Water hydrocarbon surfactants

Microemulsions are isotropic and optically clear dispersions of hydro-carbons-in-water or water-in-hydrocarbons, where oil or water droplets are small (5-50 nm). Microemulsions are also thermodynamically stable and they remain clear indefinitely. They form spontaneously when water, hydrocarbon, surfactant and cosurfactant are mixed in specific proportions. Since microemulsions contain no defined supramolecular structures whatsover, they are of limited interest to organic chemists. 

Each of the six components in the community of molecules (water, hydrocarbon, surfactant, cosurfactant, oxidant and substrate) functions only by virtue of cooperative action, i.e. water acts as a solvent for the inorganic reagent the cyclohexane droplets dissolve the substrate both immiscible components must be combined with the mediation of the surfactant SDS and the cosurfactant butanol fills the space between the charged SDS molecules. The result is, the droplets cannot grow and the emulsion becomes stable. There is a possibility that such microemulsions could work with several hydro-phobic, environmentally contaminating materials and that the structurally... 

The formation of three different condensed phases in the water-hydrocarbon-surfactant system allows one to measure the surface tension at the three interfaces, and to study the a(T) dependence at them (VI-19). Due to the dehydration of surfactant molecules, the interfacial tension at the aqueous solution - microemulsion interface, ow.me, increases with temperature, while the interfacial tension at the microemulsion - oil interface, a0.me, drops until a complete vanishing of this interface occurs. For the hydro carbon-water... 

The interfacial tension can undergo significant changes if the polarity of the medium is altered, such as in the stability/coagulation transition caused by the addition of water to hydrophobic silica dispersions in propanol or ethanol [44,52,53]. Also, the addition of small additives of various surface-active substances can have a dramatic effect on the structure and properties of disperse systems and the conditions of transitions [14,16,17,26]. The formation and structure of stable micellar systems and various surfactant association colloids, such as microemulsion systems and liquid crystalline phases formed in various multicomponent water/hydrocarbon/surfactant/alcohol systems with varying compositions and temperatures, have been described in numerous publications [14-22,78,79,84-88]. These studies provide a detailed analysis of the phase equilibria under various conditions and cover all kinds of systems with all levels of disperse phase concentration. Special attention is devoted to the role of low and ultralow values of the surface energy at the interfaces. The author s first observations of areas of stable microheterogeneity in two-, three-, and four-component systems were documented in [66-68],... 

It is of particular interest to be able to correlate solubility and partitioning with the molecular stmcture of the surfactant and solute. Likes dissolve like is a well-wom plirase that appears applicable, as we see in microemulsion fonnation where reverse micelles solubilize water and nonnal micelles solubilize hydrocarbons. Surfactant interactions, geometrical factors and solute loading produce limitations, however. There appear to be no universal models for solubilization that are readily available and that rest on molecular stmcture. Correlations of homologous solutes in various micellar solutions have been reviewed by Nagarajan [52]. Some examples of solubilization, such as for polycyclic aromatics in dodecyl sulphonate micelles, are driven by hydrophobic... 

Fluorocarbons with a hydrophilic functional group are very active surfactants [23]. Less than 1% of ionic or nonionic surfactants with perfluoroalkyl groups can reduce the surface tension of water from 72 to 15-20 dyne/cm, compared with 25-35dyne/cm for typical hydrocarbon surfactants [24] Perfluoroether surfactants are about as active as their perfluoroalkyl counterparts of similar chain length [25, 26], but fluorosurfactants with more polar alkyl end groups are considerably less active than their perfluoroalkyl analogues (Table 7)... 

Figure 2 schematically presents a synthetic strategy for the preparation of the structured catalyst with ME-derived palladium nanoparticles. After the particles formation in a reverse ME [23], the hydrocarbon is evaporated and methanol is added to dissolve a surfactant and flocculate nanoparticles, which are subsequently isolated by centrifugation. Flocculated nanoparticles are redispersed in water by ultrasound giving macroscopically homogeneous solution. This can be used for the incipient wetness impregnation of the support. By varying a water-to-surfactant ratio in the initial ME, catalysts with size-controlled monodispersed nanoparticles may be obtained. 

