Ionic surfactants solution properties

Calculated concentrations, using (4.9), for the various components, surfactant monomers, counter-ions and micelles, for the case of CTAB micellization (with a cmc of 0.9mM), is shown in Figure 4.5. Clearly, the micelle concentration increases rapidly at the cmc, which explains the sharp transition in surfactant solution properties referred to earlier. It is also interesting to note that the law of mass action (in the form of equation 4.9) predicts an increase in counterion (Br ions) concentration and a decrease in free monomer concentration above the cmc. It has been proposed that for ionic surfactants, a useful definition of the cmc would be... 

Solutions of highly surface-active materials exhibit unusual physical properties. In dilute solution the surfactant acts as a normal solute (and in the case of ionic surfactants, normal electrolyte behaviour is observed). At fairly well defined concentrations, however, abrupt changes in several physical properties, such as osmotic pressure, turbidity, electrical conductance and surface tension, take place (see Figure 4.13). The rate at which osmotic pressure increases with concentration becomes abnormally low and the rate of increase of turbidity with concentration is much enhanced, which suggests that considerable association is taking place. The conductance of ionic surfactant solutions, however, remains relatively high, which shows that ionic dissociation is still in force. 

It may be concluded that the theory presented for single ionic surfactants can be extended to predict the surface properties of mixed ionic surfactant solutions from the characteristic parameters of the single surfactants. 

The existence of an electric double layer can remarkably influence the dynamic interfacial properties of ionic surfactant solutions [96, 97, 98, 99, 100]. The equilibrium state of such interfacial layers has been described in much detail in Paragraph 2.5. The dynamic problems, however, are rather complex and difficulties arise in solving the respective set of non-linear equations. 

A detailed physicochemical model of the micelle-monomer equilibria was proposed [136], which is based on a full system of equations that express (1) chemical equilibria between micelles and monomers, (2) mass balances with respect to each component, and (3) the mechanical balance equation by Mitchell and Ninham [137], which states that the electrostatic repulsion between the headgroups of the ionic surfactant is counterbalanced by attractive forces between the surfactant molecules in the micelle. Because of this balance between repulsion and attraction, the equilibrium micelles are in tension free state (relative to the surface of charges), like the phospholipid bilayers [136,138]. The model is applicable to ionic and nonionic surfactants and to their mixtures and agrees very well with the experiment. It predicts various properties of single-component and mixed micellar solutions, such as the compositions of the monomers and the micelles, concentration of counterions, micelle aggregation number, surface electric charge and potential, effect of added salt on the CMC of ionic surfactant solutions, electrolytic conductivity of micellar solutions, etc. [136,139]. 

As already mentioned, the surfactants are used to stabilize the liquid films in foams, in emulsions, on solid surfaces, and so forth. We will first consider the equilibrium and kinetic properties of surfactant adsorption monolayers. Various two-dimensional equations of state are discussed. The kinetics of surfactant adsorption is described in the cases of dijfusion and barrier control. Special attention is paid to the process of adsorption from ionic surfactant solutions. Theoretical models of the adsorption from micellar surfactant solutions are also presented. The rheological properties of the surfactant adsorption mono-layers, such as dilatational and shear surface viscosity and suiface elasticity, are introduced. The specificity of the proteins as high-molecular-weight surfactants is also discussed. 

The mechanisms that affect heat transfer in single-phase and two-phase aqueous surfactant solutions is a conjugate problem involving the heater and liquid properties (viscosity, thermal conductivity, heat capacity, surface tension). Besides the effects of heater geometry, its surface characteristics, and wall heat flux level, the bulk concentration of surfactant and its chemistry (ionic nature and molecular weight), surface wetting, surfactant adsorption and desorption, and foaming should be considered. 

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. 

Tomasic V, Chittofrati A, Kallay N (1995) Thermodynamic properties of aqueous solutions of perfluorinated ionic surfactants. Colloids and Surfaces, Physicochemical and Engeneering Aspects 104 95-99... 

