Amphiphiles surface tension

Lattice models have been studied in mean field approximation, by transfer matrix methods and Monte Carlo simulations. Much interest has focused on the occurrence of a microemulsion. Its location in the phase diagram between the oil-rich and the water-rich phases, its structure and its wetting properties have been explored [76]. Lattice models reproduce the reduction of the surface tension upon adsorption of the amphiphiles and the progression of phase equilibria upon increasmg the amphiphile concentration. Spatially periodic (lamellar) phases are also describable by lattice models. Flowever, the structure of the lattice can interfere with the properties of the periodic structures. 

The monolayer resulting when amphiphilic molecules are introduced to the water—air interface was traditionally called a two-dimensional gas owing to what were the expected large distances between the molecules. However, it has become quite clear that amphiphiles self-organize at the air—water interface even at relatively low surface pressures (7—10). For example, x-ray diffraction data from a monolayer of heneicosanoic acid spread on a 0.5-mM CaCl2 solution at zero pressure (11) showed that once the barrier starts moving and compresses the molecules, the surface pressure, 7T, increases and the area per molecule, M, decreases. The surface pressure, ie, the force per unit length of the barrier (in N/m) is the difference between CJq, the surface tension of pure water, and O, that of the water covered with a monolayer. Where the total number of molecules and the total area that the monolayer occupies is known, the area per molecules can be calculated and a 7T-M isotherm constmcted. This isotherm (Fig. 2), which describes surface pressure as a function of the area per molecule (3,4), is rich in information on stabiUty of the monolayer at the water—air interface, the reorientation of molecules in the two-dimensional system, phase transitions, and conformational transformations. 

Bilayers have received even more attention. In the early studies, water has been replaced by a continuous medium as in the monolayer simulations [64-67]. Today s bilayers are usually fully hydrated , i.e., water is included exphcitly. Simulations have been done at constant volume [68-73] and at constant pressure or fixed surface tension [74-79]. In the latter case, the size of the simulation box automatically adjusts itself so as to optimize the area per molecule of the amphiphiles in the bilayer [33]. If the pressure tensor is chosen isotropic, bilayers with zero surface tension are obtained. Constant... 

The formation of a microphase structure leads to a surface-active effect [31]. The surface tension of water is considerably lowered when amphiphilic copolymers are dissolved. The surface-active effect appears more significantly in the copolymers with more hydrophobic units. 

Phosphorus-containing surfactants are amphiphilic molecules, exhibiting the same surface-active properties as other surfactants. That means that they reduce the surface tension of water and aqueous solutions, are adsorbed at interfaces, form foam, and are able to build micelles in the bulk phase. On account of the many possibilities for alteration of molecular structure, the surface-active properties of phosphorus-containing surfactants cover a wide field of effects. Of main interest are those properties which can only be realized with difficulty or in some cases not at all by other surfactants. Often even quantitative differences are highly useful. 

There is a group of substances, in the presence of which significant changes in the surface tension of the ITIES were observed, which are also likely to influence the differential capacity of the ITIES correspondingly. These substances include various ionic and nonionic surfactants (Section IV.B.2) and amphiphilic phospholipids (Section IV.B.3) or affinity dyes. Attention has focused on phospholipids. 

Surface active agents (surfactants) are active (adsorb) at surfaces and reduce surface tensions. Surfactants work because they are amphiphilic they have opposing solubility tendencies in one molecule, such as a hydrocarbon chain and a polar end. Because of this disparity in solubility, they tend to form concentration gradients at dissimilar phase interfaces. Surfactant additives are classified according to the interface at which they are active. 

Onset of micellization is detected by sharp changes in such properties as surface tension, refractivity or conductivity (of ionic micelles). To a first approximation the solution is assumed to contain monomeric amphiphiles, whose concentration is given by the cmc, and fully formed micelles, with submicellar aggregates playing a minor role. 

A special class ofblock copolymers with blocks of very different polarity is known as amphiphilic (Figure 10.1). In general, the word amphiphile is used to describe molecules that stabilize the oil-water interface (e.g., surfactants). To a certain extent, amphiphilic block copolymers allow the generalization of amphi-philicity. This means that molecules can be designed that stabilize not only the oil-water interface but any interface between different materials with different cohesion energies or surface tensions (e.g., water-gas, oil-gas, polymer-metal, or polymer-polymerinterfaces). This approach is straightforward, since the wide variability of the chemical structure of polymers allows fine and specific adjustment of both polymer parts to any particular stabilization problem. 

For instance, surfactants dissolve in water and give rise to low surface tension even at very low concentrations (a few grams per liter or 1-100 mmol/L) of the solution therefore, these substances are also called surface-active molecules (surface-active agents or substances). On the other hand, most inorganic salts increase the surface tension of water. All surfactant molecules are amphiphilic, which means that these molecules exhibit hydrophilic and hydrophobic properties. Ethanol reduces the surface tension of water, but one will need over a few moles per liter to obtain the same reduction as when using a few millimoles of surface-active agents. 

The effect of chain length on surface tension arises from the fact that, as the hydrophobicity increases with each -CH2- group, the amphiphile molecule adsorbs more at the surface. This will thus be a general trend in more complicated molecules also, such as proteins and other polymers. In proteins, the amphiphilic property arises from the different kinds of amino acids (25 different amino acids). Some amino acids have lipophilic groups (such as phenylalanine, valine, leucine, etc.), while others have hydrophilic groups (such as glycine, aspartic acid, etc.) (Figure 3.4). 

