Formation micelles

Micelle formation or micellization occurs at a narrow surfactant concentration range, called the critical micelle concentration (cmc). Below the cmc, the surfactant dissolves in the molecular state. At cmc, monomeric surfactant molecules associate to form micelles and the solubility of the surfactant increases abruptly. The physical properties of the surfactant solution, such as surface tension, electric 

Micelles are in a dynamic state [15,16]. Surfactants in a micelle are mobile. Above the cmc, the molecularly dissolved surfactant molecules are in a dynamic equilibrium with the associated surfactant molecules in a micelle. A surfactant molecule may leave one micelle and adjoin another micelle. 

Micelle formation has been explained by several theories which regard the micelle as either a chemical species or a separate phase. The simplest to understand and probably the most adequate is the mass action model [17-29], which regards the micelle as a chemical species. The mass action model is based on association of monomeric surfactant molecules in dynamic equilibrium with the micelle  

The stepwise association theory, developed by Aniansson and co-workers [30-36], describes micellization as a stepwise process involving the association 

Because the association of the monomeric surfactant molecules occurs stepwise, the mass action model requires an association constant, K, , for every association step. Because of experimental limitations, numerical values for each association constant cannot be determined and have to be assumed [26,37,38]. Usually, as an approximation, a micellar solution is described with one K , value as if the solution were monodisperse. 

The situation that exists in the trough is rather more complex than this simple picture portrays. In very dilute solution, the molecules may be soluble in the water and hence there is a distribution between the bulk and surface. However, as the concentration is increased the possibility of the surfactant molecules 

A micelle will contain a number of molecules, the exact number depending upon the alkyl chain length. As the chain length is increased, so the number of molecules contained in the micelle will proportionally increase  

7 Stability Energy and Surface Area Considerations in Colloids 

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The type of behavior shown by the ethanol-water system reaches an extreme in the case of higher-molecular-weight solutes of the polar-nonpolar type, such as, soaps and detergents [91]. As illustrated in Fig. Ul-9e, the decrease in surface tension now takes place at very low concentrations sometimes showing a point of abrupt change in slope in a y/C plot [92]. The surface tension becomes essentially constant beyond a certain concentration identified with micelle formation (see Section XIII-5). The lines in Fig. III-9e are fits to Eq. III-57. The authors combined this analysis with the Gibbs equation (Section III-SB) to obtain the surface excess of surfactant and an alcohol cosurfactant. 

The examples in the preceding section, of the flotation of lead and copper ores by xanthates, was one in which chemical forces predominated in the adsorption of the collector. Flotation processes have been applied to a number of other minerals that are either ionic in type, such as potassium chloride, or are insoluble oxides such as quartz and iron oxide, or ink pigments [needed to be removed in waste paper processing [92]]. In the case of quartz, surfactants such as alkyl amines are used, and the situation is complicated by micelle formation (see next section), which can also occur in the adsorbed layer [93, 94]. 

Fuerstenau and Healy [100] and to Gaudin and Fuerstenau [101] that some type of near phase transition can occur in the adsorbed film of surfactant. They proposed, in fact, that surface micelle formation set in, reminiscent of Langmuir s explanation of intermediate type film on liquid substrates (Section IV-6). 

Other properties of association colloids that have been studied include calorimetric measurements of the heat of micelle formation (about 6 kcal/mol for a nonionic species, see Ref. 188) and the effect of high pressure (which decreases the aggregation number [189], but may raise the CMC [190]). Fast relaxation methods (rapid flow mixing, pressure-jump, temperature-jump) tend to reveal two relaxation times t and f2, the interpretation of which has been subject to much disagreement—see Ref. 191. A fast process of fi - 1 msec may represent the rate of addition to or dissociation from a micelle of individual monomer units, and a slow process of ti < 100 msec may represent the rate of total dissociation of a micelle (192 see also Refs. 193-195). 

