Mixed micelle formation

In an earlier review [3], mixed micelles formed by bile salts were classified into those with (i) non-polar lipids (e.g., linear or cyclic hydrocarbons) (ii) insoluble amphiphiles (e.g., cholesterol, protonated fatty acids, etc.) (iii) insoluble swelling amphiphiles (e.g., phospholipids, monoglycerides, acid soaps ) and (iv) soluble amphiphiles (e.g., mixtures of bile salts with themselves, with soaps and with detergents) and the literature up to that date (1970) was critically summarized. Much recent work has appeared in all of these areas, but the most significant is the dramatic advances that have taken place in our understanding of the structure, size, shape, equilibria, and thermodynamics of bile salt-lecithin [16,18,28,29,99-102,127, 144,218,223,231-238] and bile salt-lecithin-cholesterol [238,239] micelles which are of crucial importance to the solubihty of cholesterol in bile [1]. This section briefly surveys recent results on the above subclasses. Information on solubilization, solubilization capacities or phase equilibria of binary, ternary or quaternary systems or structures of liquid crystalline phases can be found in several excellent reviews [5,85,207,208,210,211,213,216,217] and, where relevant, have been referred to earlier. 

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In this system, in the aqueous phase, the micellar system, NaDDS, on addition of butanol would change in free energy due to mixed micelle formation (i. je. NaDDS+n-Butanol), as we showed in an earlier study (23). The cahnge in free energy is also observed from the fact that both the critical micelle concentration (c.m.c.) and the Krafft point of NaDDS solution change on addition of n-Butanol (23,... 

NA Mazer, GB Benedeck, MC Carey. Quasielastic light-scattering studies of aqueous biliary lipid systems. Mixed micelles formation in bile salt-lecithin solutions. Biochemistry 19 601-615, 1980. 

Except for some anionic/cationic surfactant mixtures which form ion pairs, in a typical surfactant solution, the concentration of the surfactant components as monomeric species is so dilute that no significant interactions between surfactant monomers occur. Therefore, the monomer—mi celle equilibria is dictated by the tendency of the surfactant components to form micelles and the interaction between surfactants in the micelle. Prediction of monomer—micelle equilibria reduces to modeling of the thermodynamics of mixed micelle formation. 

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 ... 

Mixed Micelles Showing Negative Deviation -from Ideality. In an aqueous solution containing a mixture o-f Cll an ionic sur-factant and a nonionic sur-factant, or C21 an anionic sur-factant and a cationic sur-factant, or C33 a zwitterionic sur-factant and an anionic sur-factant, the CMC o-f the mixed sur-factant system exhibits a CMC which is substantially less than that predicted by Equation 1 (9.12.18-37). This means that the mixed micelle -formation is enhanced and that the mixing process in the micelle shows negative deviation -from ideality. This is demonstrated -for a cationic/nonionic system in Figure 1. 

The adsorption of mixed surfactants at the air—water interface (monolayer formation) is mechanistically very similar to mixed micelle formation. The mixed monolayer is oriented so that the surfactant hydrophilic groups are adjacent to each other. The hydrophobic groups are removed from the aqueous environment and are in contact with other hydrophobic groups or air. Therefore, the forces tending to cause monolayers to form are similar to those causing micelles to form and the thermodynamics and interactions between surfactants are similar in the two aggregation processes. 

The same effect is seen when a non—aromatic cationic surfactant/nonionic surfactant system is used. Since the nonideality of mixed micelle formation in this case is due almost entirely to the electrostatic effects and not to any specific interactions between the dissimilar hydrophilic groups, the geometrical effect just discussed will cause the EO groups to be less compactly structured... 

This brief review has attempted to discuss some of the important phenomena in which surfactant mixtures can be involved. Mechanistic aspects of surfactant interactions and some mathematical models to describe the processes have been outlined. The application of these principles to practical problems has been considered. For example, enhancement of solubilization or surface tension depression using mixtures has been discussed. However, in many cases, the various processes in which surfactants interact generally cannot be considered by themselves, because they occur simultaneously. The surfactant technologist can use this to advantage to accomplish certain objectives. For example, the enhancement of mixed micelle formation can lead to a reduced tendency for surfactant precipitation, reduced adsorption, and a reduced tendency for coacervate formation. The solution to a particular practical problem involving surfactants is rarely obvious because often the surfactants are involved in multiple steps in a process and optimization of a number of simultaneous properties may be involved. An example of this is detergency, where adsorption, solubilization, foaming, emulsion formation, and other phenomena are all important. In enhanced oil recovery. 

A brief accounting of the thermodynamics of mixed micelle formation is given here primarily to clarify certain important issues which appear to have been previously overlooked. The necessity for measuring the monomer and micellar composition will be demonstrated. 

Mixed surfactant systems are of importance from a fundamental and practical point of view. Therefore, many recent papers have reported on the micellar properties of mixed surfactant solutions. For example, Tokiwa et al. have measured the NMF spectra W Ingram has measured surface tension ( 5). Previously, we have reported the solution properties of anionic-nonlonlc surfactant mixed systems from the point of view of electrical (., 7) and surface tension measurements (8-10), and investigated the mixed micelle formation. 

