Surfactant monomers

Resolution at tire atomic level of surfactant packing in micelles is difficult to obtain experimentally. This difficulty is based on tire fundamentally amoriDhous packing tliat is obtained as a result of tire surfactants being driven into a spheroidal assembly in order to minimize surface or interfacial free energy. It is also based upon tire dynamical nature of micelles and tire fact tliat tliey have relatively short lifetimes, often of tire order of microseconds to milliseconds, and tliat individual surfactant monomers are coming and going at relatively rapid rates. 

The model was tested by the micellar liquid chromatography separ ation of the five rarbornicin derivatives and four ethers of hydroxybenzoic acid. Micellar mobile phases were made with the sodium dodecylsulfate and 1-pentanol or isopentanol as modifier. In all cases the negative signs of the coefficients x and y indicate that at transition of the sorbat from the mobile on the stationar y phase the number of surfactant monomers as well as the number of modifier molecules increases in its microenvironment. 

The structure of these globular aggregates is characterized by a micellar core formed by the hydrophilic heads of the surfactant molecules and a surrounding hydrophobic layer constituted by their opportunely arranged alkyl chains whereas their dynamics are characterized by conformational motions of heads and alkyl chains, frequent exchange of surfactant monomers between bulk solvent and micelle, and structural collapse of the aggregate leading to its dissolution, and vice versa [2-7]. 

Moreover, taking into account that reversed micelles coexist with surfactant monomers, in principle, further effects due to the aggregation of polar and amphiphilic so-lubihzates with surfactant monomers and the shift of the monomer/reversed micelle equilibrium must be also considered [25,26],... 

The differences between the two curves can be explained by the sulfonate (the most adsorbed surfactant) monomer concentrations at equilibrium, which were reached in both cases, considering the amounts of surfactants, liquid and solid present. Figure 4 shows a distinct evolution of monomer concentrations for the two solid/liquid ratios considered. 

But this static picture is clearly inadequate, because solutes and surfactant monomers move rapidly from water to micelles, and the surfactant head groups will oscillate about some mean position at the micelle surface (Aniansson, 1978). Non-ionic substrates are not localized within the micelle or its Stern layer and there is no reason to believe that they are distributed uniformly within the Stern layer. 

Figure 10.11 As the aggregate number n increases, so the fraction of the added surfactant that goes into the micelle (as y ) varies more steeply with total concentration of surfactant monomer (as V). The critical micelle concentration (CMC) is the midpoint of the region over which the concentration of the micelle changes (Reproduced by permission of Wiley Interscience, from The Colloidal Domain by D. Fennell Evans and Hakan Wennerstrom)...

The association forces between juxtaposed surfactant monomers is physical, not chemical, so the motion of the hydrocarbon tails within a micelle is similar to the local motion in a sample of pure hydrocarbon. 

Each micelle has a polar periphery and an oil-like core. When molecules of monomer collide with the solid surface of, say, a dirty plate, the non-polar ( hydrophobic ) end adsorbs to the non-polar grease. Conversely, the polar ( hydrophilic ) end readily solvates with water. Soon, each particle of oil or grease is surrounded with a protective coating of surfactant monomer, according to Figure 10.13. 

Plateau adsorption could correspond to either complete surface coverage or a value limited by constant surfactant monomer activity in solution as a result of bulk micellization. 

While CMC is assumed to be an observable and definite value in the case of surfactant monomers, there are frequent reports in the literature of the formation of aggregates or micelle-like associations in solutions of organic solutes so dilute as to preclude apparently the formation of micelles [208, 267-269, 272, 275,278]. Work with different types of commercial surfactants has indicated that molecularly non-homogeneous surfactants do not display the sharp inflection in surface tension associated with CMC in molecularly homogeneous monomers, but rather the onset of aggregation is broad and indistinct [253,267,268]. The lack of well-defined CMCs for non-homogeneous surfactants is speculated to result from the successive micellization of the heterogeneous monomers at different stoichiometric concentrations of the surfactant, which results in a breadth of the monomeric-micelle transition zone. 

Since oleic acid is relatively polar, it may become emulsified by the surfactant monomer. The removal of oleic acid comes mainly from two contributions monomer emulsification and micellar solubilization. Although the Vgjj has been decreased with increasing EO number in dodecanol ethoxylates, in higher EO numbers than 5, this factor has been compensated by the Increase of monomer with increasing EO number (CMC decreases with EO number). The levelling of detergency of dodecanol ethoxylates from EO number 5 to EO number 8 has been interpreted by these reasons. The monomer emulsification of oleic acid has been clearly shown in this paper in SDS solution. The nonionic surfactants we used here have low EO numbers and show mainly the effect of solubilization. 

NSD ionic surfactant monomers + Cs+ counter = micelle with charge... 

Consequently, the SDS microemulsion system is the best model for indirect measurement of log Pow. However, this is valid only for neutral solutes. We reported that the relationship between MI and log Pow for ionic solutes is different from that for neutral solutes (49). This would be caused by the ionic interaction between ionic solutes and the ionic microemulsion as well as ionic surfactant monomer in the aqueous phase. Kibbey et al. used pH 10 buffer for neutral and weak basic compounds and pH 3 buffer for weak acidic compounds (53). Although their purpose was to avoid measuring electrophoretic mobility in the aqueous phase, this approach is also helpful for measuring log Pow indirectly. 

Typical radii for spherical micelles (related to the length of a typical surfactant tail) are around 5 nm. Aggregation numbers N (surfactant monomers per micelle) are typically 40-100. The fractional counterion binding of micelles [3 generally lies... 

Calculated concentrations, using (4.9), for the various components, surfactant monomers, counter-ions and micelles, for the case of CTAB micellization (with a cmc of 0.9mM), is shown in Figure 4.5. Clearly, the micelle concentration increases rapidly at the cmc, which explains the sharp transition in surfactant solution properties referred to earlier. It is also interesting to note that the law of mass action (in the form of equation 4.9) predicts an increase in counterion (Br ions) concentration and a decrease in free monomer concentration above the cmc. It has been proposed that for ionic surfactants, a useful definition of the cmc would be... 

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. 

In order to illustrate the eFFect oF micellar nonidealities oF mixing on total surFactant monomer concentrations and micelle compositions in a system at the CHC, consider a hypothetical binary surFactant pair, A and B. Assume CMCa = 1 mli and CMCb = 2 mil. For a equimolar mixture oF A and B as monomer, the values oF Cn and micelle compositions are tabulated in Table I at various values oF W/RT. 

In the case of non—eutectic systems, the solid phase shows nearly ideal mixing, so that the surfactant components distribute themselves between the micelle and the solid in about the same relative proportions (i.e., both the mixed micelle and mixed solid are approximately ideal). However, in the case of the eutectic type system, the crystal is extremely non-ideal (almost a single component), while the micelle has nearly ideal mixing. As seen in earlier calculations for ideal systems, even though the total surfactant monomer concentration is intermediate between that of the pure components, the monomer concentration of an individual component decreases as its total proportion in solution decreases. As the proportion of surfactant A decreases in solution (proportion of surfactant B increases) from pure A, there is a lower monomer concentration of A. Therefore, it requires a lower temperature or a higher added electrolyte level to precipitate it. At some... 

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