Surfactants solution theory

AH these mechanisms except high bulk viscosity require a stabilizer in the surface layers of foam films. Accordingly, most theories of antifoaming are based on the replacement or modification of these surface-active stabilizers. This requires defoamers to be yet more surface active most antifoam oils have surface tensions in the 20 to 30 mN/m range whereas most organic surfactant solutions and other aqueous foaming media have surface tensions between 30 and 50 mN/m(= dyn/cm). This is illustrated in Table 3. 

The corresponding monomer/micelle equilibria can be dealt with by the regular solution theory (RST), as shown in particular by Rubingh in 1979 (1). The application of this theory to numerous binary surfactant systems (2 - 4) has followed and led to a set of coherent results (5). 

Taking Simultaneous Micellizadon and Adsorption Phenomena into Consideration In the presence of an adsorbent in contact with the surfactant solution, monomers of each species will be adsorbed at the solid/ liquid interface until the dual monomer/micelle, monomer/adsorbed-phase equilibrium is reached. A simplified model for calculating these equilibria has been built for the pseudo-binary systems investigated, based on the RST theory and the following assumptions ... 

A Proposed Theory. In earlier publications (1-3), a theory was proposed to correlate solubilization rate, interfacial tension and size of the surfactant aggregate (1) the interfacial tension lowering between the oil-surfactant solution interface is a function of the rate of solubilization of oil, and (2) the rate of solubilization (AS/At) is a function of the effective volume for solubilization ... 

For a binary system of surfactants A and B, the mixed micelle formation can be modeled by assuming that the thermodynamics of mixing in the micelle obeys ideal solution theory. When monomer and micelles are in equilibrium in the system, this results in ... 

The mixture CMC is plotted as a function of monomer composition in Figure 1 for an ideal system. Equation 1 can be seen to provide an excellent description of the mixture CMC (equal to Cm for this case). Ideal solution theory as described here has been widely used for ideal surfactant systems (4.6—18). Equation 2 can be used to predict the micellar surfactant composition at any monomer surfactant composition, as illustrated in Figure 2. This relation has been experimentally confirmed (ISIS) As seen in Figure 2, for an ideal system, if the ratio XA/yA < 1 at any composition, it will be so over the entire composition range. In classical phase equilibrium thermodynamic terms, the distribution coefficient between the micellar and monomer phases is independent of composition. 

Below the CMC, the surfactant mixing in monolayers composed of similarly structured surfactants approximately obeys ideal solution theory. This means that the total surfactant concentration required to attain a specified surface tension for a mixture is intermediate between those concentrations for the pure surfactants involved. For mixtures of ionic/nonionic or anionic/cationic surfactants, below the CMC, the surfactant mixing in the monolayer exhibits negative deviation from ideality (i.e., the surfactant concentration required to attain a specified surface tension is less than that predicted from ideal solution theory). The same guidelines already discussed to select surfactant mixtures which have low monomer concentrations when micelles are present would also apply to the selection of surfactants which would reduce surface tension below the CMC. 

When two similarly structured anionic surfactants adsorb on minerals, the mixed admicelle approximately obeys ideal solution theory (jUL - Below the CMC, the total adsorption at any total surfactant concentration is intermediate between the pure component adsorption levels. Adsorption of each surfactant component in these systems can be easily predicted from pure component adsorption isotherms by combining ideal solution theory with an empirical correspond ng states theory approach (Z3). ... 

Equation 1 has proved to be a better predictor of the equilibrium which exists between monomer and micelles for mixed surfactant systems than is the regular solution theory model. It also predicts well the mixture CMC and shows the heat of mixing to be smaller than that predicted by the regular solution theory in agreement with the experiment (13). The purpose of this paper is to further explore... 

Non-ideal solution theory is used to calculate the value of a parameter, S, that measures the interaction between two surfactants in mixed monolayer or mixed micelle formation. The value of this parameter, together with the values of relevant properties of the individual, pure surfactants, determines whether synergism will exist in a mixture of two surfactants in aqueous solution. 

It was recently ascertained that the behavior of the adsorbed film of two surfactants in equilibrium with their micelle can be explained by assuming both the surface region and the micelle particle to be mixtures of the surfactants (1 - ) - Further, the application of the regular solution theory to the mixtures was shown to be useful to describe the nonideal behavior of ionic surfactants ( - ) However, the above treatments are incomplete from the thermodynamic viewpoint, because they do not consider the dissociation of surfactants and ignore the presence of solvent (T). In addition, it is impossible to suppose that the regular solution theory is applicable to both the adsorbed film and the micelle of ionic surfactants accompanied by the electrical double layer ( ). 

