 

The repulsion between oil droplets will be more effective in preventing flocculation Ae greater the thickness of the diffuse layer and the greater the value of 0. the surface potential. These two quantities depend oppositely on the electrolyte concentration, however. The total surface potential should increase with electrolyte concentration, since the absolute excess of anions over cations in the oil phase should increase. On the other hand, the half-thickness of the double layer decreases with increasing electrolyte concentration. The plot of emulsion stability versus electrolyte concentration may thus go through a maximum. 

If an ionic surfactant is present, the potentials should vary as shown in Fig. XIV-5c, or similarly to the case with nonsurfactant electrolytes. In addition, however, surfactant adsorption decreases the interfacial tension and thus contributes to the stability of the emulsion. As discussed in connection with charged monolayers (see Section XV-6), the mutual repulsion of the charged polar groups tends to make such films expanded and hence of relatively low rr value. Added electrolyte reduces such repulsion by increasing the counterion concentration the film becomes more condensed and its film pressure increases. It thus is possible to explain qualitatively the role of added electrolyte in reducing the interfacial tension and thereby stabilizing emulsions. 

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