A. I. Frolov, R. S. Khisamov, 1.1. Rjabov, and M. Z. Taziev. Recovery of oil from reservoir—by injection of water and surfactant solution also additionally of wide hydrocarbon(s) fraction and of surfactant solution. Patent RU 2103492-C, 1998. 

Ryoo, W., Webber, S.E. and Johnston, K.P. (2003) Water-in-carbon dioxide microemulsions with methylated branched hydrocarbon surfactants. Industrial and Engineering Chemistry Research, 42 (25), 6348-6358. 

Further information on the dependence of structure of microemulsions formed on the alcohol chain length was obtained from measurement of self diffusion coefficient of all the constitutents using NMR techniques (29-34). For microemulsions consisting of water, hydrocarbon, an anionic surfactant and a short chain alcohol and C ) the self diffusion... 

Microemulsions are thermodynamically stable, homogeneous, optically isotropic solutions comprised of a mixture of water, hydrocarbons and amphiphilic compoxmds. The microemulsions are usually four- or three-component systems consisting of surfactant and cosurfactant (termed as emulsifier), oil and water. The cosurfactants are either lower alkanols (like butanol, propanol and hexanol) or amines (Hke butylamine, hexylamine). Microemulsions are often called swollen micelles (Fig. 3) and swollen re-... 

Phase diagrams of water, hydrocarbon, and nonionic surfactants (polyoxyethylene alkyl ethers) are presented, and their general features are related to the PIT value or HLB temperature. The pronounced solubilization changes in the isotropic liquid phases which have been observed in the HLB temperature range were limited to the association of the surfactant into micelles. The solubility of water in a liquid surfactant and the regions of liquid crystals obtained from water-surfactant interaction varied only slightly in the HLB temperature range. 

Figure 3. General features of micellar phases in the system water, hydrocarbon, and a nonionic surfactant (wt %). A 0/W solubilization B surfactant phase C W/0 solubilization.

Because like dissolves like, when placed into water the surfactant molecule will strive to get the greasy, nonpolar hydrocarbon tail away from the polar water molecules. There are three potential strategies for achieving this outcome formation of monolayers, formation of bilayers, and formation of micelles. 

To give some sense of the extent to which surfactants can lower surface and interfacial tension, many hydrocarbon surfactants, at high concentrations (above the critical micelle concentration see Section 3.5.3), can lower the surface tension of water at 20 °C from 72.8 mN/m to about 28 mN/m. Polysiloxane surfactants can reduce it further, to about 20 mN/m, and perfluoroalkyl surfactants can reduce it still further, to about 15 mN/m. Similarly, hydrocarbon surfactants can reduce the interfacial tension of water-mineral oil from about 40 down to about 3 mN/m. 

It is generally accepted that the soft-core RMs contain amounts of water equal to or less than hydration of water of the polar part of the surfactant molecules, whereas in microemulsions the water properties are close to those of the bulk water (Fendler, 1984). At relatively small water to surfactant ratios (Wo < 5), all water molecules are tightly bound to the surfactant headgroups at the soft-core reverse micelles. These water molecules have high viscosities, low mobilities, polarities which are similar to hydrocarbons, and altered pHs. The solubilization properties of these two systems should clearly be different (El Seoud, 1984). The advantage of the RMs is their thermodynamic stability and the very small scale of the microstructure 1 to 20 nm. The radii of the emulsion droplets are typically 100 nm (Fendler, 1984 El Seoud, 1984). 

As discussed in Section 2.2, surfactant has a tendency to adsorb at interfaces since the polar head group has a strong preference for remaining in water while the hydrocarbon tail prefers to avoid water. The surfactant concentration affects the adsorption of surfactants at interfaces. Surfactant molecules lie flat on the surface at very low concentration. Surfactant molecules on the surface increase with increasing surfactant concentration in the bulk and surfactant tails start to orient towards gas or non-polar liquid since there is not enough space for the surfactant molecules to lie flat on the surface. Surfactant molecules adsorb at the interface and form monolayer until the surface is occupied at which point surfactant molecules start forming self-assembled structures in the liquid (Section 2.3). 

