Micelle formation Krafft temperature

We may consider precipitation in these systems in the context of competitive aggregate formation between micelles and precipitate. Even systems forming ideal mixed micelles can exhibit synergisms in salinity/hardness tolerance in such systems, the more components present, the higher the tolerance. This is the reason that mixtures of isomeric surfactants generally have Krafft temperatures considerably lower than those of the individual compounds (90). 

For ionic surfactants micellization is surprisingly little affected by temperature considering that it is an aggregation process later we see that salt has a much stronger influence. Only if the solution is cooled below a certain temperature does the surfactant precipitate as hydrated crystals or a liquid crystalline phase (Fig. 12.4). This leads us to the Krafft temperature1 also called Krafft point [526]. The Krafft temperature is the point at which surfactant solubility equals the critical micelle concentration. Below the Krafft temperature the solubility is quite low and the solution appears to contain no micelles. Surfactants are usually significantly less effective in most applications below the Krafft temperature. Above the Krafft temperature, micelle formation becomes possible and the solubility increases rapidly. 

Rico, I. and Lattes, A. (1986). Krafft temperatures and micelle formation of ionic surfactants in formamide. Journal of Physical Chemistry, 90, 5870-2. 

Various approaches have been employed to tackle the problem of micelle formation. The most simple approach treats micelles as a single phase, and this is referred to as the phase-separation model. In this model, micelle formation is considered as a phase-separation phenomenon, and the cmc is then taken as the saturation concentration of the amphiphile in the monomeric state, whereas the micelles constitute the separated pseudophase. Above the cmc, a phase equilibrium exists with a constant activity of the surfactant in the micellar phase. The Krafft point is viewed as the temperature at which a solid-hydrated surfactant, the micelles, and a solution saturated with undissociated surfactant molecules are in equiUbrium at a given pressure. 

The solubility of the surfactant in decane is also quite small at 25°C, about 0.04 wt%, but over a narrow temperature range around 50°C it rises dramatically, as in the Krafft point range of a single-chain surfactant in water (11a). Such a phenomenon with a surfactant in a nonpolar solvent is not uncommon (35). Incidentally, the absence of a Krafft point range for the surfactant in water between 10 and 90°C argues for the absence of micelles in solution. Abrupt change in the slope of such a property as surface tension versus concentration (9) can be due to precipitation of a new phase as well as to onset of appreciable micelle formation, and so does not constitute conclusive evidence for the latter. 

Due to micelle formation the total surfactant concentration undergoes an abrupt increase. Since true (molecular) solubility of surfactants, determined by the CMC, remains essentially constant, an increased surfactant concentration in solution is caused by an increase in a number of formed micelles. Micellar solubility increases with increase in temperature, and thus a continuous transition from pure solvent and true solution to micellar solution, and further to different liquid crystalline systems and swollen surfactant crystals (see below), may take place in the vicinity of the Krafft point. 

Fig. 1. The fatty acid soap-water phase diagram of McBain (58) modified (1) to show the molecular arrangement in relation to aqueous concentration (abscissa) and temperature (ordinate). Ideal solution, i.e., true molecular solution, is to the left of the vertical dashed line, indicating the critical micellar concentration (CMC), which varies little with temperature. At concentrations above the CMC, provided that the temperature is above the critical micellar temperature (CMT), a micellar phase is present. At high concentrations, the soap exists in a liquid crystalline arrangement, provided that the solution is above the transition temperature of the system, i.e., the temperature at which a crystalline phase becomes liquid crystalline. The Krafft point is best defined (D. M. Small, personal communication) as the triple point, i.e., the concentration and temperature at which the three phases (true solution, micelles, and solid crystals) coexist, but in the past the Krafft point has been equated with the CMT. The diagram emphasizes the requirement for micelle formation (a) a concentration above the CMC, (b) temperature above the CMT, and (c) a concentration below that at which the transition from micelles to liquid crystals occurs. Modified from Hofmann and Small (1).

The Krafft point is the temperature at which the solubility of hydrated surfactant crystals increases sharply with increasing temperature and forming micelles. This increase is so sharp that the solid hydrate dissolution temperature is essentially independent of concentration above the critical micelle concentration (cmc) and is therefore often called the Krafft point without specifying the surfactant concentration. The steep increase in solubility above the sharp bend is caused by micelle formation. Micelles exist only at the temperature designated as the Krafft point. This is a triple point at which surfactant mole-... 

The monomeric aqueous solubility of surfactants also depends on pressure, and decreases with increasing pressure. This effect is opposite to that of temperature. In other words, with decreasing pressure the monomeric solubility increases up to the CMC, at which micellization is accompanied by a rapid solubility increase (Fig. 4.19). The pressure at which a solubility-pressure cruve intercepts the CMC-pressure curve is the critical solution pressure Pc for micelle formation, which corresponds to the conventional Krafft point for temperature (see Chapter 6). The presence of Pc is observed... 

In the previous chapters, the dissolution and micellization of surfactants in aqueous solutions were discussed from the standpoint of the degrees of freedom as given by the phase rule. The mass-action model for micelle formation was found to be better for explaining the phenomena of surfactant solutions than the phase-separation model. Two models have similarly been used to explain the Krafft point, one postulating a phase transition at the Krafft point and the other a solubility increase up to the CMC at the Krafft point. The most recent version of the first approach is a melting-point model for a hydrated surfactant solid. The most direct approach to the second model of the Krafft point rests entirely on measurements of the solubility and CMC of surfactants with temperature. From these mesurements the concept of the Krafft point can be made clear. This chapter first reviews the concepts used to relate the dissolution of surfactants to their micellization, and then shows that the concept of a micelle temperature range (MTR) can be used to elucidate various phenomena concerning dissolution... 

The term micelle temperature range expresses the relation between solubility and micelle formation better than Krafft point... 

In MEKC, an ionic surfactant is used as a pseudo-stationary phase, and the Krafft point is also an important temperature. At a temperatures lower than the Krafft point, C f does not exceed the CMC, due to reduced solubility and, therefore, no micelle is formed. At the Krafft point, C f reaches the CMC and then the formation of the micelle is begun. The Krafft point of SDS is 16°C in a pure water, whereas it is 31°C for potassium dodecyl sulfate in pure water. Thus, a potassium salt is not an adequate buffer component for the SDS-MEKC system. 

The solubility characteristics of surfactants are quite different from ordinary salts in water. For instance, the solubility of sodium n-dodecyl sulfate (NaDDS) in water is low, ca. 8 mM, at temperatures lower than 16 °C, while it abruptly increases at temperatures greater than 16 °C. This dependence of solubility on temperature as found for all ionic surfactants, is called the Krafft point. [5]. On the other hand, the solubility of nonionic surfactants (such as alkyl ethoxyethanol with varying number of ethyleneoxide units) exhibits negative solubility in water, that is they become insoluble at a temperature called the Cloud point. In the case of ionic surfactants, the solubility increases drastically at the Krafft point due to the formation of micelles. On the other hand, in the case of nonionic surfactant aqueous solutions, the micellar phase separates into an almost pure surfactant phase at temperatures greater than Cloud point [5,6]. 

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