Ionic surfactants adsorption

Keywords Adsorption Ionic surfactant Counterion Alkali decyl sulfate Surface tension... 

Key words Clay minerals — adsorption — ionic surfactants — heat of wetting — surface hydrophobicity — humic acids — rheology — SAXS experiments... 

If an ionic surfactant is present, the potentials should vary as shown in Fig. XIV-5c, or similarly to the case with nonsurfactant electrolytes. In addition, however, surfactant adsorption decreases the interfacial tension and thus contributes to the stability of the emulsion. As discussed in connection with charged monolayers (see Section XV-6), the mutual repulsion of the charged polar groups tends to make such films expanded and hence of relatively low rr value. Added electrolyte reduces such repulsion by increasing the counterion concentration the film becomes more condensed and its film pressure increases. It thus is possible to explain qualitatively the role of added electrolyte in reducing the interfacial tension and thereby stabilizing emulsions. 

Physical and ionic adsorption may be either monolayer or multilayer (12). Capillary stmctures in which the diameters of the capillaries are small, ie, one to two molecular diameters, exhibit a marked hysteresis effect on desorption. Sorbed surfactant solutes do not necessarily cover ah. of a sohd iaterface and their presence does not preclude adsorption of solvent molecules. The strength of surfactant sorption generally foUows the order cationic > anionic > nonionic. Surfaces to which this rule apphes include metals, glass, plastics, textiles (13), paper, and many minerals. The pH is an important modifying factor in the adsorption of all ionic surfactants but especially for amphoteric surfactants which are least soluble at their isoelectric point. The speed and degree of adsorption are increased by the presence of dissolved inorganic salts in surfactant solutions (14). 

SG sols were synthesized by hydrolysis of tetraethyloxysilane in the presence of polyelectrolyte and surfactant. Poly (vinylsulfonic acid) (PVSA) or poly (styrenesulfonic acid) (PSSA) were used as cation exchangers, Tween-20 or Triton X-100 were used as non- ionic surfactants. Obtained sol was dropped onto the surface of glass slide and dried over night. Template extraction from the composite film was performed in water- ethanol medium. The ion-exchange properties of the films were studied spectrophotometrically using adsorption of cationic dye Rhodamine 6G or Fe(Phen) and potentiometrically by sorption of protons. 

The change in surface wettability (measured by the contact angle) with concentration for the three surfactants is plotted in Fig. 2.54 (Zhang and Manglik 2005). The contact angle reaches a lower plateau around the CMC where bilayers start to form on the surface. Wettability of non-ionic surfactants in aqueous solutions shows that the contact angle data attains a constant value much below CMC. Direct interactions of their polar chain are generally weak in non-ionics, and it is possible for them to build and rebuild adsorption layers below CMC. The reduced contact an-... 

One important advantage of the polarized interface is that one can determine the relative surface excess of an ionic species whose counterions are reversible to a reference electrode. The adsorption properties of an ionic component, e.g., ionic surfactant, can thus be studied independently, i.e., without being disturbed by the presence of counterionic species, unlike the case of ionic surfactant adsorption at nonpolar oil-water and air-water interfaces [25]. The merits of the polarized interface are not available at nonpolarized liquid-liquid interfaces, because of the dependency of the phase-boundary potential on the solution composition. 

Kakiuehi et al. [84] studied the adsorption properties of two types of nonionic surfactants, sorbitan fatty acid esters and sucrose alkanoate, at the water-nitrobenzene interface. These surfactants lower the interfacial capacity in the range of the applied potential with no sign of desorption. On the other hand, the remarkable adsorption-desorption capacity peak analogous to the adsorption peak seen for organic molecules at the mercury-electrolyte interface can be observed in the presence of ionic surfactants, such as triazine dye ligands for proteins [85]. 

Surfactants are separated according to adsorption or partitioning differences with a polar stationary phase in NPLC. This retention of the polar surfactant moiety allows for the separation of the ethylene oxide distribution. Of all the NPLC packings that have been utilized to separate nonionic surfactants, the aminopropyl-bonded stationary phases have been shown to give the best resolution (Jandera et al., 1990). The separation of the octylphenol ethoxylate oligomers on an amino silica column is shown in Fig. 18.4. Similar to the capabilities of CE for ionic surfactants, the ethylene oxide distribution can be quantitatively determined by NPLC if identity and response factors for each oligomer are known. 

Trathnigg, B., Rappel, C., Rami, R., Gorbunov, A. (2002b). Liquid exclusion-adsorption chromatography a new technique for isocratic separation of non-ionic surfactants V. Two-dimensional separation of fatty acid polyglycol ethers. J. Chromatogr. A 953(1-2), 89-99. 

Hydrophobic polar surfaces, adsorption of ionic surfactants on, 24 140-141 Hydrophobic precipitated silica, 22 399 Hydrophobic solvents, 16 413 Hydrophobic surfaces, 1 584-585... 

Ionic styrene polymerization, 23 384-388 Ionic surfactant adsorption, 24 137 Ionic surfactants, 24 133... 

It is also noteworthy that the surface tension of mixed solutions of anionic and cationic surfactants is controlled by the activity of the salt (38). These results indicate that, in adsorption of an ionic surfactant at the solution surface, the accompanying adsorption of the counter ion also plays an important role. 

