Surfactant solutions diffusion

It was determined, for example, that the surface tension of water relaxes to its equilibrium value with a relaxation time of 0.6 msec [104]. The oscillating jet method has been useful in studying the surface tension of surfactant solutions. Figure 11-21 illustrates the usual observation that at small times the jet appears to have the surface tension of pure water. The slowness in attaining the equilibrium value may partly be due to the times required for surfactant to diffuse to the surface and partly due to chemical rate processes at the interface. See Ref. 105 for similar studies with heptanoic acid and Ref. 106 for some anomalous effects. 

For example, for alkyl (8-16) glycoside (Plantacare 818 UP) non-ionic surfactant solution of molecular weight 390 g/mol, an increase in surfactant concentration up to 300 ppm (CMC concentration) leads to a significant decrease in surface tension. In the range 300 < C < 1,200 ppm the surface tension was almost independent of concentration. In all cases an increase in liquid temperature leads to a decrease in surface tension. This surface tension relaxation is a diffusion rate-dependent process, which typically depends on the type of surfactant, its diffusion/absorption kinetics, micellar dynamics, and bulk concentration levels. As the CMC is approached the absorption becomes independent of the bulk concentration, and the surfactant... 

Thus, the enhancement of heat transfer may be connected to the decrease in the surface tension value at low surfactant concentration. In such a system of coordinates, the effect of the surface tension on excess heat transfer (/z — /zw)/ (/ max — w) may be presented as the linear fit of the value C/Cq. On the other hand, the decrease in heat transfer at higher surfactant concentration may be related to the increased viscosity. Unfortunately, we did not find surfactant viscosity data in the other studies. However, we can assume that the effect of viscosity on heat transfer at surfactant boiling becomes negligible at low concentration of surfactant only. The surface tension of a rapidly extending interface in surfactant solution may be different from the static value, because the surfactant component cannot diffuse to the absorber layer promptly. This may result in an interfacial flow driven by the surface tension gradi-... 

In order to solve the mathematical model for the emulsion hquid membrane, the model parameters, i. e., external mass transfer coefficient (Km), effective diffu-sivity (D ff), and rate constant of the forward reaction (kj) can be estimated by well known procedures reported in the Hterature [72 - 74]. The external phase mass transfer coefficient can be calculated by the correlation of Calderback and Moo-Young [72] with reasonable accuracy. The value of the solute diffusivity (Da) required in the correlation can be calculated by the well-known Wilke-Chang correlation [73]. The value of the diffusivity of the complex involved in the procedure can also be estimated by Wilke-Chang correlation [73] and the internal phase mass transfer co-efficient (surfactant resistance) by the method developed by Gu et al. [75]. 

The adsorption and desorption kinetics of surfactants, such as food emulsifiers, can be measured by the stress relaxation method [4]. In this, a "clean" interface, devoid of surfactants, is first formed by rapidly expanding a new drop to the desired size and, then, this size is maintained and the capillary pressure is monitored. Figure 2 shows experimental relaxation data for a dodecane/ aq. Brij 58 surfactant solution interface, at a concentration below the CMC. An initial rapid relaxation process is followed by a slower relaxation prior to achieving the equilibrium IFT. Initially, the IFT is high, - close to the IFT between the pure solvents. Then, the tension decreases because surfactants diffuse to the interface and adsorb, eventually reaching the equilibrium value. The data provide key information about the diffusion and adsorption kinetics of the surfactants, such as emulsifiers or proteins. 

The formation of an adsorbed surface layer is not an instantaneous process but is governed by the rate of diffusion of the surfactant through the solution to the interface. It might take several seconds for a surfactant solution to attain its equilibrium surface tension, especially if the solution is dilute and the solute molecules are large and unsymmetrical. Much slower ageing effects have been reported, but these are now known to be due to traces of impurities. The time factor in adsorption can be demonstrated by measuring the surface tensions of freshly formed surfaces by a dynamic method for example, the surface tensions of sodium oleate solutions measured by... 

Early oxidation hair dyes were used in solution form these have been replaced by cream- or gel-based formulas. The oil-in-water emulsions commonly used can be supplemented with auxiliary ingredients, such as polymers to improve combing ability, as well as other conditioning additives. Extensive patent literature is available on this point [35], Gel formulations may be based on alcoholic solutions of nonionic surfactants or fatty acid alkanolamide solutions, which form a gel when mixed with the oxidant. The type (emulsion or gel) and the basic composition of the preparation strongly influence dyeing [47], Different base formulations with the same dye content yield varying color depths and shading due to the distribution of the dye between the different phases of the product, interaction with surfactants, and diffusion from the product into the hair. 

Pharmaceutical surfactants seem to nullify the limiting effect on solute diffusion of the stagnant aqueous layer. 

Table 3.2 presents the potential values at the surfactant solution/air interface, corresponding to the plateau in the h(C) curves and the values of the charge density Ob of the diffuse electric layer, calculated according to the following formula [161,169]... 

In conclusion it is worth noting that the method of equilibrium foam film proved to be very appropriate for the determination of the equilibrium diffuse electric layer potential at the solution/air interface. Though it is an indirect experimental technique, it provides reliable results about the appearance of a negative surface charge in the case of surfactant-free solutions as well as in the case of non-ionic surfactant solutions. The existence of an isoeletric point and the re-charging of the interface can be considered as a direct evidence. 

