Micellar solution mixed micelles

Medium-chain alcohols such as 2-butoxyethanol (BE) exist as microaggregates in water which in many respects resemble micellar systems. Mixed micelles can be formed between such alcohols and surfactants. The thermodynamics of the system BE-sodlum decanoate (Na-Dec)-water was studied through direct measurements of volumes (flow denslmetry), enthalpies and heat capacities (flow microcalorimetry). Data are reported as transfer functions. The observed trends are analyzed with a recently published chemical equilibrium model (J. Solution Chem. 13,1,1984). By adjusting the distribution constant and the thermodynamic property of the solute In the mixed micelle. It Is possible to fit nearly quantitatively the transfer of BE from water to aqueous NaDec. The model Is not as successful for the transfert of NaDec from water to aqueous BE at low BE concentrations Indicating self-association of NaDec Induced by BE. The model can be used to evaluate the thermodynamic properties of both components of the mixed micelle. 

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-... 

Fig. 2 (a-c) Physical polymer-network cross-linking provided by mixed micelles in hydrogels formed via hydrophobic interactions in surfactant solutions. Mixed micelles are formed by aggregation of hydrophobic blocks of per-se hydrophilic polymers and surfactant alkyl tails, (b) Nonionic polymer and ionic surfactant gel system at the state of preparation. For clarity, charges are not shown, (c) Ionic polymer and oppositely charged surfactant gel system after extraction of free micelles, (d) Structure of the hydrophobic monomers used in the micellar polymerization... 

Tian et al. used sedimentation velocity measurements to study the rate of micelle hybridization when two micellar solutions containing micelles made up from two different di-or triblock copolymers of st3rrene and methacrylic acid are mixed. Dioxane/water mixtures were used as solvents. In contrast to results reported in References 71 and 72, the exchange kinetics was found to depend veiy strongly on the composition, molecular weight, and architecture of the copolymer and also on the quality of the solvent (thermod3mamic control). 

Small micelles in dilute solution close to the CMC are generally beheved to be spherical. Under other conditions, micellar materials can assume stmctures such as oblate and prolate spheroids, vesicles (double layers), rods, and lamellae (36,37). AH of these stmctures have been demonstrated under certain conditions, and a single surfactant can assume a number of stmctures, depending on surfactant, salt concentration, and temperature. In mixed surfactant solutions, micelles of each species may coexist, but usually mixed micelles are formed. Anionic-nonionic mixtures are of technical importance and their properties have been studied (38,39). 

Kang, J. W., De Reymaeker, G., Van Schepdael, A., Roets, E., and Hoogmartens, J. (2001). Analysis of bacitracin by micellar electrokinetic capillary chromatography with mixed micelle in acidic solution. Electrophoresis 22, 1356-1362. 

Of the possible types of measurements, heats of micellar mixing obtained from the mixing of pure surfactant solutions are perhaps of the greatest interest. Also of interest is the titration (dilution) of mixed micellar solutions to obtain mixed erne s. While calorimetric measurements have been applied in studies of pure surfactants (6,7) and their interaction with polymers ( ), to our knowledge, applications of calorimetry to problems of nonideal mixed micellization have not been previously reported in the literature. 

Among the purposes of this paper is to report the results of calorimetric measurements of the heats of micellar mixing in some nonideal surfactant systems. Here, attention is focused on interactions of alkyl ethoxylate nonionics with alkyl sulfate and alkyl ethoxylate sulfate surfactants. The use of calorimetry as an alternative technique for the determination of the cmc s of mixed surfactant systems is also demonstrated. Besides providing a direct measurement of the effect of the surfactant structure on the heats of micellar mixing, calorimetric results can also be compared with nonideal mixing theory. This allows the appropriateness of the regular solution approximation used in models of mixed micellization to be assessed. 

The finding that the assumptions of the regular solution approximation do not hold for the mixed micellar systems investigated here suggests a re-examination of how the thermodynamics of mixing enter the nonideal mixed micelle model. 

The mixed cmc behavior of these (and many other) mixed surfactant systems can be adequately described by a nonideal mixed micelle model based on the psuedo-phase separation approach and a regular solution approximation with a single net interaction parameter B. However, the heats of micellar mixing measured by calorimetry show that the assumptions of the regular solution approximation do not hold for the systems investigated in this paper. This suggests that in these cases the net interaction parameter in the nonideal mixed micelle model should be interpreted as an excess free energy parameter. 

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,... 

For Eq. (2) it is assumed that the volume of the micellar phase is proportional to the tenside concentration and that the partial molar volume v remains constant. (See Chapter 2.) A further prerequisite for the application of Eq. (2) is a constant ionic mobility of the micellar phase independent of the uptake of a solute (/x, . = const.). In contrast to HPLC, substances that have an infinitely high kP value, i.e., that are completely dissolved in the micellar phase, can be detected. In this case the sample molecule migrates with the mobility of the micelle. In the presence of several different micellar phases (coexistence of simple and mixed micelles), the calculation of kP is possible only when partial capacity factors are known (20). The determination of kP is then considerably more complicated. 

