Surfactant molecules, packing

Let us now discuss some applications of microemulsions in catalytic processes. It has been shown in [298] that the use of microemulsions instead of organic solvents for electrochemical reactions is advantageous from both economical and ecological reasons. The electrode/fluid interface in microemulsions probably consists of a dynamic layer of surfactant molecules packed more loosely on the electrode than in aqueous solutions. Microemulsions provide good yields of carbon-carbon addition products in reactions catalysed by cobalt complexes when preparing vitamin B 2. Excellent stereo-selective control in microemulsions made with the cationic surfactant cetyl trimethyl ammonium bromide was demonstrated for the catalytic cyclisation of 2-(4-bromobutyl)-2-cycIohexene-l-one to 1-decalone. Electrochemical synthesis may be a viable future approach to environmentally friendly chemical methods. 

Effective shape of the surfactant molecule Packing parameter "m.of/r Aggregate morphology... 

The Gibbs equation allows the amount of surfactant adsorbed at the interface to be calculated from the interfacial tension values measured with different concentrations of surfactant, but at constant counterion concentration. The amount adsorbed can be converted to the area of a surfactant molecule. The co-areas at the air-water interface are in the range of 4.4-5.9 nm2/molecule [56,57]. A comparison of these values with those from molecular models indicates that all four surfactants are oriented normally to the interface with the carbon chain outstretched and closely packed. The co-areas at the oil-water interface are greater (heptane-water, 4.9-6.6 nm2/molecule benzene-water, 5.9-7.5 nm2/molecule). This relatively small increase of about 10% for the heptane-water and about 30% for the benzene-water interface means that the orientation at the oil-water interface is the same as at the air-water interface, but the a-sulfo fatty acid ester films are more expanded [56]. 

Monolayers of surfactants at the air-water interface provide an unparalleled opportunity to study energy changes due to differences in orientation of the surfactant molecules as they are packed within various areas on the surface. The work reviewed here, from a small number of studies that have been widely scattered through the literature, shows that the surface properties of monolayers are quite sensitive to stereochemistry. 

Arborol Dendrimers. The spherical topology of dendrimers resembles the size and shape of the Hartley model (1936) of a micellar aggregate formed by surfactant molecules (Fig. 11.2 Tomalia et al. 1990). Micellar stmctuies have a dynamic, spherical structure possessing a close-packed, solvent-incompatible core surrounded by an open, solvent-compatible layer. 

Different surfactants are usually characterised by the solubility behaviour of their hydrophilic and hydrophobic molecule fraction in polar solvents, expressed by the HLB-value (hydrophilic-lipophilic-balance) of the surfactant. The HLB-value of a specific surfactant is often listed by the producer or can be easily calculated from listed increments [67]. If the water in a microemulsion contains electrolytes, the solubility of the surfactant in the water changes. It can be increased or decreased, depending on the kind of electrolyte [68,69]. The effect of electrolytes is explained by the HSAB principle (hard-soft-acid-base). For example, salts of hard acids and hard bases reduce the solubility of the surfactant in water. The solubility is increased by salts of soft acids and hard bases or by salts of hard acids and soft bases. Correspondingly, the solubility of the surfactant in water is increased by sodium alkyl sulfonates and decreased by sodium chloride or sodium sulfate. In the meantime, the physical interactions of the surfactant molecules and other components in microemulsions is well understood and the HSAB-principle was verified. The salts in water mainly influence the curvature of the surfactant film in a microemulsion. The curvature of the surfactant film can be expressed, analogous to the HLB-value, by the packing parameter Sp. The packing parameter is the ratio between the hydrophilic and lipophilic surfactant molecule part [70] ... 

Introduction to the variety of types of surfactants, effect of surfactants on aqueous solution properties. Law of mass action applied to the self-assembly of surfactant molecules in water. Spontaneous self-assembly of surfactants in aqueous media. Formation of micelles, vesicles and lamellar structures. Critical packing parameter. Detergency. Laboratory project on determining the charge of a micelle. 

Explain the link between the critical packing parameter and the interaction forces between surfactant molecules in water. 

Very recently, ESR techniques have been employed to study the packing of surfactant molecules at the oil/water interface in w/o HIPEs [102,103], By including an amphiphilic ESR probe, which is adsorbed at the oil/water interfaces, it is possible to determine the microstructure of the oil phase from the distribution of amphiphiles between the films surrounding the droplets and the reverse micelles. It was found that most of the surfactant is located in the micelles, over a wide range of water fraction values. However, when the water content is very high (water droplets of the emulsion, to stabilise the large interfacial area created. 

In the gel phases of these systems [310], the surfactant molecules are in extended conformations and packed hexagonally in bilayers. A cut-away cartoon representation of the layers is presented in Figure 56 the KS and KP gel layers are nearly completely interdigitated the KSO gel layers are without interdigitation, and KS and 1-octadecanol molecules alternate within a hexagonal layer. 

The packing parameter of the neighboring surfactant molecules reflects the molecular dimension and is related to the macroscopic curvatures (Gaussian and mean curvature) of the surface imposed by the topology of the coverage relation (127). 

It is often desirable (e.g. in emulsions) to have a surface film of charged species however, as such, repulsion between the head groups usually makes such a film non-coherent. Surface films which are both charged and coherent can be produced by use of a mixture of ionic and non-ionic surfactants, especially where the structural characteristics of the surfactant molecules are such that they pack efficiently between one another. 

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