For the case of film thickness measurements in the presence of CaCl2 (po and diffuse electric layer planes due to Ca2+ ion binding. The calculation in the electrolyte concentration range 10 3 - 5-10 2 mol dm3 indicates an increase in transition concentration from 10 3 to 2-1 O 3 mol dm 3 CaCl2, the potential is comparatively low (17 mV) and remains practically constant. Further on, it increases to reach values that are usually found for films from ionic surfactant solutions [e.g. 171,186,189] (see also Section 3.4.1.3). So, the formation of CBF through initial formation of common black spots can be interpreted as due to the specific interaction of Ca2+ ions with lyso PC. 

Brawn et. al. [481] have studied the diffusion of air from bubbles formed in a surfactant solution and ascending to the surface. Bubbles were produced in a cell placed in a thermostat. Prior to use the solution surface was purified. The device was placed so that the ascending bubbles would remain immobile. Their change in size was observed under a... 

The details of the influence that electrostatic surface forces on the stability of foam films is discussed in Section 3.3. As already mentioned, the electrostatic disjoining pressure is determined (at constant electrolyte concentration) by the potential of the diffuse electric layer at the solution/air interface. This potential can be evaluated by the method of the equilibrium foam film (Section 3.3.2) which allows to study the nature of the charge, respectively, the potential. Most reliable results are derived from the dependence foam film thickness on pH of the surfactant solution at constant ionic strength. The effect of the solution pH is clearly pronounced the potential of the diffuse electric layer drops to zero at certain critical pH value. We have named it pH isoelectric (pH ). As already mentioned pH is an intrinsic parameter for each surfactant and is related to its electrochemical behaviour at the solution/air interface. Furthermore, it is possible to find conditions under which the electrostatic interactions in foam films could be eliminated when the ionic strength is not very high. 

Foam is a disperse system with a high surface area, and consequently foams tend to collapse spontaneously. Ordinarily, three-dimensional foams of surfactant solutes persist for a matter of hours in closed vessels. Gas slowly diffuses from the small bubbles to the large ones (since the pressure and hence thermodynamic activity of the gas within the bubbles is inversely proportional to bubble radius). Diffusion of gas leads to a rearrangement of the foam stmctures and this is often sufficient to rupture the thin lamellae in a well-drained film. 

Diffusion studies were made using an Isopar M/Heavy Aromatic Naptha (IM/HAN) 9 1 oil mixture (Exxon). Isopar M and HAN are refined paraffinic and aromatic oils, respectively. Figure 3 shows equilibrium salinity scans measured in the laboratory for equal-volume mixtures of the surfactant solution and oil. Since room temperature varied somewhat, the effect of temperature on phase behavior was determined. As Figure 3 shows, there is a small temperature effect, especially at the lower salinities. However, it is not large enough to have influenced the basic results of the contacting experiments. Optimum salinity, where equal volumes of oil and brine are contained in the middle phase, is approximately 1.4 gm/dl. 

The identity of the intermediate phase formed at these conditions can be deduced from the relative movement of the interfaces. Because the phase grew quickly in the direction of the aqueous surfactant solution, it contained predominantly brine. Although small in quantity, some oil did diffuse into it. From this information and from its isotropic appearance, one can conclude that the intermediate phase was an oil-in-water microemulsion. Additional support for this conclusion is that this type of microemulsion is an equilibrium phase at low salinities. 

A comparison between experimental and theoretical results shows that diffusion path analysis can qualitatively predict what is observed when an anionic surfactant solution contacts oil. Experimentally, one or two intermediate phases formed at all salinities. The growth of these phases was easily observed through the use of a vertical-orientation microscope. Except when convection occurred due to an intermediate phase being denser than the phase below it, interface positions varied as the square root of time. As a result, diffusion path theory could generally he used to correctly predict the direction of movement and relative speeds of the interfaces. 

Clusters supported on solids or confined in various structures, hard or soft matrices (Fig. 5), are produced by letting the ion solution diffuse into the matrix pores or by mixing the ion and surfactant solutions [3,6], The support is often charged superficially with a layer of counter ions of opposite charge in the liquid phase. Metal ions of the same charge can thus... 

Surfactant molecules diffuse from bulk solution to surface... 

Below, in Sections 5.2 and 5.3, we consider effects related to the surface tension of surfactant solution and capillarity. In Section 5.4 we present a review of the surface forces due to intermo-lecular interactions. In Section 5.5 we describe the hydrodynamic interparticle forces originating from the effects of bulk and surface viscosity and related to surfactant diffusion. Section 5.6 is devoted to the kinetics of coagulation in dispersions. Section 5.7 regards foams containing oil drops and solid particulates in relation to the antifoaming mechanisms and the exhaustion of antifoams. Finally, Sections 5.8 and 5.9 address the electrokinetic and optical properties of dispersions. 

If the surface of an equilibrium surfactant solution is disturbed (expanded, compressed, renewed, etc.), the system will try to restore the equilibrium by exchange of surfactant between the surface and the subsurface layer (adsorption-desorption). The change of the surfactant concentration in the subsurface layer triggers a diffusion flux in the solution. In other words, the process of equilibration (relaxation) of an expanded adsorption monolayer involves two consecutive stages ... 

---