Content material: Lindman, B. and Wennerström, H. Micelles. Amphiphile aggression in aqueous resolution. -- Eicke, H.-F. Surfactants in nonpolar solvents. Aggregation and micellization
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Extra info for Micelles
In this theory, the small system, in the present context the micelle, is regarded as immersed in a thermodynamic bath defining the value o f the intensive variables. The consequence of having a finite system, relative to the infinite systems of classical thermodynamics, is that the number o f independent intensive variables is increased by one. For a micellar system, the natural choice of independent variables is the temperature, the pressure and the chemical potential t~aq o f the monomeric amphiphile.
4 Model Calculations of the Free Energy of Micelle Formation. Micelle Size and Shape The first attempt to theoretically describe the formation of micelles in terms of molecular interactions was made by Debye is0, is1). He considered a hydrophobic and an electrostatic energy contribution and saw the formation of micelles as due to the competition of these two forces. Although the expressions for the free energies were qualitatively incorrect, in the sense that the amphiphile aggregation was predicted to be anticooperative instead of cooperative ~s2), Debye correctly identified the important interactions.
The conversion of this into a self-diffusion coefficient may become cumbersome at high surfactant concentrations. Berne and Pecora 17s) give most appropriate aspects of this problem. Thus because of concentration fluctuations, the normal spherically symmetric configuration of counterions ions around a spherical micelle can become asymmetric, so that the micelle experiences a nonzero electrical force. This instantaneous force due to the counterion distribution accelerates the micelle motion so that it becomes larger than would be expected on the basis of Stokes' law.