What characterizes surfactants is their ability to adsorb onto surfaces and to modify the surface properties. At the gas/liquid interface this leads to a reduction in surface tension. Fig. 4.1 shows the dependence of surface tension on the concentration for different surfactant types [39]. It is obvious from this figure that the nonionic surfactants have a lower surface tension for the same alkyl chain length and concentration than the ionic surfactants. The second effect which can be seen from Fig. 4.1 is the discontinuity of the surface tension-concentration curves with a constant value for the surface tension above this point. The breakpoint of the curves can be correlated to the critical micelle concentration (cmc) above which the formation of micellar aggregates can be observed in the bulk phase. These micelles are characteristic for the ability of surfactants to solubilize hydrophobic substances in aqueous solution. So the concentration of surfactant in the washing liquor has at least to be right above the cmc. 

The non-ionic surfactants do not produce ions in aqueous solution. The solubility of non-ionic surfactants in water is due to the presence of functional groups in the molecules that have a strong affinity for water. Similarly to the anionic surfactants, and any other group of surfactants, they also show the same general property of these products, which is the reduction of the surface tension of water. 

Physical properties of the protein structure should be considered in designing strategies to achieve stable formulations because they can often yield clues about which solution environment would be appropriate for stabilization. For example, the insulin molecule is known to self-associate via a nonspecific hydrophobic mechanism66 Stabilizers tested include phenol derivatives, nonionic and ionic surfactants, polypropylene glycol, glycerol, and carbohydrates. The choice of using stabilizers that are amphiphilic in nature to minimize interactions where protein hydrophobic surfaces instigate the instability is founded upon the hydro-phobic effect.19 It has already been mentioned that hydrophobic surfaces prefer... 

In spite of this wide applicability, a survey of the literature reveals that, compared to ionic and non ionic surfactants, there have been relatively few investigations of their surface and thermodynamic properties. Investigation has been hampered by the nonavailability of pure compounds and proper analytical techniques to determine their concentration in solution. 

Shinoda, K., Yamanaka, T., andKinoshita, K. Surface chemical properties in aqueous solutions of non-ionic surfactants octyl glycol ether, a-octyl glyceryl ether and octyl glycoside. J. Phys. Chem., 63(5) 648-650,1959. 

Lawrence, M.J., S.M. Lawrence, and D.J. Barlow. 1997. Aggregation and surface properties of synthetic double-chain-ionic surfactants in aqueous solution. J Pharm Pharmacol 49 594. 

Based on their data for sorption onto a lake sediment, Kiewiet et al. (1996) derived an equation predicting sorption coefficients of CnEOms as a functions of alkyl chain length and the number of oxyethylene units. Di Toro et al. (1990) proposed a model for description of sorption of anionic surfactants which includes sorbent properties (organic carbon content, cation exchange capacity, and particle concentration) and the CMC as a function of the solution properties (ionic strength, temperature). The CMC is used as a relative hydrophobicity parameter. Since the model takes the contribution of electrostatic as well as hydrophobic forces explicitly into account, it is an example of an attempt to model surfactant behavior on the basis of the underlying mechanisms. 

Most of the experimental and theoretical work on the aggregation of ionic surfactants in water has been devoted to understanding how this phenomenon is affected by such factors as concentration, temperature or chemical nature of the surfactants. Much less is known as to how surfactant aggregation is affected by an increase in hydrostatic pressure. Advances in the technique of high pressure vibrational spectroscopy (FT-IR and Raman) of aqueous systems have allowed us now to examine the effect of hydrostatic pressure on the structural and dynamic properties of a large number of surfactants in solution. 

There is a vast body of diblock copolymer studies since block choice can be such that they resemble amphiphilic surfactants. For the sake of brevity, we will skip them. Instead, we present an interesting case of triblock copolymers of poly(ethylene oxide), PEO, and poly(propylene oxide), PPO, commonly known by one of its trade names, Pluronics [117]. They have been used as non-ionic surfactants for a variety of applications such as in emulsification and dispersion stabilization. In aqueous solutions, these copolymers form micelles, and there exists a well-defined critical micelle concentration that is experimentally accessible. Several groups have investigated colloidal suspensions of these polymers [118-122], The surface properties of the adsorbed monolayers of the copolymers have been reported with respect to their structures and static properties [123-126]. 

Fig. 3.33 presents a comparison of the data for the two copolymers. It is now accepted that bulk properties of aqueous solutions of PEO-PPO-PEO triblock copolymers are essentially similar to these of non-ionic surfactants (e.g. [225]). The dependence in Fig. 3.33 resembles very much the hw(Cei) isotherm for NP(EO)20 [172]. It is very likely that in both cases the interaction behaviour is determined by the hydrophilic PEO chains protruding into the solution. 

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