Because the inverse Debye length is calculated from the ionic surfactant concentration of the continuous phase, the only unknown parameter is the surface potential i/io this can be obtained from a fit of these expressions to the experimental data. The theoretical values of FeQx) are shown by the continuous curves in Eig. 2.5, for the three surfactant concentrations. The agreement between theory and experiment is spectacular, and as expected, the surface potential increases with the bulk surfactant concentration as a result of the adsorption equilibrium. Consequently, a higher surfactant concentration induces a larger repulsion, but is also characterized by a shorter range due to the decrease of the Debye screening length. 

Carberry, J.B. Geyer, A.T. Adsorption of non-ionic surfactants by activated carbon and clay. Proceedings of the 32nd Industrial Waste Conference, Purdue University, Lafayette, IN, 1977, Vol. 32, 867. 

Carberry, J.B. Clay adsorption treatment of non-ionic surfactants in wastewater. J. Water PoU. Control Fed. 1977, 49, 452. 

Adsorption of Ionic Surfactants in Presence of Inorganic Electrolytes. .. 34... 

The deviations from the Szyszkowski-Langmuir adsorption theory have led to the proposal of a munber of models for the equihbrium adsorption of surfactants at the gas-Uquid interface. The aim of this paper is to critically analyze the theories and assess their applicabihty to the adsorption of both ionic and nonionic surfactants at the gas-hquid interface. The thermodynamic approach of Butler [14] and the Lucassen-Reynders dividing surface [15] will be used to describe the adsorption layer state and adsorption isotherm as a function of partial molecular area for adsorbed nonionic surfactants. The traditional approach with the Gibbs dividing surface and Gibbs adsorption isotherm, and the Gouy-Chapman electrical double layer electrostatics will be used to describe the adsorption of ionic surfactants and ionic-nonionic surfactant mixtures. The fimdamental modeling of the adsorption processes and the molecular interactions in the adsorption layers will be developed to predict the parameters of the proposed models and improve the adsorption models for ionic surfactants. Finally, experimental data for surface tension will be used to validate the proposed adsorption models. 

Ionic surfactants are electrolytes dissociated in water, forming an electrical double layer consisting of counterions and co-ions at the interface. The Gouy-Chapman theory is used to model the double layer. In conjunction with the Gibbs adsorption equation and the equations of state, the theory allows the surfactant adsorption and the related interfacial properties to be determined [9,10] (The Gibbs adsorption model is certainly simpler than the Butler-Lucassen-Reynders model for this case.). 

Equations 36-40 describe the entire adsorption behavior of 1 1 ionic surfactants in the absence of added salt or in the presence of salt with the... 

A new analysis of the adsorption layer of ionic surfactants with new adsorption isotherms and equations of states was made in [42]. The effect of mono and bivalent anions on the adsorption of cethyltrimethyl ammonium salts was recently examined in [43]. 

It is noted that the investigation of a mixed adsorption layer of CioEs and TPeAB (tetrapentyl ammoniiun bromide) [35] shows evidence for attractive forces / > 0), which suggests that the presence of the ionic surfactant can prevent aggregation in the extended S-L adsorption layer. Therefore, the main question of interest concerns how the Frumkin model and the aggregation model are related. One can find from Eq. 29 that the size of the elementary adsorption cell increases with the aggregation munber resulting in a reduction in the munber of cells. Negative has the same effect of de-... 

Regression analysis developed on the basis of the proposed model described by Eqs. 36 and 38-40 has been applied for the adsorption of ionic surfactants. The regression analysis minimizes the revised chi-square,... 

The theories for the adsorption of mixtures of nonionic and ionic surfactants have been validated with tetraethylene glycol mono- -octyl ether (C8E4) and... 

The adsorption of ionic surfactants creates an adsorption layer of surfactant ions, a Stern layer of counterions and a diffusive layer distributed by the electric field of the charged surface. Every layer has its own contribution to surface tension. For example, the adsorption of dodecyl sulfate (DS") ions from the sodium dodecyl sulfate solution is described by the modified Frumkin isotherm as... 

Equation 56 presents an improvement of Eq. 40 for predicting surface tension of ionic surfactants. For adsorption of alkali dodecyl sulfates, experimental data are available for the adsorption at saturation Ao and for the equihbrium constant Ki [55]. Table 6 summarizes the available data for alkali dodecyl sulfates. fSi, and A are calculated using Eqs. 52-54. The value for the di-... 

Theoretical models for equilibrium adsorption of nonionic and ionic surfactants at the gas-liquid interface have been developed, critically reviewed, and evaluated using experimental data for surface tension. The thermodynamic... 

A well-studied and often-cited adsorption isotherm of an ionic surfactant is that of sodium dodecylsulfate at the alumina-water interface at pH 6.5 and 0.1 M NaCl. At pH 6.5 and 0.1 M NaCl the S-F isotherm [23]... 

The ultrafiltration of the microemulsion is a very useful operation for separating water and oil in these mixtures [117-120]. Because of the limited availability of solvent stable membranes, most of the work pubHshed so far was performed using ceramic membranes, which show a high adsorption of surfactant at the membrane surface and comparably low rejection rates of reverse micelles. Using electro ultrafiltration, where the concentration polarisation phenomenon of the reverse micelles (using the ionic surfactant AOT) at the membrane surface is depressed by asymmetric high voltage electrical fields, the rejection rates can be increased,but not to economical values [121,122]. 

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