Critical micelle concentration temperature

Ahphatic amine oxides behave as typical surfactants in aqueous solutions. Below the critical micelle concentration (CMC), dimethyl dodecyl amine oxide exists as single molecules. Above this concentration micellar (spherical) aggregates predorninate in solution. Ahphatic amine oxides are similar to other typical nonionic surfactants in that their CMC decreases with increasing temperature. 

A positive value of ME means that the insertion of a hetero atom or group makes the molecule more lipophilic. If ME is negative, the hetero surfactant is more hydrophilic. In general, hetero atom insertion hydrophilizes the surfactant molecule as does the shift of the hetero group to the middle of the carbon chain [71]. ME values are temperature-dependent. / and ME values can also be useful to take into account the influence of various cations on the critical micelle concentration. 

Sanchez et al. [61,62] studied the stability of sodium decyl, dodecyl, and tetradecyl sulfates and sodium lauryl ether (3 EO) sulfate in acid media (pH 1) at different temperatures and concentrations above and below the critical micelle concentration. Sodium decyl sulfate was shown to be relatively stable for several hours at temperatures up to 90°C. Sodium dodecyl and tetradecyl sulfates were only stable for short periods of time at temperatures above 40-50°C. As expected, sodium lauryl ether sulfate was less stable to hydrolysis than the corresponding lauryl sulfate. 

The curve shown in Fig. 6 for sodium dodecyl sulfate is characteristic of ionic surfactants, which present a discontinuous and sharp increase of solubility at a particular temperature [80]. This temperature is known as the Krafft temperature. The Krafft temperature is defined by ISO as the temperature [in practice, a narrow range of temperatures] at which the solubility of ionic surface active agents rises sharply. At this temperature the solubility becomes equal to the critical micelle concentration (cmc). The curve of solubility vs. temperature intersects with the curve of the CMC vs. temperature at the Krafft temperature. 

An amphiphilic molecule has a single positively charged head group and is in solution with a concentration of 10 mM. If the critical micelle concentration of the molecule is 25 mM and the Krafts temperature is 25°C ... 

It was mentioned previously that the narrow range of concentrations in which sudden changes are produced in the physicochemical properties in solutions of surfactants is known as critical micelle concentration. To determine the value of this parameter the change in one of these properties can be used so normally electrical conductivity, surface tension, or refraction index can be measured. Numerous cmc values have been published, most of them for surfactants that contain hydrocarbon chains of between 10 and 16 carbon atoms [1, 3, 7], The value of the cmc depends on several factors such as the length of the surfactant chain, the presence of electrolytes, temperature, and pressure [7, 14], Some of these values of cmc are shown in Table 2. 

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. 

Micelles are extremely dynamic aggregates. Ultrasonic, temperature and pressure jump techniques have been employed to study various equilibrium constants. Rates of uptake of monomers into micellar aggregates are close to diffusion-controlled306. The residence times of the individual surfactant molecules in the aggregate are typically in the order of 1-10 microseconds307, whereas the lifetime of the micellar entity is about 1-100 miliseconds307. Factors that lower the critical micelle concentration usually increase the lifetimes of the micelles as well as the residence times of the surfactant molecules in the micelle. Due to these dynamics, the size and shape of micelles are subject to appreciable structural fluctuations. 

The Krafft Point may be defined as the temperature above which the solubility of a surfactant increases steeply. At this temperature, the solubility of the surfactant becomes equal to the critical micelle concentration (Cj ) of the surfactant. Therefore, surfactant micelles only exist at temperatures above the Krafft Point. This point is a triple point at which the surfactant coexists in the monomeric, the micellar, and the hydrated solid state (, ). 

The temperature, abbreviated c.m.t., at which a deter-gent/solvent system or a lipid/solvent system passes from a hydrated crystalline state to an isotropic micellar solution. For a number of lipids, the c.m.t. is below the freezing point of the solvent. The Krafft point,, is the c.m.t. at the critical micelle concentration. 

FORMATION. Aqueous solutions of highly surface-active substances spontaneously tend to reduce interfacial energy of solute-solvent interactions by forming micelles. The critical micelle concentration (or, c.m.c.) is the threshold surfactant concentration, above which micelle formation (also known as micellization) is highly favorable. For sodium dodecyl sulfate, the c.m.c. is 5.6 mM at 0.01 M NaCl or about 3.1 mM at 0.03 M NaCl. The lower c.m.c. observed at higher salt concentration results from a reduction in repulsive forces among the ionic head groups on the surface of micelles made up of ionic surfactants. As would be expected for any entropy-driven process, micelle formation is less favorable as the temperature is lowered. 

ARRHENIUS EQUATION PLOT CRITICAL MICELLE CONCENTRATION CRITICAL MICELLE TEMPERATURE Critical protein concentration,... 

The variation of the mixture critical micelle concentration (CMCf ) with temperature and with overall surfactant composition has been studied using ultrafiltration for two binary mixed nonionic/anionic systems. 

The temperature (or salinity) at which optimal temperature (or optimal salinity), because at that temperature (or salinity) the oil—water interfacial tension is a minimum, which is optimum for oil recovery. For historical reasons, the optimal temperature is also known as the HLB (hydrophilic—lipophilic balance) temperature (42,43) or phase inversion temperature (PIT) (44). For most systems, all three tensions are very low for Tlc < T < Tuc, and the tensions of the middle-phase microemulsion with the other two phases can be in the range 10 5—10 7 N/m. These values are about three orders of magnitude smaller than the interfacial tensions produced by nonmicroemulsion surfactant solutions near the critical micelle concentration. Indeed, it is this huge reduction of interfacial tension which makes micellar-polymer EOR and its SEAR counterpart physically possible. 

The state of the hydrocarbon chains in mesophases and micelles is reflected in the Krafft phenomena. In aqueous solutions of surfactants the Krafft point is defined as the temperature at which the solubility reaches the critical micelle concentration when the temperature is increased further, the solubility rises rapidly since the monomers form micelles (Figure 5) (10). Lipids that do not form micelles frequently start to swell by the uptake of water at a well-defined temperature they are transformed into a mesomorphous state (Figure 6) (11) The relation between these two Krafft phenomena is explained to some extent by the... 

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