Emulsifier critical micelle concentration

At low concentrations surfactant molecules adsorbed at the surface are in equilibrium with other molecules in solution. Above a threshold concentration, called the critical micelle concentration (cmc, for short), another equilibrium must be considered. This additional equilibrium is that between individual molecules in solution and clusters of emulsifier molecules known as micelles. 

During Stage I the number of polymer particles range from 10 to 10 per mL. As the particles grow they adsorb more emulsifier and eventually reduce the soap concentration below its critical micelle concentration (CMC). Once below the CMC, the micelles disappear and emulsifier is distributed between the growing polymer particles, monomer droplets, and aqueous phase. 

The kinetic mechanism of emulsion polymerization was developed by Smith and Ewart [10]. The quantitative treatment of this mechanism was made by using Har-kin s Micellar Theory [18,19]. By means of quantitative treatment, the researchers obtained an expression in which the particle number was expressed as a function of emulsifier concentration, initiation, and polymerization rates. This expression was derived for the systems including the monomers with low water solubility and partly solubilized within the micelles formed by emulsifiers having low critical micelle concentration (CMC) values [10]. 

One of the most important characteristics of the emulsifier is its CMC, which is defined as the critical concentration value below which no micelle formation occurs. The critical micelle concentration of an emulsifier is determined by the structure and the number of hydrophilic and hydrophobic groups included in the emulsifier molecule. The hydrophile-lipophile balance (HLB) number is a good criterion for the selection of proper emulsifier. The HLB scale was developed by W. C. Griffin [46,47]. Based on his approach, the HLB number of an emulsifier can be calculated by dividing... 

Like other emulsifiers, an EUP forms micelles at a critical micelle concentration (CMC). For comonomer-free EUP-emulsions of the (MA+HD)- type the CMC is about 5 X 10"4 g/ml [115,118]. The CMC depends on the composition and chain length of the polyester, the presence of an electrolyte [118] and the temperature. 

Fig. 13. Relation between the critical micelle concentration (CMC) of self-emulsifying unsaturated polyesters (EUP) and their Mn[119,120].

Surfactants that form micelles have also been shown to accelerate the formation of nitrosamlnes from amines and nitrite (33.) A rate enhancement of up to 80 0-fold was observed for the nitrosation of dihexylamine by nitrite in the presence of the cationic surfactant decyltrimethylammonium bromide (DTAB) at pH 3.5. A critical micelle concentration (CMC) of 0.08% of DTAB was required to cause this effect, which was attributed to a micelle with the hydrocarbon chains buried in the interior of the micelle. The positively-charged ends of the micelle would then cause an aggregation of free nitrosatable amine relative to protonated amine and thus lead to rate enhancements. Since surfactants are commonly used in water-based fluids (25-50% lubricating agent or 10-2 0% emulsifier in concentrates), concentrations above the CMC of a micelle-forming surfactant could enhance the formation of nitrosamines. 

In order to more closely represent the volatilization environment that would be encountered in an evaporation pond, Triton X-100, a non-ionic emulsifier similar to those used in some pesticide formulations, was added to prepared pesticide solutions at 1000 ppm. The presence of this emulsifier caused a decrease in the percent pesticide volatilized in one day in all cases except for mevinphos (Table VI). Three mechanisms are probably in operation here. First, Triton X-100 micelles will exist in solution because its concentration of 1000 ppm is well above its critical micelle concentration of 194 ppm (30). Pesticide may partition into these micelles, reducing the free concentration in water available for volatilization, which will in turn reduce the Henry s law constant for the chemical (31). Second, the pesticides may exhibit an affinity for the thin film of Triton that exists on the water surface. One can no longer assume that equilibrium exists across the air-water interface, and a Triton X-100 surface film resistance... 

Figure 20 A schematic figure showing how to find critical micelle concentration (CMC) from surface tension analysis at varying emulsifier concentrations.

