Surfactant activity, interfacial

For a compound to be qualified as a surfactant, it should also exhibit surface activity. It means that when the compound is added to a liquid at low concentration, it should be able to adsorb on the surface or interface of the system and reduce the surface or interfacial excess free energy. The surface is a boundary between air and liquid and the interface is a boundary between two immiscible phases (liquid-liquid, liquid-solid and solid-solid). Surface activity is achieved when the number of carbon atoms in the hydrophobic tail is higher than 8 [3]. Surfactant activities are at a maximum if the carbon atoms are between 10 and 18 at which level a surfactant has good but limited solubility in water. If the carbon number is less than 8 or more than 18, surfactant properties become minimal. Below 8, a surfactant is very soluble and above 18, it is insoluble. Thus, the solubility and practical surfactant properties are somewhat related [1]. 

During emulsification an increase in the interfacial area A takes place and this causes a reduction in T. The equilibrium is restored by the adsorption of surfactant from the bulk, but this takes time (shorter times occur at higher surfactant activity). Thus, e is small whether a is small or large. Because of the lack or slowness of equilibrium with polymeric surfactants, e will not be the same for expansion and compression of the interface. 

In most systems, it is of interest to determine how a change in the alkyl part of the organic molecule (i.e., the hydrophobic part) affects the surface and interfacial tension. In spite of its importance (both in biology and technical industry), no such systematic analysis is found in the current literature. These molecular considerations are pertinent in any reaction where the hydrophobicity might be of major importance in the system, e.g., surfactant activity, EOR, protein structure and activity, and pharmaceutical molecules and activity. 

One of the most widely used indexes for evaluating surfactant activity is the critical micelle concentration (CMC). The CMC is in effect the solubility of a surfactant within an aqueous phase, or the minimum surfactant concentration required for reaching the lowest interfacial or surface tension values y. At concentrations above the CMC, surfactants associate readily to form micelles that can be spherical, oblate, tablet shaped, or rod-like, with a hydrophilic surface and a hydrophobic interior. Such micellar structures usually have hydrodynamic radii, ranging from 200 to 400 A. The CMC value is estimated from the inflection point in the y vs log C curve. 

To summarize, the mechanisms involved in the two different cases of highly immiscible systems and nearly compatible blends are quite different. In the first case, it is the surfactant activity of the block copolymer chains that cause the interfacial tension reduction whereas, in the second case, it is the presence of copolymer molecules in the bulk homopolymer phases that causes the compatibi-lizing behavior. 

During droplet deformation, its interfacial area is increased. The drop will commonly have acquired some surfactant, and it may even have a F value close to equilibrium at the prevailing (local) surfactant activity. Will this surfactant be able to distribute itself evenly over the enlarged interface in the very short times available Evening out can occur by surface diffusion or by spreading. 

The most important properties of a surfactant are its solubility and its interfacial activity. When a nonionic surfactant is added to a two-phase liquid-liquid system, it preferentially adsorbs at the interface forming an adsorbed layer. At low surfactant concentrations an equilibrium exists between surfactant monomers dissolved in the oil phase, surfactant monomers dissolved in the water phase and the interfacial surfactant. In the case of a separated system (constant interfacial area), as the concentration of surfactant in the system increases, the amount of surfactant at the interface reaches a maximum possible concentration and, on further increase in surfactant concentration, excess surfactant will now form micelles in either the oil or aqueous phase, or form a surfactant phase depending on its affinity for the oil and water phases. The break point is termed the critical micelle concentration (CMC). 

In addition to lowering the interfacial tension between a soil and water, a surfactant can play an equally important role by partitioning into the oily phase carrying water with it [232]. This reverse solubilization process aids hydrody-namically controlled removal mechanisms. The partitioning of surface-active agents between oil and water has been the subject of fundamental studies by Grieser and co-workers [197, 233]. 

In the aqueous biphasic hydroformylation reaction, the site of the reaction has been much discussed (and contested) and is dependent on reaction conditions (temperature, partial pressure of gas, stirring, use of additives) and reaction partners (type of alkene) [35, 36]. It has been suggested that the positive effects of cosolvents indicate that the bulk of the aqueous liquid phase is the reaction site. By contrast, the addition of surfactants or other surface- or micelle-active compounds accelerates the reaction, which apparently indicates that the reaction occurs at the interfacial layer. 