After reviewing various earlier explanations for an adsorption maximum, Trogus, Schechter, and Wade [244] proposed perhaps the most satisfactory one so far (see also Ref. 243). Qualitatively, an adsorption maximum can occur if the surfactant consists of at least two species (which can be closely related) what is necessary is that species 2 (say) preferentially forms micelles (has a lower CMC) relative to species 1 and also adsorbs more strongly. The adsorbed state may also consist of aggregates or hemi-micelles, and even for a pure component the situation can be complex (see Section XI-6 for recent AFM evidence of surface micelle formation and [246] for polymeric surface micelles). Similar adsorption maxima found in adsorption of nonionic surfactants can be attributed to polydispersity in the surfactant chain lengths [247], Surface-active impuri-... 

Micelle formation can be treated as a mass action equilibrium, for example. 

The CMC for sodium dodecylbenzenesulfonate is about lO Af at 25°C. Calculate K for the preceding reaction, assuming that it is the only process that occurs in micelle formation. Calculate enough points to make your own quantitative plot corresponding to Fig. Xni-13. Include in your graph a plot of (Na )(R ). Note It is worthwhile to invest the time for a little reflection on how to proceed before launching into your calculation ... 

Likewise, Grieco, while working with amphiphile-like reactants, observed an enhanced preference for endo-adduct in aqueous solutions, which he attributed to orientational effects within the micelles that were presumed to be present in the reaction mixture ". Although under the conditions used by Grieco, the presence of aggregates cannot be excluded, other studies have clearly demonstrated that micelle formation is not the reason for the improved selectivities . Micellar a peg tes even tend to diminish the preference for endo adduct. ... 

Effects of Surfactants on Solutions. A surfactant changes the properties of a solvent ia which it is dissolved to a much greater extent than is expected from its concentration effects. This marked effect is the result of adsorption at the solution s iaterfaces, orientation of the adsorbed surfactant ions or molecules, micelle formation ia the bulk of the solution, and orientation of the surfactant ions or molecules ia the micelles, which are caused by the amphipathic stmcture of a surfactant molecule. The magnitude of these effects depends to a large extent on the solubiUty balance of the molecule. An efficient surfactant is usually relatively iasoluble as iadividual ions or molecules ia the bulk of a solution, eg, 10 to mol/L. 

Critical Micelle Concentration. The rate at which the properties of surfactant solutions vary with concentration changes at the concentration where micelle formation starts. Surface and interfacial tension, equivalent conductance (50), dye solubilization (51), iodine solubilization (52), and refractive index (53) are properties commonly used as the basis for methods of CMC determination. 

Mass-action model of surfactant micelle formation was used for development of the conceptual retention model in micellar liquid chromatography. The retention model is based upon the analysis of changing of the sorbat microenvironment in going from mobile phase (micellar surfactant solution, containing organic solvent-modifier) to stationary phase (the surfactant covered surface of the alkyl bonded silica gel) according to equation ... 

Salt formation. The resin acids have a low acid strength. The pa s (ionization constants) values of resin acids are difficult to obtain, and values of 6.4 and 5.7 have been reported [23] for abietic and dehydroabietic acids, respectively. Resin acids form salts with sodium and aluminium. These salts can be used in detergents because of micelle formation at low concentrations. Other metal salts (resinates) of magnesium, barium, calcium, lead, zinc and cobalt are used in inks and adhesive formulations. These resinates are prepared by precipitation (addition of the heavy metal salt to a solution of sodium resinate) or fusion (rosin is fused with the heavy metal compound). 

One of the most important characteristics of the emulsifier is its CMC, which is defined as the critical concentration value below which no micelle formation occurs. The critical micelle concentration of an emulsifier is determined by the structure and the number of hydrophilic and hydrophobic groups included in the emulsifier molecule. The hydrophile-lipophile balance (HLB) number is a good criterion for the selection of proper emulsifier. The HLB scale was developed by W. C. Griffin [46,47]. Based on his approach, the HLB number of an emulsifier can be calculated by dividing... 

Kitahara, A., Kon-No, R. Micelle formation in non aqueous media, in Colloidal dispersions and micellar behaviour. ACS-Symposia Series 9, 225 (1975)... 