Adsorption can be measured by direct or indirect methods. Direct methods include surface microtome method [46], foam generation method [47] and radio-labelled surfactant adsorption method [48]. These direct methods have several disadvantages. Hence, the amount of surfactant adsorbed per unit area of interface (T) at surface saturation is mostly determined by indirect methods namely surface and interfacial tension measurements along with the application of Gibbs adsorption equations (see Section 2.2.3 and Figure 2.1). Surfactant structure, presence of electrolyte, nature of non-polar liquid and temperature significantly affect the T value. The T values and the area occupied per surfactant molecule at water-air and water-hydrocarbon interfaces for several anionic, cationic, non-ionic and amphoteric surfactants can be found in Chapter 2 of [2]. 

The efficiency of the nonionic trisiloxane surfactants is comparable to nonionic hydrocarbon surfactants with a linear dodecyl hydrophobe. The surface properties of a homologous series of trisiloxane surfactants M(DE OH)M with n = 4—20 show that the CAC, the surface tension at the CAC and the area per molecule each vary with molecular structure in a way that is consistent with an umbrella model for the shape of the trisiloxane hydrophobe at the air/water interface [29]. The log(CAC) and the surface tension at the CAC both increased linearly with EO chain length. 

A term to describe the aforementioned quotient is cohesive energy density (CED heat of vaporization/unit volume). To a first approximation, the lower the CED, the lower will be the surface tension and this is the source of the increased efficiency in surface tension reduction of fluorosurfactants versus hydrocarbon surfactants. Therefore, fluorosurfactants are often the choice for applications demanding ultimately low surface tension. Furthermore, fluorosurfactants are far less compatible with water than are hydrocarbon surfactants. This is the origin of the increased effectiveness compared to hydrocarbon surfactants. 

The ideas underlying elemental structures models are to establish microstructures experimentally, to compute free energies and chemical potentials from models based on these structures, and to use the chemical potentials to construct phase diagrams. Jonsson and Wennerstrom have used this approach to predict the phase diagrams of water, hydrocarbon, and ionic surfactant mixtures [18]. In their model, they assume the surfactant resides in sheetlike structures with heads on one side and tails on the other side of the sheet. They consider five structures spheres, inverted (reversed) spheres, cylinders, inverted cylinders, and layers (lamellar). These structures are indicated in Fig. 12. Nonpolar regions (tails and oil) are cross-hatched. For these elemental structures, Jonsson and Wennerstrom include in the free energy contributions from the electrical double layer on the water... 

In solutions of water and surfactant, the surfactant monolayers can join, tail side against tail side, to form bilayers, which form lamellar liquid crystals whose bilayers are planar and are arrayed periodically in the direction normal to the bilayer surface. The bilayer thickens upon addition of oil, and the distance between bilayers can be changed by adding salts or other solutes. In the oil-free case, the hydrocarbon tails can be fluidlike (La) lamellar liquid crystal or can be solidlike (Lp) lamellar liquid crystal. There also occurs another phase, Pp, called the modulated or rippled phase, in which the bilayer thickness varies chaotically in place of the lamellae. Assuming lamellar liquid crystalline symmetry, Goldstein and Leibler [19] have constructed a Hamiltonian in which (1) the intrabilayer energy is calculated... 

There are presently several groups around the world conducting molecular dynamics simulations of micellization and liquid crystallization of more or less realistic models of water, hydrocarbon, and surfactants. The memory and speed of a supercomputer required to produce reliably equilibrated microstructures constitute a challenge not yet met, in my opinion. By taking advantage of identified or hypothesized elemental structures one can, however, hope to learn a great deal about the dynamics and stability of the various identified microstructures. 

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