Nonionic, phase diagram

At constant pressure, it is convenient to present the composition-temperature phase behaviour in terms of a phase prism, as illustrated in Figure 17.1. A sequence of constant temperature sections is illustrated in Figure 17.2. Applied to nonionics, phase diagram (a) would correspond to the lowest temperature (< Tq) and (i) to the highest temperature (> To). At lower temperatures (a), a water-rich microemulsion is stable. We note that the phase boundary corresponding to the maximum solubility limit of oil is essentially a straight... 

The Kraft point (T ) is the temperature at which the erne of a surfactant equals the solubility. This is an important point in a temperature-solubility phase diagram. Below the surfactant cannot fonn micelles. Above the solubility increases with increasing temperature due to micelle fonnation. has been shown to follow linear empirical relationships for ionic and nonionic surfactants. One found [25] to apply for various ionic surfactants is ... 

Of all the characteristic points in the phase diagram, the composition of the middle phase is most sensitive to temperature. Point M moves in an arc between the composition of the bottom phase (point B) at and the composition of the top phase (point T) at reaching its maximum surfactant concentration near T = - -T )/2. (Points B and Tmove by much smaller amounts, also.) The complete nonionic-amphiphile—oh—water—temperature... 

Fig. 3. Typical nonionic amphiphile—oil—water—temperature phase diagram, illustrating (a) the S-shaped curve of T, M, and B compositions, (b) the lines of plait points, (c) the lower and upper critical end points (at and respectively), and (d) the lower and upper critical tielines.

Figure 9 shows the effect of acyl chain length (N) on the binary phase diagram of G type nonionics. The area of neat phase spreads with increasing N and the extension of the area takes rapid strides between N of 12 and 14. This N is just in accord with that of the sharp minimum in the cloud point - N curve of the G type. The same thing has also been found for the relation between the effect of OE number on the area of the neat phase and the minimum in the cloud point - OE number curve of CiaGE j (m = 2 - 4). 

Acyl chain length, effect on binary phase diagram of G type nonionics, 42 Adhesion, LAS detergency performance, 250f Adsorption... 

The well-known empirical Bancroft s rule [84] states that the phase in which the surfactant is preferentially soluble tends to become the continuous phase. An analogous empirical correlation has been reported by Shinoda and Saito [85]. Eor a nonionic surfactant of the polyethoxylated type [R-(CH2-CH2-0) -0H, where R is an alkyl chain], as temperature increases, the surfactant head group becomes less hydrated and hence the surfactant becomes less soluble in water and more soluble in oil. Its phase diagram evolves as schematically shown in Fig. 1.4. At low... 

Figure 1.4. For a nonionic surfactant, influence of the temperature on (a) the surfactant morphology and hence the spontaneous curvature, (b) the type of self-assembly, (c) the phase diagram, the number of coexisting phases is indicated (d) the coexisting phases at equilibrium, and (e) the corresponding emulsions.

The influence of a cream containing 20% glycerin and its vehicle on skin barrier properties has been investigated. Recent studies have shown that polymers offer several advantages and can be used in skin care products. Phase diagrams were determined for lactic and isohexanoic hydroxy acids as well as salicylic acid with water, a nonionic surfactant and a paraffinic oil, to outline the influence of hydroxy acids on the structure in a model for a skin lotion. The results showed the influence of the acid to be similar to that of the oil but that the difference in chain length between the two alpha acids had only insignificant influence. The results are discussed from two aspects the structures involved in the lotion as applied, and the action of the lotion residue on the skin after the evaporation of the water. 

A considerable amount of experimental work has been carried out on the so-called gel emulsions of water/nonionic surfactant/oil systems [9-14, 80, 106, 107]. These form in either the water-rich or oil-rich regions of the ternary phase diagrams, depending on the surfactant and system temperature. The latter parameter is important as a result of the property of nonionic surfactants known as the HLB temperature, or phase inversion temperature (PIT). Below the PIT, nonionic surfactants are water-soluble (hydrophilic form o/w emulsions) whereas above the PIT they are oil-soluble (hydrophobic form w/o emulsions). The systems studied were all of very high phase volume fraction, and were stabilised by nonionic polyether surfactants. 

We saw in Section 8.6 that phase diagrams are an effective way of representing the complex behavior of surfactant systems. Let us take a look at microemulsions in terms of phase diagrams. It turns out that nonionic surfactants form microemulsions at certain temperatures without requiring cosurfactants. Since only three components are present, these have somewhat simpler phase diagrams this kind of system offers a convenient place to begin. 

