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On the Theory of Micellization Kinetics
Author(s) -
Nyrkova Irina A.,
Semenov Alexander N.
Publication year - 2005
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200500010
Subject(s) - micelle , chemistry , thermodynamics of micellization , critical micelle concentration , dissociation (chemistry) , temperature jump , aggregation number , amphiphile , kinetics , relaxation (psychology) , thermodynamics , activation energy , chemical physics , copolymer , organic chemistry , physics , aqueous solution , polymer , psychology , social psychology , quantum mechanics
Summary: We consider certain general features of aggre‐ gation (micellization) processes in solutions of amphiphilic molecules, in particular, block‐copolymers. We demonstrate that non‐equilibrium effects can be very important for micellization. In particular, we show that micelle formation at the conventional (equilibrium) critical micelle concentration (CMC, $c_c$ ) can be inhibited by high activation energy barriers. This is likely to be the case when the micelles are large. In this case an aggregation actually occurs at higher concentrations, above an apparent CMC, $c_{\rm a}$ . The concentration $c_{\rm a}$ can be much higher than the equilibrium CMC. Hence significant hysteresis effects are inherent in amphiphilic systems since micelle formation and dissociation are activation processes. To further clarify this idea we consider relaxation of a micellar system after a temperature jump (or a jump of another essential parameter) and discuss qualitatively different relaxation times corresponding to the relaxations of the micellar sizes and of the total number of micelles. We also discuss different kinetic pathways of micelle formation and relaxation and show that in certain cases the ideal‐gas (combinatorial) contribution to the micelle free energy is significant for the kinetics.Micelle association and dissociation times vs. reduced concentration.