Krafft point, surfactants

The Krafft point has practical implications for the solubility of surfactants. Only above the Krafft temperature can concentrated surfactant solutions be prepared. Otherwise, on cooling a hot surfactant solution a sudden precipitation may occur. A linear correlation between the Krafft temperature TK (°C) and the carbon number nc of sodium alkanesulfonates C10-C22 is given by the following equation ... 

FIG. 2 Krafft points 7" of hqucous surfactant solutions vs. mixing ratio of c16/c, a-ester sulfonates. (From Ref. 58.)... 

Micelles only form above a crucial temperature known as the Krafft point temperature (also called the Krafft boundary or just Krafft temperature). Below the Krafft temperature, the solubility of the surfactant is too low to form micelles. As the temperature rises, the solubility increases slowly until, at the Krafft temperature 7k, the solubility of the surfactant is the same as the CMC. A relatively large amount of surfactant is then dispersed into solution in the form of micelles, causing a large increase in the solubility. For this reason, IUPAC defines the Krafft point as the temperature (or, more accurately, the narrow temperature range) above which the solubility of a surfactant rises sharply. 

In reverse, the surfactant precipitates from solution as a hydrated crystal at temperatures below 7k, rather than forming micelles. For this reason, below about 20 °C, the micelles precipitate from solution and (being less dense than water) accumulate on the surface of the washing bowl. We say the water and micelle phases are immiscible. The oils re-enter solution when the water is re-heated above the Krafft point, causing the oily scum to peptize. The way the micelle s solubility depends on temperature is depicted in Figure 10.14, which shows a graph of [sodium decyl sulphate] in water (as y ) against temperature (as V). 

The value of TK is best determined by warming a dilute solution of surfactant, and noting the temperature at which it becomes clear. Table 10.4 lists the Krafft points for a series of colloidal systems based on aqueous solutions of sodium alkyl sulphate (cf. structure III). 

Domain Where Physics, Chemistry, Biology, and Technology Meet (see above) p. 11. The paper, Use of quantitative structure-property relationships in predicting the Krafft point of anionic surfactants by M. Jalali-Heravi and E. Konouz, Internet Electronic Journal of Molecular Design, 2002, 1, 410, has a nice introduction and useful references. It can be downloaded at http //www.biochempress.com/av01 0410.html. 

Performance Indices Quality Factors Optimum E1LB Critical micelle concentration (CMC) Soil solubilization capacity Krafft point (ionic surfactants only) Cloud point (nonionic surfactants only) Viscosity Calcium binding capacity Surface tension reduction at CMC Dissolution time Material and/or structural attributes... 

Krafft point (for ionic surfactants) and cloud point (for nonionic surfactants) are both a limit to surfactant solubility. The solubility of ionic surfactants decreases significantly below the Krafft point, since its concentration falls below the CMC and individual surfactant molecules cannot form micelles. Therefore, the Krafft point of an ionic surfactant must be below the desired wash temperature for maximum soil removal. In contrast, the solubility of some nonionic surfactants decreases with increasing temperature. Above the cloud point, the surfactant becomes insoluble. Thus, the cloud point of a nonionic surfactant should be 15-30°C above the intended wash temperature [8],... 

Krafft point, Tyaff, Surfactant chain length, l Increases with increasing l... 

Alkyl ether sulfates are/after alkyl benzene sulfonates(LAS),the group of technically important anionic surfactants with the largest production voluJne and product value. They have in comparison with other anionic surfactants special properties which are based on the particular structure of the molecule. These are expressed,for example,in the general adsorption properties at different interfaces, and in the Krafft-Point. Alkyl ether sulfates may be used under conditions, at which the utilization of other surfactant classes is very limited. They possess particularly favorable interfacial and application properties in mixtures with other surfactants. The paper gives a review of all important mechanisms of action and properties of interest for application. 

The great technical and economic Tmportance of this product group was reached despite its higher price only because of its special properties. Due to the ionic sulfate group and the adjacent ether groups, ether sulfates combine the classical elements of ionic and nonionic surfactants in one molecule. This provides a number of properties, one of which, the Krafft-Point, is of special importance for the technical application of these compounds. 

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 (, ). 

Below the Krafft Point, the surfactant dissolved in a molecularly dispersed manner until the saturation concentration is reached. At higher concentrations, a hydrated solid is in equilibrium with individual molecules. Above the Krafft Pointy the hydrated solid is in equilibrium with micelles and individual molecules. 

Therefore, the physical meaning of the solubility curve of a surfactant is different from that of ordinary substances. Above the critical micelle concentration the thermodynamic functions, for example, the partial molar free energy, the activity, the enthalpy, remain more or less constant. For that reason, micelle formation can be considered as the formation of a new phase. Therefore, the Krafft Point depends on a complicated three phase equilibrium. 

