Surfactants behavior, aqueous solution

R. Zana, C. Weill. Effect of temperature on the aggregation behavior of nonionic surfactants in aqueous solutions. J Physique Lett 46 L953-L960, 1985. 

When the variation of any colligative property of a surfactant in aqueous solution is examined, two types of behavior are apparent. At low concentrations, properties approximate those to be expected from ideal behavior. However, at a concentration value that is characteristic for a given surfactant system (critical micelle concentration, CMC), an abrupt deviation from such behavior is observed. At concentrations above the CMC, molecular aggregates called micelles are formed. By increasing the concentration of the surfactant, depending on the chemical and physical nature of the molecule, structural changes to a more... 

Zhang et al. [135] have studied the physicochemical behavior of mixtures of -dodecyl-/l-D-maltoside with anionic, cationic and nonionic surfactants in aqueous solutions. To acquire information on the property of mixed micelles, the characteristic change of pyrene with changes in polarity was monitored. The polarity parameter at low concentrations was found to be 0.5-0.6. 

This explanation for the entropy-dominated association of surfactant molecules is called the hydrophobic effect or, less precisely, hydrophobic bonding. Note that relatively little is said of any direct affinity between the associating species. It is more accurate to say that they are expelled from the water and —as far as the water is concerned —the effect is primarily entropic. The same hydrophobic effect is responsible for the adsorption behavior of amphi-pathic molecules and plays an important role in stabilizing a variety of other structures formed by surfactants in aqueous solutions. 

Silicone surfactants in aqueous solutions show the same general behavior as conventional hydrocarbon surfactants - the surface tension decreases with increasing concentration until a densely packed film is formed at the surface. Above this concentration, the surface tension becomes constant. The concentration at the transition is called the critical micelle concentration (CMC) or critical aggregation concentration (CAC). The surface and interfacial activity of silicone surfactants was reviewed by Hoffmann and Ulbricht [27]. Useful discussions of the dependence of the surface activity of polymeric silicone surfactants on molecular weight and structure are given by Vick [28] and for the trisiloxane surfactants by Gentle and Snow [29]. 

Amphoteric Surfactants. Amphoteric surfactants in aqueous solution contain both positive and negative charges in the same molecule. Thus, a hydrophobic fatty chain is attached to a hydrophilic group that contains both positive and negative charges. Its behavior depends on the condition of the medium or its pH value. Examples of this type are the alkyl betaines. 

Table I. Phase behavior of polymer/surfactant-cosurfactant aqueous solutions as observed in polarized light...

The PO-EO sulfonate formulation composed by Wellington and Richardson [15] contained small amounts of a cationic surfactant with EO groups. Contrary to traditional anionc surfactants, an aqueous solution of this formulation passes through a cloud point by increasing the temperature, i.e. a phase separation takes place. In the presence of oil, the system will move towards the II( +) state as the temperature is increased. This is the same behavior as for nonionic surfactants. 

Figure 25 Morphological behavior of surfactant in aqueous solution surfactant volume fraction <1> verses molar ratio CJC of salt over surfactant concentrations. (Reprinted with permission from Ref. 66. Copyright 1994 American Chemical Society).

HEM He, M., Hill, R. M., Lin, Z., Scriven, L.E., and Davis, H.T., Phase behavior and microstmcture of polyoxyethylene trisiloxane surfactants in aqueous solution, J. 

The effective surface viscosity is best found by experiment with the system in question, followed by back calculation through Eq. (22-55). From the precursors to Eq. (22-55), such experiments have yielded values of [L, on the order of (dyn-s)/cm for common surfactants in water at room temperature, which agrees with independent measurements [Lemhch, Chem. Eng. ScL, 23, 932 (1968) and Shih and Lem-lich. Am. Inst. Chem. Eng. J., 13, 751 (1967)]. However, the expected high [L, for aqueous solutions of such sldn-forming substances as saponin and albumin was not attained, perhaps because of their non-newtonian surface behavior [Shih and Lemhch, Ind. Eng. Chem. Fun-dam., 10, 254 (1971) andjashnani and Lemlich, y. Colloid Inteiface ScL, 46, 13(1974)]. 

Monoamidotriphosphate compounds have been evaluated for their combined detergent-sequestrant action [65,66]. Good surfactant properties are also attributed to organoaminodialkylenephosphonic acids. Typical compounds of this kind are the tetra- and trialkali salts of decyl-, dodecyl-, and tetradecylaminodi (methylphosphonate). Values of surface tension and detergency are given in Refs. 118 and 216-219. Wash test results, foam behavior, wetting performance, and surface tensions of aqueous solutions of phosphate esters have been tabulated [12,17,18,33,37,50,52,56,90,220]. 

