Cloud point consolute solution temperature

The cloud point is close to, but not necessarily equal to the lower consolute solution temperature for polydisperse nonionic surfactants (97). These are equal if the surfactant is monodisperse. Since the lower consolute solution temperature is like a critical point for liquid—liquid mixtures, the dilute and coacervate phases have the same composition, and the volume fraction of solution which the coacervate comprises is a maximum at this temperature (98). If a coacervate phase containing a high concentration of surfactant is desired, the solution should be at a temperature well above the cloud point. 

The cloud point phenomena as a lower consolute solution temperature is becoming better understood in terms of critical solution theory and the fundamental forces involved for pure nonionic surfactant systems. However, the phenomena may still occur if some ionic surfactant is added to the nonionic surfactant system. A challenge to theoreticians will be to model these mixed ionic/nonionic systems. This will require inclusion of electrostatic considerations in the modeling. 

Early researchers sought to choose appropriate surfactants for mobility control from the hundreds or thousands that might be used, but very little of the technology base that they needed had yet been created. Since then, work on micellar/polymer flooding has established several phase properties that must be met by almost any EOR surfactant, regardless of the application. This list of properties includes a Krafft temperature that is below the reservoir temperature, even if the connate brine contains a high concentration of divalent ions (i.e., hardness tolerance), and a lower consolute solution temperature (cloud point) that is above the reservoir temperature. 

A plot of the temperatures required for clouding versus surfactant concentration typically exhibits a minimum in the case of nonionic surfactants (or a maximum in the case of zwitterionics) in its coexistence curve, with the temperature and surfactant concentration at which the minimum (or maximum) occurs being referred to as the critical temperature and concentration, respectively. This type of behavior is also exhibited by other nonionic surfactants, that is, nonionic polymers, // - a I k y I s u I Any lalcoh o I s, hydroxymethyl or ethyl celluloses, dimethylalkylphosphine oxides, or, most commonly, alkyl (or aryl) polyoxyethylene ethers. Likewise, certain zwitterionic surfactant solutions can also exhibit critical behavior in which an upper rather than a lower consolute boundary is present. Previously, metal ions (in the form of metal chelate complexes) were extracted and enriched from aqueous media using such a cloud point extraction approach with nonionic surfactants. Extraction efficiencies in excess of 98% for such metal ion extraction techniques were achieved with enrichment factors in the range of 45-200. In addition to metal ion enrichments, this type of micellar cloud point extraction approach has been reported to be useful for the separation of hydrophobic from hydrophilic proteins, both originally present in an aqueous solution, and also for the preconcentration of the former type of proteins. 

From absolute zero (0°K) to 25°C, most hydrophilic solute remains separated in water to an upper critical solution or upper consolute temperature (Tc) (Glasstone and Lewis, 1963) whereupon they merge. In the opposite direction (from high to low temperature), solute and solvent or two solute phases in a common solvent may remain separated to a lower Tc, where they again merge. Many cellulose derivatives have a lower Tc in the vicinity of 45°C. The lower and upper Tc are called cloud points because of the incipient cloudiness observed there. This incipient cloudiness in a formerly translucent dispersion is evidence that the solute has emerged from a secondary minimum on its way to a gel (Walstra et al., 1991). 

CPE is a technique in which an aqueous solution, upon addition of a surfactant and raising the temperature to its cloud point, becomes turbid and amenable to splitting into two phases a surfactant phase and a dilute aqueous phase (Hinze and Pramauro, 1993). A consolute curve (i.e., cloud point versus concentration curve) may be determined, separating the one-phase and two-phase regions of... 

Aqueous solutions of many nonionic amphiphiles at low concentration become cloudy (phase separation) upon heating at a well-defined temperature that depends on the surfactant concentration. In the temperature-concentration plane, the cloud point curve is a lower consolution curve above which the solution separates into two isotropic micellar solutions of different concentrations. The coexistence curve exhibits a minimum at a critical temperature T and a critical concentration C,. The value of Tc depends on the hydrophilic-lypophilic balance of the surfactant. A crucial point, however, is that near a cloud point transition, the properties of micellar solutions are similar to those of binary liquid mixtures in the vicinity of a critical consolution point, which are mainly governed by long-range concentration fluctuations [61]. 

Aqueous solutions of complex soaps (1-3) are drag reducers, as are certain conventional soaps (4-6) and nonionic surfactants (7-11), and they do not have some of these deficiencies. They have the advantage of regaining their drag reducing effectiveness after subjection to high shear fields. The latter two are effective near their coacervation temperature or cloud point (upper consolute temperature). The addition of electrolyte lowers the cloud point and therefore the temperature at which effective drag reduction occurs. Cloud points can be adjusted to convenient temperatures in this manner. 

Lower consolute boundary (or cloud point) The temperature above which micelles separate from solution and form a cloudy suspension at a particular nonionic surfactant concentration. 

The solubility-temperature relationship for nonionic surfactants shows a different behavior from ionic surfactants. Figure 20.6 shows the phase diagram of Ci2E06-The nonionic surfactant forms a clear solution (micellar phase) up to a certain temperature (that depends on concentration) above which the solution becomes cloudy. This critical temperature, denoted as the cloud point (CP) of the solution, decrease with increase in surfactant concentration reaching a minimum at a given concentration (denoted as the lower consolute temperature) above which the CP increases with further increase in surfactant concentration. Above the CP curve the system separates into two layers (water -I- solution). Below the CP curve, several liquid crystalline phases can be identified as the surfactant concentration exceeds a certain limit. Three different liquid crystalline phases can be identified, namely, the hexagonal, the cubic, and lamellar phases. A schematic picture of the structure of these three phases is shown in Fig. 20.7. 

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