Liquid interfaces emulsion

Complex fluids composed of several pseudophases with a liquid-liquid interface (emulsions, macroemul-sions, cells, liposomes) or liquid-solid interface (suspensions of silica, carbon black, latex, etc.) can, from a dielectric point of view, be considered as classical heterogeneous systems. Several basic theoretical approaches have been developed in order to describe the dielectric behavior of such systems. Depending on the concentration, the shape of the dispersed phase, and the conductivity of both the media and disperse phase, different mixture formulas can be applied to describe the electric property of the complex liquids (11-15). 

It was pointed out in Section XIII-4A that if the contact angle between a solid particle and two liquid phases is finite, a stable position for the particle is at the liquid-liquid interface. Coalescence is inhibited because it takes work to displace the particle from the interface. In addition, one can account for the type of emulsion that is formed, 0/W or W/O, simply in terms of the contact angle value. As illustrated in Fig. XIV-7, the bulk of the particle will lie in that liquid that most nearly wets it, and by what seems to be a correct application of the early oriented wedge" principle (see Ref. 48), this liquid should then constitute the outer phase. Furthermore, the action of surfactants should be predictable in terms of their effect on the contact angle. This was, indeed, found to be the case in a study by Schulman and Leja [49] on the stabilization of emulsions by barium sulfate. 

Phenomena at Liquid Interfaces. The area of contact between two phases is called the interface three phases can have only aline of contact, and only a point of mutual contact is possible between four or more phases. Combinations of phases encountered in surfactant systems are L—G, L—L—G, L—S—G, L—S—S—G, L—L, L—L—L, L—S—S, L—L—S—S—G, L—S, L—L—S, and L—L—S—G, where G = gas, L = liquid, and S = solid. An example of an L—L—S—G system is an aqueous surfactant solution containing an emulsified oil, suspended soHd, and entrained air (see Emulsions Foams). This embodies several conditions common to practical surfactant systems. First, because the surface area of a phase iacreases as particle size decreases, the emulsion, suspension, and entrained gas each have large areas of contact with the surfactant solution. Next, because iaterfaces can only exist between two phases, analysis of phenomena ia the L—L—S—G system breaks down iato a series of analyses, ie, surfactant solution to the emulsion, soHd, and gas. It is also apparent that the surfactant must be stabilizing the system by preventing contact between the emulsified oil and dispersed soHd. FiaaHy, the dispersed phases are ia equiUbrium with each other through their common equiUbrium with the surfactant solution. 

The droplet analogs to the adsubble methods have been termed the adsoplet methods (from adsorptive droplet separation methods) [LeiTilich, Adsorptive Bubble Separation Methods, Ind. E/ig. Chem., 60(10), 16 (1968)]. They are omitted from Fig. 22-41, since they involve adsorption or attachment at liquid-liquid interfaces. Among them are emulsion fractionation [Eldib, Foam and Emulsion Fractionation, in Kobe and McKetta (eds.). Advances in Petroleum Chemistry and Refining, vol. 7, Interscience, New York, 1963, p. 66], which is the analog of foam fractionation and droplet fractionation [Lemlich, loc. cit. and Strain, J. Phys. Chem., 57, 638... 

Food typically is a complicated system with diverse interfaces. Stable air-water or oil-water interfaces are essential for the production of food foams and emulsions. Interface phenomena, therefore, attract great interest in the food industry. AFM provides enough resolution to visualize the interface structures, but it cannot be directly applied on air-liquid or liquid-liquid interfaces. Fortunately, the interface structure can be captured and transferred onto a freshly cleaved mica substrate using Langmuir-Blodgett techniques for AFM scan. Images are normally captured under butanol to reduce adhesion between the probe and the sample. Then, sample distortion or damage can be avoided (Morris et al, 1999). 

Biphasic media are macroheterogenous, with a well-defined liquid-liquid interface [25,63] [Fig. 1(g), (h)], or microheterogeneous consisting of an emulsion with a very important interface area [37,38] [Fig. 1-f]. The first medium is used for kinetic studies... 

An interface is defined as a boundary between two phases. The solid/liquid and the liquid/liquid interfaces are of primary interest in suspensions and emulsion, respectively. Other types of interfaces such as liquid/gas (foams) or solid/gas interfaces also play a major role in certain pharmaceutical dosage forms, e.g., aerosols. 

Of special interest in liquid dispersions are the surface-active agents that tend to accumulate at air/ liquid, liquid/liquid, and/or solid/liquid interfaces. Surfactants can arrange themselves to form a coherent film surrounding the dispersed droplets (in emulsions) or suspended particles (in suspensions). This process is an oriented physical adsorption. Adsorption at the interface tends to increase with increasing thermodynamic activity of the surfactant in solution until a complete monolayer is formed at the interface or until the active sites are saturated with surfactant molecules. Also, a multilayer of adsorbed surfactant molecules may occur, resulting in more complex adsorption isotherms. 

Very finely disperse solids, which are adsorbed at the liquid/liquid interfaces, forming films of particles around the disperse globules. Certain powders can very effectively stabilize against coalescence. The solid s particle size must be very small compared with the emulsion droplet size and must exhibit an appropriate angle of contact at the three-phase (oil/water/solid) boundary [141]. 

The effect of ultrasound on liquid-liquid interfaces between immiscible fluids is emulsification. This is one of the major industrial uses of ultrasound (74-76) and a variety of apparatus have been devised which will generate micrometer-sized emulsions (9). The mechanism of ultrasonic emulsification lies in the shearing stresses and deformations created by the sound field of larger droplets. When these stresses become greater than the interfacial surface tension, the droplet will burst (77,78). The chemical effects of emulsification lie principally in the greatly increased surface area of contact between the two immiscible liquids. Results not unlike phase transfer catalysis may be expected. 