An especially effective reduction of the Krafft Point results from the insertion of ether groups into the molecule of the anionic surfactant. In table I this is examplified with Na dodecyl sulfate and Na-tetra-decyl sulfate in comparison to various n-alkyl ether sulfates of the same chain length (10). As a measure of the Krafft Point, a temperature is deTined at which a 1 7o solution dissolves clearly. By the incorporation of oxyalkylene groups into the molecule, the Krafft -Point and the melting point are greatly depressed. This depression is especially effective if there is branching in the oxyalkylene groups. 

The lower Krafft Points resulting from the incorporation of oxyethylene groups into the surfactant molecule is an essential, but not sufficient, property for the utilizationof alkyl ether sulfates. 

Washing and Cleaning Action. The properties of alkyl ether sulfates, due to the good solubility and the special hydrophilic/hydrophobic properties of the molecule, are of particular practical interest. From the investigations described in sections 2 and 3, it can be concluded that, in addition to the decrease in the Krafft Point, favorable properties for practical applications can be expected as a result of the inclusion of the oxyethylene groups into the hydrophobic part of the molecule. As is true for other anionic surfactants, the electrical double layer will be compressed by the addition of multivalent cations. By this means, the adsorption at the interface is increased, the surface activity is raised, and, furthermore, the critical micelle concentration decreased. In the case of the alkyl ether sulfates, however these effects can be obtained without encountering undesirable salting out effects. 

Further, it is well known that the addition of electrolytes to ionic surfactant aqueous solutions increase the Krafft point (24,... 

FIGURE 3.6 Solubility (Krafft point KP) of ionic (anionic or cationic) surfactants in water (as a function of temperature). 

Carrying out an emulsion polymerization requires an awareness of the krafft point of an ionic surfactant and the cloud point of a nonionic surfactant. Micelles are formed only at temperatures above the Krafft point of an ionic surfactant. For a nonionic surfactant, micelles are formed only at temperatures below the cloud point. Emulsion polymerization is carried out below the cloud temperature of a nonionic surfactant and above the Krafft temperature of an ionic surfactant. 

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... 

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. 

Han, S. K., S. M. Lee, M. Kim, and H. Schott. 1989. Effect of protein denaturants on cloud point and Krafft point of nonionic surfactants . Colloid Interface Sci132 444-450. 

Micelle-forming surfactants exhibit another unusual phenomenon in that their solubilities show a rapid increase above a certain temperature, known as the Krafft point. The explanation of this behaviour arises from the fact that unassociated surfactant has a limited solubility, whereas the micelles are highly soluble. Below the Krafft temperature the solubility of the surfactant is insufficient for micellisation. As the temperature is raised, the solubility slowly increases until, at the Krafft temperature, the c.m.c. is reached. A relatively large amount of surfactant can now be dispersed in the form of micelles, so that a large increase in solubility is observed. 

Fig. 2.8. Temperature dependence of surfactant solubility in the region of the Krafft point. (From Ref.2 )...

There exists, actually, another aspect regarding a temperature variation of surfactant solutions the well-known Krafft-point determination128). Since, however, not a micellar property is concerned but the temperature dependence of the monomer activity of the soap molecules, this section is considered more as an appendix to the foregoing discussion. 

In comparison to aqueous soap solutions there exist relatively few determinations of Krafft points in nonpolar surfactant solutions. An interesting example is due to Addison and Furmidge21 who determined the solubilities of four alkylpyri-dinium iodides (dodecyl-, tetradecyl-, hexadecyl-, and octadecyl-) in xylene (mixture of isomers, b.p. 138 °C). The solubilities were plotted against 1/T (see Fig. 22). The breaks in the curves and the chain length effect (which is much less pronounced compared to aqueous solutions) are clearly shown. Similar experiments have been reported by Mehrotra et al.146 on copper soaps in various organic solvents and by Malik et al.140 on cobalt hexamine soaps. 

Another important transition of surfactants involving micelles, the critical micellization temperature (CMT), has been found to be readily amenable to study by FT-IR, largely because of the relatively high surfactant concentrations involved (>0.1 M). The CMT is concentration dependent up to concentrations of about 0.1 to 0.3 M, above which the dependence decreases significantly. The Krafft point is thus found at lower temperatures than the CMT, and can be considered the CMT at the cmc (63-65). A thermostatted transmission cell for control of the temperature of the surfactant solutions, held between CaF2 or BaF2 windows, is necessary. Automation of the entire spectroscopic CMT experiment has been described (66). 

The solubilities of micelle-forming surfactants show a strong increase above a certain temperature, termed the Krafft point (Tk). This is explained by the fact that the single surfactant molecules have limited solubility whereas the micelles are very soluble. Referring to Figure 3.22, below the Krafft point the solubility of the surfactant... 

Non-ionic surfactants do not exhibit Krafft points. Rather the solubility of nonionic surfactants decreases with increasing temperature and the surfactants begin to lose their surface active properties above a transition temperature referred to as the cloud point. This occurs because above the cloud point a separate surfactant-rich phase of swollen micelles separates the transition is visible as a marked increase in dispersion turbidity. As a result, the foaming ability of, for example, polyoxyethyle-nated non-ionics, decreases sharply above their cloud points. The addition of electro-... 

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