Figure 20 shows the plot of the surface tension vs. the logarithm of the concentration (or-lg c-isotherms) of sodium alkanesulfonates C,0-C15 at 45°C. In accordance with the general behavior of surfactants, the interfacial activity increases with growing chain length. The critical micelle concentration (cM) is shifted to lower concentration values. The typical surface tension at cM is between 38 and 33 mN/m. The ammonium alkanesulfonates show similar behavior, though their solubility is much better. The impact of the counterions is twofold First, a more polarizable counterion lowers the cM value (Fig. 21), while the aggregation number of the micelles rises. Second, polarizable and hydrophobic counterions, such as n-propyl- or isopropylammonium and n-butylammonium ions, enhance the interfacial activity as well (Fig. 22). Hydrophilic counterions such as 2-hydroxyethylammonium have the opposite effect. Table 14 summarizes some data for the dodecane 1-sulfonates.

The interfacial activity is determined by the sterical properties of the molecule. At the interface the spatial demand A0 of the hydrophobic part of the molecule is higher because of the second chain of the internal sulfonate compared with the terminal sulfonate. Thus, the surface concentration of the surfactant molecules is lower. That means that the hydrocarbon chains are laterally oriented and therefore cover the interface between the solution surface and air more completely. Because the ratio of the spatial demand of the head group to the volume of the alkyl chain governs the radius of the micellar surface, it... 

Tests were performed at 75°C using a University of Texas Model 500 spinning drop tensiometer. Active surfactant concentration in the aqueous phase prior to addition of the oil phase was 0.5% wt. Interfacial tension values are the average of duplicate or triplicate determinations. 

The recovery of petroleum from sandstone and the release of kerogen from oil shale and tar sands both depend strongly on the microstmcture and surface properties of these porous media. The interfacial properties of complex liquid agents—mixtures of polymers and surfactants—are critical to viscosity control in tertiary oil recovery and to the comminution of minerals and coal. The corrosion and wear of mechanical parts are influenced by the composition and stmcture of metal surfaces, as well as by the interaction of lubricants with these surfaces. Microstmcture and surface properties are vitally important to both the performance of electrodes in electrochemical processes and the effectiveness of catalysts. Advances in synthetic chemistry are opening the door to the design of zeolites and layered compounds with tightly specified properties to provide the desired catalytic activity and separation selectivity. 

The B. licheniformis JF-2 strain produces a very effective surfactant under conditions typical of oil reservoirs. The partially purified biosurfactant from JF-2 was shown to be the most active microbial surfactant found, and it gave an interfacial tension against decane of 0.016 mN/m. An optimal production of the surfactant was obtained in cultures grown in the presence of 5% NaCl at a temperature of 45° C and pH of 7. TTie major endproducts of fermentation were lactic acid and acetic acid, with smaller amounts of formic acid and acetoin. The growth and biosurfactant formation were also observed in anaerobic cultures supplemented with a suitable electron acceptor, such as NaNO3[1106]. 

Modem oil spill-dispersant formulations are concentrated blends of surface-active agents (surfactants) in a solvent carrier system. Surfactants are effective for lowering the interfacial tension of the oil slick and promoting and stabilizing oil-in-water dispersions. The solvent system has two key functions (1) to reduce the viscosity of the surfactant blend to allow efficient dispersant application and (2) to promote mixing and diffusion of the surfactant blend into the oil film [601]. 

We recently synthesized several reasonably surface-active crown-ether-based ionophores. This type of ionophore in fact gave Nernstian slopes for corresponding primary ions with its ionophore of one order or less concentrations than the lowest allowable concentrations for Nernstian slopes with conventional counterpart ionophores. Furthermore, the detection limit was relatively improved with increased offset potentials due to the efficient and increased primary ion uptake into the vicinity of the membrane interface by surfactant ionophores selectively located there. These results were again well explained by the derived model essentially based on the Gouy-Chapman theory. Just like other interfacial phenomena, the surface and bulk phase of the ionophore incorporated liquid membrane may naturally be speculated to be more or less different. The SHG results presented here is one of strong evidence indicating that this is in fact true rather than speculation. 

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