The structure and thermodynamics of formation of mixed micelles is of great theoretical interest. Micelles are also present and often integrally involved in practical processes. For example, in a small pore volume surfactant flooding process (sometimes called micellar flooding), the solution injected into an oil field generally contains 5-12 weight X surfactant (i) and the surfactant is predominately in micellar form in the reservoir water. In detergency, solubilization can be... 

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. 

Most of the studies on thermodynamics of mixed micellar systems are based on the variation of the critical micellar concentration (CMC) with the relative concentration of both components of the mixed micelles (1-4). Through this approach It Is possible to obtain the free energies of formation of mixed micelles. However, at best, the sign and magnitude of the enthalpies and entropies can be obtained from the temperature dependences of the CMC. An Investigation of the thermodynamic properties of transfer of one surfactant from water to a solution of another surfactant offers a promising alternative approach ( ), and, recently, mathematical models have been developed to Interpret such properties (6-9). 

The chemical equilibrium model of Roux et al (6) is a powerful tool for the study of the thermodynamics of mixed micellar solutions. It can estimate the distribution constant of the surfactant 3 between water and micelles of the surfactant 2 and the thermodynamic properties of the surfactant 3 in the mixed micelles. For this it is necessary to obtain reliable data over a large concentration range of solute 2. 

A generalized nonideal mixed monolayer model based on the pseudo-phase separation approach is presented. This extends the model developed earlier for mixed micelles (J. Phys. Chem. 1983 87, 1984) to the treatment of nonideal surfactant mixtures at interfaces. The approach explicity takes surface pressures and molecular areas into account and results in a nonideal analog of Butler s equation applicable to micellar solutions. Measured values of the surface tension of nonideal mixed micellar solutions are also reported and compared with those predicted by the model. 

The purpose of this paper will be to develop a generalized treatment extending the earlier mixed micelle model (I4) to nonideal mixed surfactant monolayers in micellar systems. In this work, a thermodynamic model for nonionic surfactant mixtures is developed which can also be applied empirically to mixtures containing ionic surfactants. The form of the model is designed to allow for future generalization to multiple components, other interfaces and the treatment of contact angles. The use of the pseudo-phase separation approach and regular solution approximation are dictated by the requirement that the model be sufficiently tractable to be applied in realistic situations of interest. 

In a previous publication ( ), results were presented on the micellar properties of binary mixtures of surfactant solutions consisting of alkyldimethylamine oxide (C12 to Cig alkyl chains) and sodium dodecyl sulfate. It was reported that upon mixing, striking alteration in physical properties was observed, most notably in the viscosity, surface tension, and bulk pH values. These changes were attributed to 1) formation of elongated structures, 2) protonation of amine oxide molecules, and 3) adsorption of hydronium ions on the mixed micelle surface. In addition, possible solubilisation of a less soluble 1 1 complex, form between the protonated amine oxide and the long chain sulfate was also considered. 

Surfactant Activity in Micellar Systems. The activities or concentrations of individual surfactant monomers in equilibrium with mixed micelles are the most important quantities predicted by micellar thermodynamic models. These variables often dictate practical performance of surfactant solutions. The monomer concentrations in mixed micellar systems have been measured by ultraf i Itration (I.), dialysis (2), a combination of conductivity and specific ion electrode measurements (3), a method using surface tension of mixtures at and above the CMC <4), gel filtration (5), conductivity (6), specific ion electrode measurements (7), NMR <8), chromatograph c separation of surfactants with a hydrophilic substrate (9> and by application of the Bibbs-Duhem equation to CMC data (iO). Surfactant specific electrodes have been used to measure anionic surfactant activities in single surfactant systems (11.12) and might be useful in mixed systems. ... 

As already discussed in Chapter 1, the relative tendency of a surfactant component to adsorb on a given surface or to form micelles can vary greatly with surfactant structure. The adsorption of each component could be measured below the CMC at various concentrations of each surfactant in a mixture. A matrix could be constructed to tabulate the (hopefully unique) monomer concentration of each component in the mixture corresponding to any combination of adsorption levels for the various components present. For example, for a binary system of surfactants A and B, when adsorption of A is 0.5 mmole/g and that of B is 0.3 mmole/g, there should be only one unique combination of monomer concentrations of surfactant A and of surfactant B which would result in this adsorption (e.g., 1 mM of A and 1.5 mM of B). Uell above the CMC, where most of the surfactant in solution is present as micelles, micellar composition is approximately equal to solution composition and is, therefore, known. If individual surfactant component adsorption is also measured here, it would allow computation of each surfactant monomer concentration (from the aforementioned matrix) in equilibrium with the mixed micelles. Other processes dependent on monomer concentration or surfactant component activities only could also be used in a similar fashion to determine monomer—micelle equilibrium. 

In aqueous surfactant solutions, either by circumstance or design, non—surface active organic species may be present. Examples are oil recovery, where crude oil is present, or micellar—enhanced ultrafiltration, where micelles are being used to effect a separation of dissolved organic pollutants from water. The ability of mixed micelles to solubilize organic solutes has received relatively little study. In addition, the solubilization of these compounds by micelles may change the monomer—micelle equilibrium compositions. 

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