The nature of surface adsorption and micelle formation of various mixed FC- and HC-surfactants systems can be conveniently and well investigated by the non-ideal solution theory semi-emplrlcally applied in the surface layer and micelles. The weak "mutual phobic" interaction between FC- and HC-chains has been clearly revealed in the anionic-anionic and nonlonic-nonionic systems as Indicated by the positive values. value cannot be obtained... 

It is evident that the non-ideal solution theory of surface adsorption and micellization is a convenient and useful tool for obtaining the surface and the micelle compositions and for studing the molecular interaction in the binary surfactant system. 

Scamehorn et. al. (20) also presented a simple, semi—empirical method based on ideal solution theory and the concept of reduced adsorption isotherms to predict the mixed adsorption isotherm and admicellar composition from the pure component isotherms. In this work, we present a more general theory, based only on ideal solution theory, and present detailed mixed system data for a binary mixed surfactant system (two members of a homologous series) and use it to test this model. The thermodynamics of admicelle formation is also compared to that of micelle formation for this same system. 

The mixed admicelle is very analogous to mixed micelles, the thermodynamics of formation of which has been widely studied. If the surfactant mixing in the micelle can be described by ideal solution theory, the Critical Micelle Concentration (CMC) or minimum concentration at which micelles first form can be described by (21) ... 

A previously proposed theory to describe mixed adsorption in these systems (20) depended not only on ideal solution theory, but also on the correspond ng states theory to apply to surfactant mixtures. In that model, it was assumed that the adsorption isotherms for the pure components coincided when plotted against a reduced concentration. This occurs when the ratio CACB E/CACrt is the same at any adsorption level. When true, this simplifies the prediction of mixed adsorption isotherms somewhat, but that model is really a special case of the model presented here. 

By extending regular solution theory for binary mixtures of AEg in aqueous solution to the adsorption of mixture components on the surface (3,4), it is possible to calculate the mole fraction of AEg, Xg, on the mixed surface layer at tt=20, the molecular interaction parameter, 6, the activity coefficients of AEg on the mixed surface layer, fqg and f2s and mole concentration of surfactant solution, CTf=20 3t surface pressure tt=20 mn-m l (254p.l°C). The results from the following equations are shown in Table I and Table II. 

The cloud point phenomena as a lower consolute solution temperature is becoming better understood in terms of critical solution theory and the fundamental forces involved for pure nonionic surfactant systems. However, the phenomena may still occur if some ionic surfactant is added to the nonionic surfactant system. A challenge to theoreticians will be to model these mixed ionic/nonionic systems. This will require inclusion of electrostatic considerations in the modeling. 

Others have studied the volumetric changes occurring in mixed micelles of anionic-anionic and nonionic-nonionic surfactants as a determinant of intermolecular interactions and a measure of the thermodynamic ideality of mixing. In particular, Funasaki et al. (1986) have studied the volumetric behavior of mixed micelles of ionic and nonionic surfactants and analyzed their results in terms of regular solution theory. They found that in water, anionic surfactants such as SDS bind to PEG,... 

In an effort to go beyond regular solution theory and better understand the molecular basis of mixed surfactant system behavior, several molecular-thermodynamic theories for surfactant mixtures have been developed. The molecular-thermodynamic theory will be brieLy introduced and discussed below. Readers are referred to a recent summary (Shiloach and Blankschtein, 1998) o can obtain more detailed description and discussion in literature (Nagarajan, 1985, 1986 Puwada and Blankschtein, 1990,1992 Nargarajan and Ruckenstein, 1991 Bergstroem and Eriksson, 1992 Sarmoria et al., 1992 Zoeller and Blankschtein, 1995, 1998 Almgren et al., 1996 Barzykin and Almgren, 1996 Bergstroem, 1996 Zoeller et al., 1996 Blankschtein et al., 1997 Shiloach and Blankschtein, 1997,1998 Thomas et al., 1997 Shiloach et al., 1998). 

Radio frequency heating, 500 Steam stripping, 500 Vacuum extraction, 500 Aeration, 501 Bioremediation, 501 Soil flushing/washing, 502 Surfactant enhancements, 502 Cosolvents, 502 Electrokinetics, 503 Hydraulic and pneumatic fracturing, 503 Treatment walls, 505 Supercritical Water Oxidation, 507 Solid Solution Theory, 202 Solubility products, 48-53 Metal carbonates, 433-434 Metal hydroxides, 429-433 Metal sulfides, 437 Sorption, 167 See Adsorption Specific adsorption, 167 See Chemisorption Stem Layer, 152-154 Sulfate, 261... 

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