New Micelle Theory

Shortly after the publication of Meyer s paper Staudinger denounced the work of Meyer and Mark as what he called the "New Micelle Theory" (84). In a short time Staudinger and Meyer embarked on an exchange of polemical letters and papers which lasted for more than ten years. Mark, caught between recalled ... 

Then, a few months afterward Meyer repeated and generalized the cellulose structure to include crystalline knots at regular intervals (28). This model was useful in explaining not only the properties of cellulose, but those of rubber as well. Staudinger called the concept unusable, incorrect, and dubbed it "the New Micelle Theory". 

Their disagreement was slight when Meyer reiterated their views in a second paper. Shortly afterward, in October, 1928, Staudinger formally criticized their views and dubbed their model "the new Micelle Theory" (15). The most important issues to Staudinger were the importance of secondary bonding to physical properties and priority. 

Romsted LS (1977) A general kinetic theory of rate enhancements for reactions between organic substrates and hydrophUic ions in micellar systems. In Mittal KL (ed) Micellization, Solubilization, Microemulsions. Plenum Press, New York... 

Case B Radicals enter both micelles and polymer particles at rates that are proportional to their surface areas (collision theory), so that the rate of new particle formation is given by... 

Halle, B., Carlstrom, G., Anderson, T., Wennerstrom, H., and Lindman, B. NMR of water nuclei in heterogeneous systems-relaxation theory and oxygen-17 data from aqueous solutions of proteins, polyelectrolytes and micelles. Biophysics of Water, E Franks, ed., Wiley, New York, pp. 221, 1982. 

We have investigated theoretically film-thickness stability and structure formation inside a liquid film by Monte Carlo numerical simulations and analytical methods, using the Omstein-Zemicke (0-Z) statistical mechanics theory (21-24). The formation of longrange, ordered microstructures (giving rise to an oscillating force) within the liquid film leads to a new mechanism of stabilization of emulsions (3,4,25). In addition to the effective volume of micelles or other colloidal particles and polydispersity in micelle size, the film size is also found to be flic main parameter governing emulsion stability (15). 

The implications on selectivity ofthe direct transfer furnishes a new evidence of the solubility limit theory. The retention mechanism of several hydrophobic compounds (i.e., benzene derivatives, polycyclic aromatic hydrocarbons (P AHs), and dihydropyridines) was studied in SDS and CTAB micellar systems, by comparing experimental selectivity coefficients with those theoretically calculated assuming a direct transfer mechanism [7,8]. A mathematical expression was derived by using the three-partition equilibria theory, which explains the tendency of selectivity coefficients to the ratio of P s coefficients of the solutes, when the concentration of surfactant increases. Expressing the equation that relates the retention with the concentration of micelles as a function of Pms and Pwm-... 

An alternative new approach was that of Kuni and coworkers [90] using nucle-ation theory to derive a new kinetic model acconnting fully for the size distribution of micelles. Their work follows the theory that nncleation is an activated process, although this has yet to become widely accepted. 

In this chapter we shall rederive some of the theories dealt with in the previous chapters and see where the solvent might modify the theory. We shall also discuss some new processes where the solvent plays a crucial role the association and folding of proteins, the formation of micelles, or the aggregation of biological molecules. 

Whilst the theories of Smith and Ewart have dominated academic ideas on emulsion polymerisation, they have had less of an impact on the thinking behind industrial polymerisations. These theories largely describe the formation of particles by radicals entering micelles. When no further micelles exist, then no new particles can be formed. The number of particles is controlled by the amount of surfactant required to cover the surface of the particles, and is proportional to the 0.6 power of the surfactant concentration. 

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