Surfactant solutions, thermodynamics

Physico-Chemical Properties of Surfactant Solutions. Thermodynamic and... 

That surfactant molecules form aggregates designed to remove unfavourable hydrocarbon-water contact is not surprising but the question that should be asked is why the aggregates form sharply at a concentration characteristic of the surfactant (the cmc). From the basic equation of ideal solution thermodynamics... 

Except for some anionic/cationic surfactant mixtures which form ion pairs, in a typical surfactant solution, the concentration of the surfactant components as monomeric species is so dilute that no significant interactions between surfactant monomers occur. Therefore, the monomer—mi celle equilibria is dictated by the tendency of the surfactant components to form micelles and the interaction between surfactants in the micelle. Prediction of monomer—micelle equilibria reduces to modeling of the thermodynamics of mixed micelle formation. 

Medium-chain alcohols such as 2-butoxyethanol (BE) exist as microaggregates in water which in many respects resemble micellar systems. Mixed micelles can be formed between such alcohols and surfactants. The thermodynamics of the system BE-sodlum decanoate (Na-Dec)-water was studied through direct measurements of volumes (flow denslmetry), enthalpies and heat capacities (flow microcalorimetry). Data are reported as transfer functions. The observed trends are analyzed with a recently published chemical equilibrium model (J. Solution Chem. 13,1,1984). By adjusting the distribution constant and the thermodynamic property of the solute In the mixed micelle. It Is possible to fit nearly quantitatively the transfer of BE from water to aqueous NaDec. The model Is not as successful for the transfert of NaDec from water to aqueous BE at low BE concentrations Indicating self-association of NaDec Induced by BE. The model can be used to evaluate the thermodynamic properties of both components of the mixed micelle. 

In this paper we apply basic solution thermodynamics to both the adsorption of single surfactants and the competitive adsorption of two surfactants on a latex surface. The surfactant system chosen in this model study is sodium dodecyl sulfate (SDS) and nonylphenol deca (oxyethylene glycol) monoether (NP-EO o) These two surfactants have very different erne s, i.e. the balance between their hydrophobic and hydrophilic properties are very different while both are still highly soluble in water. 

Critical Micelle Concentration. In order to demonstrate the analogy between our treatment of mixed adsorption and earlier treatments of mixed micellization, we will briefly review the thermodynamics of mixed micelles. The thermodynamics of formation of ideal mixed micelles by two surfactants has been treated by Lange and Beck (9 ) and Cling (10). Rubingh ( ) extended the treatment to account for interactions between the surfactants, essentially by writing the cmc in the mixed surfactant solution as. 

Surfactant Activity in Micellar Systems. The activities or concentrations of individual surfactant monomers in equilibrium with mixed micelles are the most important quantities predicted by micellar thermodynamic models. These variables often dictate practical performance of surfactant solutions. The monomer concentrations in mixed micellar systems have been measured by ultraf i Itration (I.), dialysis (2), a combination of conductivity and specific ion electrode measurements (3), a method using surface tension of mixtures at and above the CMC <4), gel filtration (5), conductivity (6), specific ion electrode measurements (7), NMR <8), chromatograph c separation of surfactants with a hydrophilic substrate (9> and by application of the Bibbs-Duhem equation to CMC data (iO). Surfactant specific electrodes have been used to measure anionic surfactant activities in single surfactant systems (11.12) and might be useful in mixed systems. ... 

There s another example of water-in-oil compartmentation, which can circumvent this problem water-in-oil emulsions. These can be prepared by adding to the oil a small amount of aqueous surfactant solution, with the formation of more or less spherical aggregates (water bubbles) having dimensions in the range of 20-100 p,m in diameter. These systems are generally not thermodynamically stable, and tend to de-nfix with time. However, they can be long-lived enough to permit the observation of chemical reactions and a kinetic study. 

Above the CMC, a number of solutes that would normally be insoluble or only slightly soluble in water dissolve extensively in surfactant solutions. The process is called solubilization, the substance dissolved is called the solubilizate, and —in this context —the surfactant is called the solubilizer. The result is a thermodynamically stable, isotropic solution in which the solubilizate is somehow taken up by micelles since the enhancement of solubility begins at the CMC. This observation, in fact, provides one method for determining the CMC of a surfactant it... 

Two principal approaches have been used to describe the thermodynamics of surfactant solutions — the pseudo-phase model and the mass action model. 

By using equation (18.72), equations can be obtained for relating the other thermodynamic properties to m. The total Gibbs free energy G of the surfactant solution is the sum of the contributions from the solvent, the monomer, and the micelle. That is,... 

The Mass Action Model The mass action model represents a very different approach to the interpretation of the thermodynamic properties of a surfactant solution than does the pseudo-phase model presented in the previous section. A chemical equilibrium is assumed to exist between the monomer and the micelle. For this reaction an equilibrium constant can be written to relate the activity (concentrations) of monomer and micelle present. The most comprehensive treatment of this process is due to Burchfield and Woolley.22 We will now describe the procedure followed, although we will not attempt to fill in all the steps of the derivation. The aggregation of an anionic surfactant MA is approximated by a simple equilibrium in which the monomeric anion and cation combine to form one aggregate species (micelle) having an aggregation number n, with a fraction of bound counterions, f3. The reaction isdd... 