To single out the peculiarities in the phase behavior of ionic fluids, it is convenient to consider first the behavior of nonionic (e.g., van der Waals-like) mixtures. We note, however, that the subsequent considerations ignore liquid-solid phase equilibria, which in real electrolyte solutions can lead to far more complex topologies of the phase diagrams than discussed here [150],... 

Phase diagrams of water, hydrocarbon, and nonionic surfactants (polyoxyethylene alkyl ethers) are presented, and their general features are related to the PIT value or HLB temperature. The pronounced solubilization changes in the isotropic liquid phases which have been observed in the HLB temperature range were limited to the association of the surfactant into micelles. The solubility of water in a liquid surfactant and the regions of liquid crystals obtained from water-surfactant interaction varied only slightly in the HLB temperature range. 

The presence of a liquid crystalline phase at high surfactant concentrations has been shown by Shinoda (31), but the method of presentation renders the evaluation of the temperature dependence of necessary emulsifier concentrations to obtain the liquid crystalline phase difficult. Although several phase diagrams of the system (water, emulsifier, and nonionic surfactant) have been published (4, 45, 46, 47, 48), no results have been given on the relation between the surfactant phase and the lamellar liquid crystalline phase in these systems. 

Peters and Luthy (1993, 1994) performed a detailed analysis of the equilibrium behavior of solvent coal tar water mixtures in work that was complementary to column studies performed by Roy, et. al. (1995). Peters and Luthy successfully modeled ternary phase diagrams of coal tar/n-butylamine/water systems. In addition, Peters and Luthy identified n-butylamine as the leading solvent for coal tar extraction. Pennell and Abriola (1993) report the solubilization of residual dodecane in Ottawa sand using a nonionic surfactant, polyoxyethylene sorbitan monooleate, which achieved a 5 order of magnitude increase over the aqueous solubility, but is still 7 times less than the equilibrium batch solubility with the same surfactant system. 

A limited number of studies have considered the use of surfactant and cosolvent mixtures to enhance the recovery of NAPLs (Martel et al., 1993 Martel and Gelinas, 1996). Martel et al. (1993) and Martel and Gelinas (1996) employed ternary phase diagrams to select surfactant+cosolvent formulatons for treatment of NAPL-contaminated aquifers. The surfactant+cosolvent formulations used in their work, which included lauryl alcohol ethersulfate/n-amyl alcohol, secondary alkane sulfonate/n-butanol, and alkyl benzene sulfonate/n-butanol, were shown to be effective solubilizers of residual trichloroethene (TCE) and PCE in soil columns (Martel et al., 1993). However, very little information is available regarding the effect of cosolvents on the solubilization capacity and phase behavior of ethoxylated nonionic surfactants. 

The phase diagrams of two-component surfactant-water systems are typically quite different for nonionic and ionic compounds. As exemplified in Fig. 2.22 there are at low temperatures different liquid crystalline phases while at intermediate temperatures there may be a total mutual solubility of surfactant and water98. At higher temperatures, there is, as already noted, a separation into two phases with a very large two-phase region. One of the phases contains very little surfactant, while the other contains appreciable amounts of both components. The cloud-point curve can be described as a liquid-liquid solubility curve with a lower consolute tempera-... 

Schomacker compared the use of nonionic microemulsions with phase transfer catalysis for several different types of organic reactions and concluded that the former was more laborious since the pseudo-ternary phase diagram of the system had to be determined and the reaction temperature needed to be carefully monitored [13,29]. The main advantage of the microemulsion route for industrial use is related to the ecotoxicity of the effluent. Whereas nonionic surfactants are considered relatively harmless, quaternary ammonium compounds exhibit considerable fish toxicity. 

Figure 6. Phase diagram for a typical nonionic surfactant. region refers to an isotropic amphiphile solution whereas and indicates the two co-existing isotropic phases.

Karlstrom, G. Carlsson, A. Lindman, B., "Phase Diagrams of Nonionic Polymer-Water Systems. Experimental and Theoretical Studies of the Effects of Surfactants and Other Cosolutes," J. Phys. Chem., 94, 5005 (1990). 

Fig. 10 Binary phase diagram of a a) monomeric nonionic surfactant, b) non-ionic polysurfactant in aqueous solution A heterogeneous mixed crystals B heterogeneous melt C homogeneous isotropic solution D homogeneous mesomorphous phases...

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