Thermodynamic data, micellization

Table IX. Thermodynamic Data for Surfactants Micellization at 25°C of Nonionic...

In the work presented here, these processes have been studied primarily by calorimetry. Planned measurements of partial specific heat and partial molal volume will give additional thermodynamic data on the structure of micellar systems. Heat capacity measurements will allow "simple" extrapolation of measured enthalpy terms to higher temperatures. In addition, a direct measure of the effect of temperature variation is of interest for solution structure studies. Partial molal volume measurements give information on the packing of surfactant monomers and micelles within the water structure. The effect of cosurfactants on the partial molal volume will be of particular interest. 

Experimental data indicate that the changes in rates of variation of physical properties near the CMC actually occur over a narrow range of concentrations and not discontinuously at a single concentration. Hraice a chemical reaction or mass action model should be more realistic than the phase separation model for describing the thermodynamics of micellization. That is, we consider that micelle formation occurs as follows ... 

The enthalpy of micellization of many surfactants in aqueous solution has been determined in the past, using mostly cell type and flow microcalorimeters [6-8]. These determinations were based on measurements of the excess heat associated with dilution of a surfactant from a concentration above the cmc to a concentration below the cmc, which results in demicellization of the preexisting micelles. One diffleulty with these determinations relates to the dependence of the heat evolution (AQ) on the initial and final concentrations, probably due to secondary self-aggregations of the surfactants at high concentrations and/or pre-micellar dimer formation at low surfactant concentrations [6,9], These difficulties are at least partially responsible for the lack of consistent data on the thermodynamics of micelle formation [6]. 

In order to obtain thermodynamic data, all of these constants have to be transformed into thermodynamic constants, Ky. Because of co-operative effects in the micelles, the solution is not ideal and the activity of the solute has to be used instead of the molar fraction or concentration. This approach requires the precise definition of standard states. In the articles of Ben-Naim (21) or of Tanford (22), some different standard states are proposed for the solute, i.e. a pure solute or an infinitely dilute state. 

Table II. Thermodynamic Parameters of Micellization for Nonionic of n-C j2H250(EO)jj H at 25°C, data from Rosen et at.(3 ) ...

In contrast to this, there is little information available (11) on the thermodynamics of adsorption of alkyl betaines and no data on the thermodynamic parameters of adsorption or micellization for sulfobetaines. 

In the present work, we have synthesized two betaines and three sulfobetaines in very pure form and have determined their surface and thermodynamic properties of micellization and adsorption. From these data on the two classes of zwitterionics, energetics of micellization and adsorption of the hydrophilic head groups have been estimated and compared to those of nonionic surfactants. 

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. 

Work Is presently under way to extend the above model so as to extract from the experimental data the relevant parameters from a least-squares analysis (13). This model should be applicable to non-lonlc and Ionic systems. In the latter case, an extra term Is required to account for the shift In the CMC of solute 2 due to the sal-tlng-out of the monomers of 2 by solute 3 (7 ). The model In Its present form can still be used to estimate the thermodynamic properties of solute 3 In the micelle of surfactant 2 by adjusting the parameters to get a good fit with the experimental data. 

The chemical equilibrium model of Roux et al (6) is a powerful tool for the study of the thermodynamics of mixed micellar solutions. It can estimate the distribution constant of the surfactant 3 between water and micelles of the surfactant 2 and the thermodynamic properties of the surfactant 3 in the mixed micelles. For this it is necessary to obtain reliable data over a large concentration range of solute 2. 

Scamehorn et. al. (20) also presented a simple, semi—empirical method based on ideal solution theory and the concept of reduced adsorption isotherms to predict the mixed adsorption isotherm and admicellar composition from the pure component isotherms. In this work, we present a more general theory, based only on ideal solution theory, and present detailed mixed system data for a binary mixed surfactant system (two members of a homologous series) and use it to test this model. The thermodynamics of admicelle formation is also compared to that of micelle formation for this same system. 

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. ... 

In. my opinion, the study o-f monolayer -formation has less practical importance than the study o-f micelles. Yet, the thermodynamics of monolayer formation has seen substantial study. I think that this is largely due to the fact that the monomer—monolayer equilibrium can be unambiguously and relatively easily measured using the Hutchinson method (25), as exploited by Rosen and Hua ( ), while this cannot be said for monomer—micelle equilibrium. Therefore, mixed monolayer formation will be a more fruitful field for model development in the near future than mixed micelles because of the availability of a method of obtaining experimental data for comparison. 

The same thermodynamic quantities needed for mixed micelle formation (already discussed) are also needed for mixed admicelle formation. Luckily, the monomer-admicelle equilibrium data can be fairly easily and unambiguously obtained (e.g., see Chapter 15). This should be combined with calorimetric data for a more complete thermodynamic picture of the mixed admicelle. As with micelles, counterion bindings on mixed admicelles also need to be obtained in order to account for electrostatic forces properly. Only one study has measured counterion binding on single-component admicelles (3 .), with none reported for mixed admicelles. 

These studies throw light on the initial aggregation phenomena, which results in micelles and may also (17) constitute the necessary basis for understanding the subsequent agglomeration to liquid crystals. Very little is known about the thermodynamic conditions for the latter associations. Instead we must rely on empirical data to illuminate the basic mechanisms which determine the association behavior of those substances in concentrated systems. Valuable information for understanding the drastic influence of weak intermolecular forces on the association structures (Figure 1) is obtained from the pronounced temperature dependence of the solubilization which was observed early by Shinoda (29). He and his collaborators (30, 31, 32 33) have since developed this subject. 

The micelle formation process and structure can be described by thermodynamic functions (AG°mjc, AH°mjc, AS°mic), physical parameters (surface tension, conductivity, refractive index) or by using techniques such NMR spectroscopy, fluorescence spectroscopy, small-angle neutron scattering and positron annihilation. Experimental data show that the dependence of the aggregate nature, whether normal or reverse micelle is formed, depends on the dielectric constant of the medium (Das et al., 1992 Gon and Kumar, 1996 Kertes and Gutman, 1976 Ward and du Reau, 1993). The thermodynamic functions for micellization of some surfactants are presented in Table 1.1. 

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