In this paper, we report the solution properties of sodium dodecyl sulfate (SDS)-alkyl poly(oxyethylene) ether (CjjPOEjj) mixed systems with addition of azo oil dyes (4-NH2, 4-OH). The 4-NH2 dye interacts with anionic surfactants such as SDS (11,12), while 4-OH dye Interacts with nonionic surfactants such as C jPOEn (13). However, 4-NH2 is dependent on the molecular characteristics of the nonionic surfactant in the anlonlc-nonlonic mixed surfactant systems, while in the case of 4-OH, the fading phenomena of the dye is observed in the solubilized solution. This fading rate is dependent on the molecular characteristics of nonionic surfactant as well as mixed micelle formation. We discuss the differences in solution properles of azo oil dyes in the different mixed surfactant systems. 

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. 

The conditions for synergism in surface tension reduction efficiency, mixed micelle formation, and Surface tension reduction effectiveness in aqueous solution have been derived mathematically together with the properties of the surfactant mixture at the point of maximum synergism. This treatment has been extended to liquid-liquid (aqueous solution/hydrocarbon) systems at low surfactant concentrations.) The effect of chemical structure and molecular environment on the value of B is demonstrated and discussed. 

The evaluation of the Interaction parameters is based upon equations (1 and 2), derived by Rubingh (7) for mixed micelle formation from the thermodynamics of the system ... 

C 2 re needed for determlng 3 (the interaction parameter for mixed micelle formation in aqueous solution), the critical micelle... 

Figure 2. Synergism in surface tension reduction efficiency (Ci2 < C ° or 2°) or in mixed micelle formation...

Synergism in mixed micelle formation. Synergism in this respect is present when the critical micelle concentration of any mixture is lower than that of either pure surfactant. This is illustrated in Figure 2. 

By mathematical treatment similar to that for synergism in surface tension reduction efficiency, we have found that the conditions for synergism in mixed micelle formation are ... 

At the point of maximum synergism in mixed micelle formation, M... 

The cmc at the point of maximum synergism, i.e., the minimum total mixed surfactant concentration in the solution phase required for mixed micelle formation, C 2 nin given by the relationship ... 

Table II. Synergism in Mixed Micelle Formation at 25 C System 0 2 25 V 8 17 ° 2 4 4° ...

Figure 4. Synergism in mixed micelle formation for some binary surfactant mixtures. gOH mixtures...

The thermodynamics of mixing upon formation of the bilayered surface aggregates (admicelles) was studied as well as that associated with mixed micelle formation for the system. Ideal solution theory was obeyed upon formation of mixed micelles, but positive deviation from ideal solution theory was found at all mixture... 

Mixed Micelles. The CMC values -for the two pure sur-factants and well de-fined mixtures thereo-f are shown in Figure 2. The experiments were run at a high added salt level (swamping electrolyte) so the counterion contributed by the dissolved sur-factant is negligible. Predicted mixture CMC values -for ideal mixing -from Equation 1 are also shown. Ideal solution theory describes mixed micelle -formation very well, as is usually the case -for similarly structured sur-factant mixtures (12.19.21—2A) ... 

A few papers have been published recently on the problem of surfactant adsorption maxima on solids in the region of the CMC (1-5). Scamehorn et al. (1,2) and Trogus et al. (3) expTTined the origin of these maxima by various radios of the surfactant solution to the solid, in connection with isomeric impurity of the surfactant. Ananthapadmanabhan and Soniasundaran (4) examined critically the presence of such maxima from the viewpoint of various proposed adsorption mechanisms. They have shown that a mechanism including micellar exclusion, mixed micelle formation and properties of solids, such as the pore size, cannot explain satisfac-... 

Micelles are often present in surfactant systems. In some processes, such as solubilization, they are directly involved. Micelles indirectly affect many other processes because monomer concentrations or activities of the surfactant components are dictated by the monomer— micelle equilibrium at total surfactant concentrations above the CMC. Therefore, interest in mixed micelle formation will continue to grow. 

Model Development. There is vast opportunity for development of fundamentally based models to describe the thermodynamics of mixed micelle formation. As discussed in Chapter 1, regular solution theory has yielded useful relations to describe monomer—mi cel 1e equilibrium. 

The lack of certain critical data for these systems, as already discussed, has hampered development of improved theories. Models of mixed micelle formation need to be based on the fundamental forces causing nonidealities of mixing. Some of these have been discussed in Chapter 1. Chapter 2 Schechter is an example of the... 

The same thermodynamic quantities needed for mixed micelle formation (already discussed) are also needed for mixed admicelle formation. Luckily, the monomer-admicelle equilibrium data can be fairly easily and unambiguously obtained (e.g., see Chapter 15). This should be combined with calorimetric data for a more complete thermodynamic picture of the mixed admicelle. As with micelles, counterion bindings on mixed admicelles also need to be obtained in order to account for electrostatic forces properly. Only one study has measured counterion binding on single-component admicelles (3 .), with none reported for mixed admicelles. 

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