An emulsifier is a molecule that possesses both polar and nonpolar moieties, i.e., it is amphiphilic. In very dilute water solutions, emulsifiers dissolve and exist as monomers, but when their concentration exceeds a certain minimum, the so-called critical micelle concentration (CMC), they associate spontaneously to form aggregates - micelles. Micelles are responsible for many of the processes such as enhancement of the solubility of organic compounds in water, catalysis of many reactions, alteration of reaction pathways, rates and equilibria, reaction loci for the production of polymers, etc. 

Monodispersed sols containing spherical polymer particles (e.g. polystyrene latexes22"24, 135) can be prepared by emulsion polymerisation, and are particularly useful as model systems for studying various aspects of colloidal behaviour. The seed sol is prepared with the emulsifier concentration well above the critical micelle concentration then, with the emulsifier concentration below the critical micelle concentration, subsequent growth of the seed particles is achieved without the formation of further new particles. 

The irradiation of micellar solutions effects the phase behavior and the critical micelle concentration (CMC). Because radiation sterilization of biopharmaceutical products is a common routine it is important to investigate the influence of radiation on surfactants that are widely used in the pharmaceutical industry for formulations as wetting agents, emulsifiers, or solubilizers. In particular, in drug formulations... 

Breltenbach et al. (12) established that in the case of vinyl acetate emulsion polymerization the dls-pertion rnedlim of the resultant latex contains the amoimt of emulsifier exceeding by a factor of two the critical micelle concentration (CMC), i.e. the reaction system is not depleted of the emulsifier. We obtained similar results in the case of methylacrylate polymerizing with alkyl- and al larylsulphonates. 

The Intersection of the rate curves for the polymerization on which the data for Figure 2 was obtained was at 8.0% conversion. This compares closely with 8.3% conversion at the critical micelle concentration (CMC) as determined by conductivity In Figure 2. Comparative data for other systems are shown In Table I. These results strongly suggest that the Intersection of the polymerization rate curves occurs at the CMC of the oleate soap emulsifier. 

Surface tension measurement. Adsorption titration, also called soap titration, (2.3) was carried out by the drop volume method at different polymer concentrations. The equivalent concentration of salt was held constant. The amount of emulsifier necessary to reach the critical micelle concentration (CMC) in the latex was determined by each titration. The total weight of emulsifier present in the latex is the weight of emulsifier in the water plus the weight of emulsifier adsorbed. The linear plot of emulsifier concentration (total amount of emulsifier corresponding to the end-point of each titration) versus polymer concentration gives the CMC as the intercept and the slope determines the amount of emulsifier adsorbed on the polymer surface in equilibrium with emulsifier in solution at the CMC (E ). 

AU discussions of particle nudeation start with the Smith-Ewart theory in which Smith and Ewart (1948) in a quantitative treatment of Harkins micellar theory (Harkins, 1947, 1950) managed to obtain an equation for the particle number as a function of emulsifier concentration and initiation and polymerization rates. This equation was developed mainly for systems of monomers with low water solubility (e.g., styrene), partly solubilized in micelles of an emulsifier with low critical micelle concentration (CMC) and rseeited to work well for such systems (Gerrens, 1963). Other authors have, however, argued against the Smith-Ewart theory on the grounds that (i) particles are formed even if no micelles are present, (ii) the equation for the... 

Karpov er af. (1977) studied the polymerization in the presence of a number of anionic emulsifiers below the critical micelle concentration. High molecular weight polymers with low concentrations of impurities were obtained at high rates. The overall rate was found to be about 0.5 order with respect to the dose rate with an activation energy of 5 kcal/moI, in reasonable agreement with those reported by Barriac et al. (1976). 

The surface tension of a solution of a surfactant is lower than that of the pure solvent. Surface tension is roughly a linear function of ln(surfactant concentration) up to the critical micelle concentration (CMC) (Figure 3). Above the CMC the thermodynamic activity of the surfactant does not increase with the addition of more surfactant, and the surface tension remains constant. Interfacial tension also decreases with the concentration of an emulsifier dissolved in one of the phases. In Figure 4 the decrease in y does not level off, because the emulsifier (PGMS) does not form micelles in the organic solvent phase (heptane). The changes in the slope of the plot are attributed to changes in orientation of emulsifier molecules at the interface (7). 

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