Micelles relaxation processes

Investigation of water motion in AOT reverse micelles determining the solvent correlation function, C i), was first reported by Sarkar et al. [29]. They obtained time-resolved fluorescence measurements of C480 in an AOT reverse micellar solution with time resolution of > 50 ps and observed solvent relaxation rates with time constants ranging from 1.7 to 12 ns. They also attributed these dynamical changes to relaxation processes of water molecules in various environments of the water pool. In a similar study investigating the deuterium isotope effect on solvent motion in AOT reverse micelles. Das et al. [37] reported that the solvation dynamics of D2O is 1.5 times slower than H2O motion. 

Effectiveness of a crude oil demulsifier is correlated with the lowering of shear viscosity and dynamic tension gradient of the oil-water interface. Using the pulsed drop technique, the interfacial dilational modulii with different demulsifiers have been measured. The interfacial tension relaxation occurs faster with an effective demulsifier. Electron spin resonance with labeled demulsifiers indicate that the demulsifiers form reverse micelle like clusters in bulk oil. The slow unclustering of the demulsifier at the interface appears to be the rate determining step in the tension relaxation process. 

In the early 1960s it became evident that the reaction environment had an important role in dictating the course of photochemical conversions acting on the course of the relaxation processes and stabilizing photoproducts.17 A constrained medium such as that of a porous matrix or a micelle provides the restricted environment to stop any bimolecular processes that could lead to degradation of products. These effects, however, are subtle. For instance, confinement of a molecule within a host instead of leading to inhibition of reactions of the trapped substrate often results in enhanced reactivity and selectivity because confinement does not mean steric inhibition of all motions of the entrapped host molecule which may eventually enjoy less restriction of some motions than in common solvents. 

We have thus far considered coherent processes that take place in RPs (which in some cases been have been modulated by stochastic motion). However, the common spin-lattice and spin-spin relaxation processes familiar from magnetic resonance also come to bear on the dynamics of RPs. Typical values of Ti and T2 for small organic radicals in homogeneous solution are on the microsecond timescale and as such are rather slow relative to coherent mixing and RP diffusion. Thus, for the most part, effects of incoherent spin relaxation are not manifest in such reactions. However, for reactions in which the RP lifetime is substantially extended, for instance, by constraining the RP inside a microreactor such as a micelle (many examples in Ref. 14), relaxation effects become significant. 

The relaxation time of the dissociation for the micelle-monomer exchange process (fast relaxation process) [75] is given by... 

Ultrasonic relaxation spectroscopy (URS) is nothing but a special treatment of data from ultrasonic absorption measurements. Micelle dynamics involves characteristic relaxation processes, namely micelle-monomer exchange and micelle formation-breakdown. Ultrasonics can provide information about the kinetics of the latter, the fast relaxation process also, theoretical expressions for the relaxation time and relaxation strength such as those derived by Teubner [76] provide self-consistent estimates of both. 

We now discuss the dependence of the relaxation frequency on the concentration of CuTAB along the line of the theory of Annianson for the relaxation process of mixed micelle. In this argument, the micellar solution consists of two kinds of surfactants. Under the condition that the dissociation rate constant of surfactant I is much larger than that of surfactant 2, the reciprocal of the relaxation time of the fast process is written in the following way... 

Micelles are in dynamic equilibrium with their monomer surfactants. Two relaxation processes are related to this equilibrium, a fast one in the microsecond time domain associated with the exchange of individual monomers between the micelles and the bulk aqueous phase and a slower one on millisecond time-scale associated with the complete dissolution of the micelles into monomers [8], For example, the exit rate for the SDS anion from its micelle is about lO s, which is considered to be a diffusion-controlled process [8a]. Nonpolar molecules are usually attracted to the relatively hydrophobic inner core of micelles, whereas ionic reactants and products are either associated with the Stem and Gouy-Chapman layers or repelled from the micelles, depending on the sign of electrostatic interaction. For example, NMR studies show that nonpolar molecules such as benzene and naphthalene are... 

Figure 13.22 Damping functions hf y) and hs y) for the fast and slow relaxation processes of a 15 wt% solution of a micelle-forming polystyrene-polyisoprene diblock copolymer (molecular weights, respectively, of 14,000 and 29,000) in a low-molecular-weight (A/ = 4,000) polyisoprene. Damping functions for linear and star polymers and for silica dispersion are shown for comparison. (From Watanabe et al. 1997, with permission from Macromolecules 30 5905. Copyright 1997, American Chemical Society.)...

There continues to be extensive interest in latexes and micellar systems. The structure of acrylic latex particles has been investigated by non-radiative energy transfer by labelling the co-monomers with fluorescent acceptor-donor systems. Phase separations could also be measured in this way. Excimer fluorescence has been used to measure the critical micelle temperature in diblock copolymers of polystyrene with ethylene-propylene and the results agree well with dynamic light scattering measurements. Fluorescence anisotropy has been used to measure adsorption isotherms of labelled polymers to silica as well as segmental relaxation processes in solutions of acrylic polymers. In the latter case unusual interactions were indicated between the polymers and chlorinated hydrocarbon solvents. Fluorescence analysis of hydrophobically modifled cellulose have shown the operation of slow dynamic processes while fluorescence... 

We assume here that the kinetic constants kj,kj,k,k, are independent of the length of micelles and surfactant concentration. Therefore, the relaxation of concentration f)erturbation in solutions of wormlike micelles can be essentially more complicated. Moreover, the relaxation processes enumerated above can influence at a different extent various properties of the non-equilibrium micellar solution. This gives a general possibility to determine all these relaxation times. The first of these relaxation processes can be described by model (5.185). The fifth one corresponds obviously to the fast relaxation process in the Aniansson and Wall model. Recently Waton derived an equation for the relaxation times of fusion and fission in micellar solutions, which can be applied to an arbitrary size distribution of micelles [128]. In the limiting cases of short micelles with a narrow size distribution and wormlike micelles this theory leads to relations (5.192) and (5.194), respectively. 

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