The solubility characteristics of surfactants (in water) is one of the most studied phenomena. Even though the molecular structures of surfactants are rather simple, their solubility in water is rather complex as compared to other amphiphiles such as long-chain alcohols, etc., in that it is dependent on the alkyl group. This is easily seen since the alkyl groups will behave mostly as alkanes. The hydrophobic alkyl part exhibits solubility in water, which has been related to a surface tension model of the cavity (see Appendix B). However, it is found additionally that the solubility... 

If one adds an inorganic salt, such as NaCl, instead of detergent, then no foam is formed. Foam formation indicates that the surface-active agent adsorbs at the surface, and forms a TLF (consisting of two layers of amphiphile molecules and some water). This has led to many theoretical analyses of surfactant concentration (in the bulk phase) and surface tension (consequent on the presence of surfactant molecules at the surface). The thermodynamics of surface adsorption has been extensively described by the Gibbs adsorption theory (Chattoraj and Birdi, 1984). 

If one places a very small amount of a lipid on the surface of water, it may affect surface tension in different ways. It may not show any effect (such as in the case of cholesterol), or it may show a drastic decrease in surface tension (such as in the case of stearic acid or tetra-decanol). An amphiphile molecule will adsorb at the... 

It is thus seen that the II of a monolayer is the lowering of surface tension due to the presence of monomolecular film. This arises from the orientation of the amphiphile molecules at the air-water or oil-water interface, where the polar group would be oriented towards the water phase, while the nonpolar part (hydrocarbon) would be oriented away from the aqueous phase. This orientation produces a system with minimum free energy. 

As is known, if one blows air bubbles in pure water, no foam is formed. On the other hand, if a detergent or protein (amphiphile) is present in the system, adsorbed surfactant molecules at the interface produce foam or soap bubble. Foam can be characterized as a coarse dispersion of a gas in a liquid, where the gas is the major phase volume. The foam, or the lamina of liquid, will tend to contract due to its surface tension, and a low surface tension would thus be expected to be a necessary requirement for good foam-forming property. Furthermore, in order to be able to stabilize the lamina, it should be able to maintain slight differences of tension in its different regions. Therefore, it is also clear that a pure liquid, which has constant surface tension, cannot meet this requirement. The stability of such foams or bubbles has been related to monomolecular film structures and stability. For instance, foam stability has been shown to be related to surface elasticity or surface viscosity, qs, besides other interfacial forces. 

At this stage in the literature, there is no method available by which one can directly determine the orientation of molecules of liquids at interfaces. Molecules are situated at interfaces (e.g., air-liquid, liquid-liquid, and solid-liquid) under asymmetric forces. Recent studies have been carried out to obtain information about molecular orientation from surface tension studies of fluids (Birdi, 1997). It has been concluded that interfacial water molecules, in the presence of charged amphiphiles, are in a tetrahedral arrangement similar to the structure of ice. Extensive studies of alkanes... 

Finally there are dynamic methods to measure the surface tension. For example, a liquid jet is pushed out from a nozzle, which has an elliptic cross-section. The relaxation to a circular cross-section is observed. An advantage of this method is that we can measure changes of the surface tension, which might be caused by diffusion of amphiphilic substances to the surface. 

This is a very important equation. It directly tells us that when a solute is enriched at the interface (T > 0), the surface tension decreases when the solution concentration is increased. Such solutes are said to be surface active and they are called surfactants or surface active agents. Often the term amphiphilic molecule or simply amphiphile is used. An amphiphilic molecule consist of two well-defined regions One which is oil-soluble (lyophilic or hydrophobic) and one which is water-soluble (hydrophilic). 

Plots of surface tension versus concentration for n-pentanol [49], LiCl (based on Ref. [50]), and SDS in an aqueous medium at room temperature are shown in Fig. 3.7. The three curves are typical for three different types of adsorption. The SDS adsorption isotherm is typical for amphiphilic substances. In many cases, above a certain critical concentration defined aggregates called micelles are formed (see Section 12.1). This concentration is called the critical micellar concentration (CMC). In the case of SDS at 25°C this is at 8.9 mM. Above the CMC the surface tension does not change significantly any further because any added substance goes into micelles not to the liquid-gas interface. 

The adsorption isotherm for pentanol is typical for lyophobic substances, i.e., substances which do not like to stay in solution, and for weakly amphiphilic substances. They become enriched in the interface and decrease the surface tension. If water is the solvent, most organic substances show such a behaviour. The LiCl adsorption isotherm is characteristic for lyophilic substances. Most ions in water show such behaviour. 

If there is still a significant proportion of the amphiphile dissolved in the liquid we talk about Gibbs monolayers. Solubility in water is increased by using molecules with short alkyl chain or a high polarity of the headgroup. In this case T is determined from the reduction of the surface tension according to the Gibbs adsorption isotherm (Eq. 3.52). 

At low surface excess, Gibbs monolayers can often be described as two-dimensional gases. This description is based on the observation that, at low concentration, the surface tension decreases linearly with the concentration of the added amphiphile c ... 

Keywords Interface Langmuir monolayer Adsorption process Spreading solvent Surface tension Surface isotherm Langmuir-Blodgett film Collapse pressure Amphiphilic polymer... 

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