Surfactants are widely used in industrial chemistry to modify the behavior of aqueous solutions. Common surfactant head groups include carboxylate (— CO2), sulfonate (-SO3), sulfate (-OSO3 ), and ammonium (-NH3 ). The negative charge of anionic head groups usually is neutralized by Na , and the positive charge of ammonium usually is neutralized by Cl . These ions are used because they are nontoxic and their salts are highly soluble. 

The molecular collective behavior of surfactant molecules has been analyzed using the time courses of capillary wave frequency after injection of surfactant aqueous solution onto the liquid-liquid interface [5,8]. Typical power spectra for capillary waves excited at the water-nitrobenzene interface are shown in Fig. 3 (a) without CTAB (cetyltrimethy-lammonium bromide) molecules, and (b) 10 s after the injection of CTAB solution to the water phase [5]. The peak appearing around 10-13 kHz represents the beat frequency, i.e., the capillary wave frequency. The peak of the capillary wave frequency shifts from 12.5 to 10.0kHz on the injection of CTAB solution. This is due to the decrease in interfacial tension caused by the increased number density of surfactant molecules at the interface. Time courses of capillary wave frequency after the injection of different CTAB concentrations into the aqueous phase are reproduced in Fig. 4. An anomalous temporary decrease in capillary wave frequency is observed when the CTAB solution beyond the CMC (critical micelle concentration) was injected. The capillary wave frequency decreases rapidly on injection, and after attaining its minimum value, it increases... 

Disperse systems can also be classified on the basis of their aggregation behavior as molecular or micellar (association) systems. Molecular dispersions are composed of single macromolecules distributed uniformly within the medium, e.g., protein and polymer solutions. In micellar systems, the units of the dispersed phase consist of several molecules, which arrange themselves to form aggregates, such as surfactant micelles in aqueous solutions. 

Choi and Funayama [19] also measured sodium atom emission from sodium dodecylsulfate (SDS) solutions in the concentration range of 0.1-100 mM at frequencies of 108 kHz and 1.0 MHz. The sodium line intensity observed at 1 MHz was nearly constant in the concentration range from 3 to 100 mM and was considerably higher than that at 108 kHz. This frequency dependence of the intensity is opposite that for NaCl aqueous solution. The dynamical behavior of the absorption and desorption of surfactant molecules onto the bubble surface may affect the reduction and excitation processes of sodium atom emission. This point should be clarified in the future. 

Chen H, Farahat MS, Law KY, Whitten DG (1996) Aggregation of surfactant squaraine dyes in aqueous solution and microheterogeneous media correlation of aggregation behavior with molecular structure. J Am Chem Soc 118 2584-2594... 

Li H, Hao J (2007) Phase behavior of salt-free catanionic surfactant aqueous solutions with fullerene C60 solubilized. J Phys Chem B. Ill 7719-7724. 

The mechanism of interaction of amino acids at solid/ aqueous solution interfaces has been investigated through adsorption and electrokinetic measurements. Isotherms for the adsorption of glutamic acid, proline and lysine from aqueous solutions at the surface of rutile are quite different from those on hydroxyapatite. To delineate the role of the electrical double layer in adsorption behavior, electrophoretic mobilities were measured as a function of pH and amino acid concentrations. Mechanisms for interaction of these surfactants with rutile and hydroxyapatite are proposed, taking into consideration the structure of the amino acid ions, solution chemistry and the electrical aspects of adsorption. 

Zhong et al. (2003) studied the apparent solubility of trichloroethylene in aqueous solutions, where the experimental variables were surfactant type and cosolvent concentration. The surfactants used in the experiment were sodium dihexyl sulfo-succinte (MA-80), sodium dodecyl sulfate (SDS), polyoxyethylene 20 (POE 20), sorbitan monooleate (Tween 80), and a mixture of Surfonic- PE2597 and Witconol-NPIOO. Isopropanol was used as the alcohol cosolvent. Eigure 8.20 shows the results of a batch experiment studying the effects of type and concentration of surfactant on solubilization of trichloroethylene in aqueous solutions. A correlation between surfactant chain length and solubilization rate may explain this behavior. However, the solubilization rate constants decrease with surfactant concentration. Addition of the cosolvent isopropanol to MA-80 increased the solubility of isopropanol at each surfactant concentration but did not demonstrate any particular trend in solubilization rate of isopropanol for the other surfactants tested. In the case of anionic surfactants (MA-80 and SDS), the solubility and solubilization rate increase with increasing electrolyte concentration for all surfactant concentrations. 

R Hansson and M. Akngren Interaction of Alkyltrimethylammonium Surfactants with Polyacrylate and Poly(Styrenesulfonate) in Aqueous Solution Phase Behavior and Surfactant Aggregation Numbers. Langmuir 10, 2115 (1994). 

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