Several studies have been performed to investigate the compatibalizing effect of blockcopolymers [67,158, 188,196-200], It is generally shown that the diblock copolymer concentration is enhanced at the interface between incompatible components when suitable materials are chosen. Micell formation and extremely slow kinetics make these studies difficult and specific non-equilibrium starting situations are sometimes used. Diblock copolymers are tethered to the interface and this aspect is reviewed in another article in this book [14]. 

In highly diluted solutions the surfactants are monodispersed and are enriched by hydrophil-hydrophobe-oriented adsorption at the surface. If a certain concentration which is characteristic for each surfactant is exceeded, the surfactant molecules congregate to micelles. The inside of a micelle consists of hydrophobic groups whereas its surface consists of hydrophilic groups. Micelles are dynamic entities that are in equilibrium with their surrounded concentration. If the solution is diluted and remains under the characteristic concentration, micelles dissociate to single molecules. The concentration at which micelle formation starts is called critical micelle concentration (cmc). Its value is characteristic for each surfactant and depends on several parameters [189-191] ... 

Influence of branching. The branched chain compounds are also able to form micelles, but compared to the straight-chain substances the cmc is always higher. Micelle formation is apparently complicated by the branching. Importance of the aromatic ring. Because of the higher local requirements, the benzene ring in LAS resp. TPBS causes an increase in surface activity and a reduction of cmc. 

The micelle formation enthalpies (Fig. 30) calculated according to a mass action approach by Burchfield and Woolley [52] (Table 19) become more exo-... 

TABLE 19 Enthalpies of Micelle Formation for Alkanesulfonates in Water... 

Because of their preferential use as detergents, the main interest in the physicochemical properties of the salts of a-sulfo fatty acid esters is related to their behavior in aqueous solution and at interfaces. In principle these are surface-active properties of general interest like micelle formation, solubility, and adsorption, and those of interest for special applications like detergency, foaming, and stability in hard water. 

Fujiwara et al. used the CMC values of sodium and calcium salts to calculate the energetic parameters of the micellization [61]. The cohesive energy change in micelle formation of the a-sulfonated fatty acid methyl esters, calculated from the dependency of the CMC on the numbers of C atoms, is equivalent to that of typical ionic surfactants (Na ester sulfonates, 1.1 kT Ca ester sulfonates, 0.93 kT Na dodecyl sulfate, 1.1 kT). The degree of dissociation for the counterions bound to the micelle can be calculated from the dependency of the CMC on the concentration of the counterions. The values of the ester sulfonates are also in the same range as for other typical ionic surfactants (Na ester sulfonates, 0.61 Ca ester sulfonates, 0.70 Na dodecyl sulfate, 0.66). 

Within the small intestine, bile-acid binding interferes with micelle formation. Nauss et al. [268] reported that, in vitro, chitosan binds bile acid micelles in toto, with consequent reduced assimilation of all micelle components, i.e., bile acids, cholesterol, monoglycerides and fatty acids. Moreover, in vitro, chitosan inhibits pancreatic lipase activity [269]. Dissolved chitosan may further depress the activity of lipases by acting as an alternative substrate [270]. 

The reader is encouraged to run this model and collect the average cluster size of amphiphile cells. Observing the run reveals a view of the emergent property known as micelle formation. Periodic halting of the run when these micelles are prominent will be of interest. Try a screen grab of several good examples. 

Study 5.3. Water temperature effects on micelle formation... 

L. B. Kier, C.-K. Cheng, andB. Testa, Cellular automata model of micelle formation. Pharm. Res. 1996, 13, 1419. 

Studies described in earlier chapters used cellular automata dynamics to model the hydrophobic effect and other solution phenomena such as dissolution, diffusion, micelle formation, and immiscible solvent demixing. In this section we describe several cellular automata models of the influence of the hydropathic state of a surface on water and on solute concentration in an aqueous solution. We first examine the effect of the surface hydropathic state on the accumulation of water near the surface. A second example models the effect of surface hydropathic state on the rate and accumulation of water flowing through a tube. A final example shows the effect of the surface on the concentration of solute molecules within an aqueous solution. 

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