| 1. |
- Evilevitch, Alex, et al.
(författare)
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Kinetics of oil solubilization in microemulsion droplets. Mechanism of oil transport.
- 2001
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Ingår i: Electroanalysis. - : American Chemical Society (ACS). - 1040-0397. ; 16:23, s. 8755-8762
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the kinetics of the solubilization of oil through a temperature jump into a droplet microemulsion phase in the system water-pentaethylene oxide dodecyl ether-decane at 25 C. The initial state is formed by subjecting the equilibrium system at 25 C to a temperature quench to 22, 20, and 14 C, respectively. At this lower temperature, which at equilibrium corresponds to a two-phase system, oil droplets form and grow in size with increasing time. By varying the time between the quench and the T-jump, the size of the initial oil drops is varied in a systematic and known way in the relaxation study. The relaxation process is monitored by following the turbidity of the system. We find that for all the systems the relaxation back to equlibrium is much faster than the drop growth process observed after the temperature quench. This general observation is explained by realizing that the redissolution of the oil drops is analogous to the oil transfer phase, which in the quench experiment occurs prior to the Ostwald ripening phase. More significant is that we observed a qualitative transition in the relaxation behavior when the initial aggregate distribution is varied. In all cases we have the same initial temperature and overall composition and one population of many small droplets and fewer larger drops. The size of the larger drops only affects the relaxation in a quantitative way. If the small droplets are only slightly smaller than the equilibrium size, equilibration occurs through the diffusion of oil molecules in the bulk phase. When the initial droplets are sufficiently small, a new kinetic route is available where there is an efficient direct oil transfer between the small droplets and large drops. This allows for a fast relaxation of the oil distribution between the two populations of drops.
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| 2. |
- Evilevitch, Alex, et al.
(författare)
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Molecular transport in a nonequilibrium droplet microemulsion system.
- 2001
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 17:22, s. 6893-6904
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Tidskriftsartikel (refereegranskat)abstract
- In this paper, we consider the problem of oil molecular transport between nonequilibrium microemulsion oil droplets in water. In particular, we have investigated the kinetics of solubilization of big oil drops by smaller microemulsion droplets transforming a bimodal size distribution into an equilibrium microemulsion with a unimodal size distribution. The process involves the diffusion of oil monomers across the aqueous solvent. Solubilization experiments are presented on a well-characterized nonionic microemulsion system, where interfacial area and dispersed volume are conserved and where the excess oil chemical potential is dominated by interfacial curvature energy. An analysis of the experiments shows that the solubilization kinetics depend significantly on the concentrations and sizes of big and small droplets. We formulate a quantitative model for the solubilization kinetics where the effects of size and concentrations are treated within the framework of a cell model. A quantitative agreement between model and experiment is obtained, and the analysis also shows that the majority of oil monomers are captured by small droplets already in the vicinity of the big drop surface when the concentration of small droplets is high.
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