For a more detailed discussion of the pseudo-phase model, see J. E. Desnoyers and G. Perron, Thermodynamic methods , Chapter 1 in Surfactant Solutions New Methods of Investigation, R. Zana, Editor, Marcel Dekker, Inc., New York, 1987. 

See T. E. Burchfield and E. M. Woolley, Model for thermodynamics of ionic surfactant solutions. 1. Osmotic and activity coefficients , J. Phys. Chem, 88, 2149-2155 (1984) and E. M. Woolley and T. E. Burchfield, Model for Thermodynamics of Ionic Surfactant Solutions 2. Enthalpies, Heat Capacities, and Volumes , J. Phys. Chem., 88, 2155-2163 (1984). 

Lin and Yang (1987) also calculated the thermodynamic parameters of diazepam for micellar solubilization in Pluronic surfactant solutions at different temperatures (Table 13.4). For all systems, AG was negative, indicating micellar solubilization was spontaneous. The sign of entropy has been associated with the location of solubilized molecules within the micelles. Positive values have been observed for molecules embedded in the micelle center and negative values for adsorption of the molecules on the micelle surface. The results in this paper indicate that in the F-108 and F-88 Pluronics, diazepam molecules can penetrate into the micelle interior, whereas for F-68 and lower concentrations of F-88, diazepam is adsorbed on the micelle surface without penetration into the micellar core. 

An amine oxide surfactant solution can be modeled as a binary mixture of cationic and nonionic surfactants, the composition of which is varied by adjusting the pH. The cationic and nonionic moieties form thermodynamically nonideal mixed micelles, and a model has been developed which quantitatively describes the variation of monomer and micelle compositions and concentrations with pH and... 

Thermodynamic measurements in dilute hydrocarbon surfactant solutions give negative values for the enthalpy change on micellization (AH0mic), and the entropy change (AS°mic) in the negative range (see Chapter 1, Table 1.1 for comparison). 

At constant temperature, the interfacial tension y of a water oil system containing a single surfactant solute can be calculated at thermodynamic equilibrium starting with the Gibbs adsorption equation... 

The simplest explanation of film rupture involves reaching a thermodynamically unstable state [20]. A typical example of thermodynamically unstable systems are foam films in which the disjoining pressure obeys Hamaker s relation. Such are films from some aqueous surfactant solutions containing sufficient amount of an electrolyte to suppress the electrostatic component of disjoining pressure as well as films from non-aqueous solutions (aniline, chlorobenzene) [e.g. 80],... 

Fig. 3.42 depicts a H(/j) isotherm (in arbitrary scale) of an aqueous film from a surfactant solution containing an electrolyte. The two states of black foam films are clearly distinguished. Such a presentation of the 11(6) isotherm can explain the thermodynamic state... 

In order to understand the nature of surface forces which characterise the thermodynamic state of black foam films as well as to establish the CBF/NBF transition, their direct experimental determination is of major importance. This has been first accomplished by Exerowa et al. [e.g. 171,172] with the especially developed Thin Liquid Film-Pressure Balance Technique, employing a porous plate measuring cell (see Section 2.1.8). This technique has been applied successfully by other authors for plotting 11(A) isotherms of foam films from various surfactants solutions [e.g. 235,260,261]. As mentioned in Chapter 2, Section 2.1.2, the Pressure Balance Technique employing the porous ring measuring cell has been first developed by Mysels and Jones [262] for foam films and a FI(A) isotherm was... 

In Section 3.6 it was mentioned that aqueous films on a substrate of organic solvents usually are thermodynamically unstable. A metastable asymmetric aqueous film from surfactant solutions can be obtained also when the electrostatic and/or the adsorption... 

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. 

The addition of solute will also influence the cmc of the surfactant, which in turn means that a correction is needed for the overall partial molar quantity, F This has been taken into account in the models proposed by Roux et al. and DeLisi et al. ° The models have been applied to different thermodynamic properties, mostly volumes and heat capacities, and for different surfactant-solute systems. 

Some colloidal systems such as polymer solutions and surfactant solutions containing micelles are thermodynamically stable and form spontaneously. These types of colloids are called lyophilic colloids. However, most systems encountered contain lyophobic colloids (particles insoluble in the solvent). In the preparation of such lyophobic colloidal dispersions, the presence of a stabilizing substance is essential. Because van der Waals forces usually tend to lead to agglomeration (flocculation) of the particles, stability of such colloids requires that the particles repel one another, either by carrying a net electrostatic charge or by being coated with an adsorbed layer of large molecules compatible with the solvent. 

Miller R, Fainerman VB, Aksenenko EV, Makievski AV, Kraegel J, Liggieri L, Ravera F, Wuestneck R, and Loglio G (2000) "Surfactant Adsorption Kinetics and Exchange of Matter for Surfactant Molecules with Changing Orientation within the Adsorption Layer" in Emulsion, Foams, and Thin Films, Mittal and Kumar Editors, Ch. 18, Marcel Dekker, pp. 313-327 Miller R, Fainerman VB, Makievski AV, Leser M, Michel M and Aksenenko EV (2004) Determination of Protein Adsorption by Comparative Drop and Bubble Profile Analysis Tensiometry. Colloids Surfaces B 36 123-126 Neumann AW and Spelt JK Eds., Applied Surface Thermodynamics, Surfactant Science Series, Vol. 63, Marcel Dekker Inc., New York, 1996 Noskov B and Logho G (1998) Dynamic surface elasticity of surfactant solutions. Colloids Surfaces A 143 167-183... 

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