A stable foam is likely to have ingredients that are in a low energy state at the air-liquid interface. Substances that fit this description include proteins, emulsifiers some fats and fat components such as diglycerides monoglycerides and fatty acids. Food law uses the term emulsifier and stabiliser to cover the situation where the ingredient is stabilising an emulsion rather than helping to form it. 

It is cavitation in a heterogeneous medium which is the most studied by sonoche-mists. When produced next to a phase interface, cavitation bubbles are strongly deformed. A liquid jet propagates across the bubble towards the interface at a velocity estimated to hundreds of metres per second. At a liquid-liquid interface, the intense movement produces a mutual injection of droplets of one liquid into the other one, i. e. an emulsion (Fig. 3.3). Such emulsions, generated through sonication, are smaller in size and more stable than those obtained conventionally and often require little or no surfactant to maintain stability. It can be anticipated therefore that Phase Transfer Catalysed (PTC) reactions will be improved by sonication. Examples are provided later in this chapter. 

These figures are in approximate agreement with values calculated -with the aid of the Freundlich adsorption isotherm (see p. 134) but no definite conclusions may be drawn from them since the actual area of liquid-liquid interface in all probability was variable being dependent on the amount of emulsifying agent present. More recently the quantity of various soaps required to form a stable emulsion of kerosene in water has been determined by Grifiin (J.A.C.8. XLV. 1648, 1923) for sodium oleate, potassium stearate and potassium palmitate and by der Meulen and Riemann ibid. XLVI. 876, 1924) for sodium ricinoleate. 

In the group with positive spreading coefficients (e.g., toluene-in-water and oleic acid-in-water emulsions), the values ofkj a in both stirred tanks and bubble columns decrease upon the addition of a very small amount of oil, and then increase with increasing oil fraction. In such systems, the oils tend to spread over the gas-liquid interface as thin films, providing additional mass transfer resistance and consequently lower k values. Any increase in value upon the further addition of oils could be explained by an increased specific interfacial area a due to a lowered surface tension and consequent smaller bubble sizes. 

Many experimentalists are familiar with this principle of doping a sample with a species that couples better with the microwave irradiation and so can act as a thermal dissipater. What is often less appreciated is the general nature of this process, as not only solid/liquid interfaces but also liquid/liquid biphasic systems such as emulsions show the same effects59-63. Figure 6.2 represents the heating profiles of toluene and a perfluorinated solvent first independently and then as an emulsion. A similar trend can be seen in a hexane/acetonitrile mixture, although because of the superior heating capacity of acetonitrile the effect is less pronounced. 

On top of the PU solution the same quantity of PAN solution was poured with great care to prevent emulsification at the liquid interface. Thermodynamic equilibrium between the two phases was unlikely. After three days the volume of the PU phase had decreased by about 5%. After the solution had stood for eight days, the two layers were separated, and the different emulsions were prepared by vigorous stirring of different proportions of the two liquids. The emulsions thus obtained were stable for at least one day. 

Emulsions may sometimes be broken by the addition of a few drops of alcohol or other suitable solvent from a dropper pipette, the outlet of which is sited at the emulsion-liquid interface. 

Powders often have a stabilizing effect on emulsions [548], To understand the responsible effect we have to remember that a particle assumes a stable position in the liquid-liquid interface if the contact angle is not zero (see section 7.2.2). Upon coalescence of two drops the solid particles would have to desorb from the interface. This is energetically unfavorable. A common example of the stabilizing contribution of solid particles are margarine and butter. Both are water-in-oil emulsions. The water droplets are stabilized by small fat crystals. 

One of the central questions in the stability of foams is why are liquid films between two adjacent bubbles stable, at least for some time In fact, a film of a pure liquid is not stable at all and will rupture immediately. Formally this can be attributed to the van der Waals attraction between the two gas phases across the liquid. As for emulsions, surfactant has to be added to stabilize a liquid film. The surfactant adsorbs to the two surfaces and reduces the surface tension. The main effect, however, is that the surfactant has to cause a repulsive force between the two parallel gas-liquid interfaces. Different interactions can stabilize foam films [570], For example, if we take an ionic surfactant, the electrostatic double-layer repulsion will have a stabilizing effect. 

The formation of emulsions, suspensions, and cruds at the liquid-liquid interfaces, which disturb the continuous extraction process (84, 101, 102, 107 111). 

M.C. Phillips, Protein conformation at liquid interfaces and its role in stabilizing emulsions and foams, Food Tech. 35 (1981) 50-57. 

The lamellae in a foam contain two gas/liquid interfaces separated by a layer of fluid, thin film, each interface having a surface tension. For this reason the term film tension is sometimes used, the film tension being equal to twice the surface tension of the surfaces. It should be noted that, while the film tension is twice the surface tension of the surfaces, this is not necessarily the same as twice the surface tension of the bulk solution. In fact, the surface tension of a fluid film surface is similar to that of the bulk solution when the fluid film is thick, but departs from the bulk solution value as the fluid film thins. The situation is similar for the thin films between droplets in a concentrated emulsion. 

The adsorption of surfactants at the liquid/air interface, which results in surface tension reduction, is important for many applications in industry such as wetting, spraying, impaction, and adhesion of droplets. Adsorption at the liquid/liquid interface is important in emulsification and subsequent stabilization of the emulsion. Adsorption at the solid/liquid interface is important in wetting phenomena, preparation of solid/liquid dispersions, and stabilization of suspensions. Below a brief description of the various adsorption phenomena is given. 

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