Small cloud point

Recent publications indicate the cloud-point extraction by phases of nonionic surfactant as an effective procedure for preconcentrating and separation of metal ions, organic pollutants and biologically active compounds. The effectiveness of the cloud-point extraction is due to its high selectivity and the possibility to obtain high coefficients of absolute preconcentrating while analyzing small volumes of the sample. Besides, the cloud-point extraction with non-ionic surfactants insures the low-cost, simple and accurate analytic procedures. 

Cloud Points The influence of added NaCl on the observed cloud points of 1% W/V solutions of the four nonionic surfactants under observation are given in Figure 1. Approximately linear correlations were observed as the aqueous NaCl level was increased, with negative coefficients recorded between 0.22 - 0.3 K.g "1dm3. Higher loadings of surfactant were found to increase the cloud point. It was observed also that the inclusion of small quantities of oils to surfactant solutions could either elevate or depress the cloud point. The significance of this fact will be developed later. 

As discussed in previous chapters, the phase behavior with changing temperature and pressure may be strongly influenced by small concentration gradients in multi-component systems already. Therefore, experimental control should take this into account. It is a common practice to use reactors with glass or sapphire windows. The transition of an inhomogeneous multiphase system to a homogeneous one can be observed visually as cloud point (Sect. 2.2, with the pressure and temperature values being monitored. 

The most important advantage of cloud point extraction is that only small amounts of nonionic or zwitterionic surfactants are required and consequently the procedure is less costly and more environmentally benign than other conventional extraction techniques such as liquid-liquid extraction and solid liquid extraction [107,108]. Moreover, CPE offers the possibility of combining extraction and preconcentration in one step. 

A significant increase in fp and similar elongated drops and emulsification were seen as the cloud point of 37 °C was approached for Dow s commercial secondary alcohol ethoxylate Tergitol 15-S-7 (Fig. 5). Its hydrophobe consists of various double-chain species with the sum of the chain lengths ranging between 11 and 15, and its average EO number is 7.3. In some cases a conical projection developed on the elongated drop, and a jet was emitted, which broke up into small droplets (Eig. 6). 

Chen [8] studied mixtures of the pure surfactants Ci2(EO)4 and sodium dodecyl sulfate (SDS) at 30 °C. At this temperature the former is a liquid which does not dissolve in water (see Fig. 3), and the latter is a solid. The SDS was doubly recrystallized from ethanol to remove n-dodecanol and other impurities. The solubility of SDS in pure Ci2(EO)4 at 30 °C was found to be approximately 9 wt. %. When small drops of an 8 wt. % mixture were injected into water at 30 °C, complete dissolution was observed, the time required being a linear function of the square root of initial drop radius. For instance, a drop having an initial radius of 70 (xm required approximately 100 s to dissolve, significantly more than the 16 s cited above for a slightly larger drop of pure Ci2(EO)6. Behavior was similar to that of nonionic mixtures below their cloud points discussed previously in that most of the drop dissolved rapidly, but the final small volume dissolved rather slowly with some observable emulsification. 

The explanation for this behavior is similar to that given in the preceding section for nonionic surfactant mixtures. Adding a hydrophihc anionic surfactant raises the temperature at the cloud point and other phase transitions above those for pure Ci2(EO)4. If the amount of anionic added exceeds only slightly that needed for complete solubility, the final stages of the dissolution process are slow because preferential dissolution of the anionic causes the remaining drop to rise above its cloud point and nucleate small droplets of surfactant-rich liquid. But if the amount added is sufficiently large, drop composition remains below the cloud point in spite of preferential dissolution, with the result that dissolution is fast as with pure nonionic surfactants below their cloud points. 

The equilibrium in these systems above the cloud point then involves monomer-micelle equilibrium in the dilute phase and monomer in the dilute phase in equilibrium with the coacervate phase. Prediction o-f the distribution of surfactant component between phases involves modeling of both of these equilibrium processes (98). It should be kept in mind that the region under discussion here involves only a small fraction of the total phase space in the nonionic surfactant—water system (105). Other compositions may involve more than two equilibrium phases, liquid crystals, or other structures. As the temperature or surfactant composition or concentration is varied, these regions may be encroached upon, something that the surfactant technologist must be wary of when working with nonionic surfactant systems. 

The cloud point test is one of the most commonly used methods to evaluate the low-temperature characteristics of distillate fuel. The cloud point temperature identifies the point when wax begins to form into crystals large enough to become visible in the fuel. At this temperature, wax can settle from fuel, deposit onto fuel filters, and interfere with the flow of fuel through small tubes and pipes. During cold weather months, distillate fuels with lower cloud point values are refined and blended to minimize the low-temperature problems associated with wax. 

This non-ASTM method is utilized to help predict the tendency of waxy fuel to plug small lines leading from outdoor fuel storage tanks. Fuel which flows from storage through smaller transfer lines may deposit wax on the internal surface of these lines or onto filter screens. Accumulation of wax can restrict or halt the flow of fuel from the system. This problem usually occurs slightly below the cloud point of the fuel. 

The observation of CST with practical precision is usually very simple. The two liquids are placed in a test tube and are stirred with a thermometer while heating or cooling until the liquids just mix (while heating) or just cloud (on cooling). Determinations of the cloud point are usually more precise than determinations of the temperature of disappearance of two phases. There is very little risk of subcooling a liquid mixture below the CST, and having it remain homogeneous. When the upper layer becomes small before it disappears, more of the major component of the upper layer is added, and the observation is repeated until the interface disappears near the middle of the system. This is necessary in order to... 

EOS models were derived for polymer blends that gave the first evidence of the severe pressure - dependence of the phase behaviour of such blends [41,42], First, experimental data under pressure were presented for the mixture of poly(ethyl acetate) and polyfvinylidene fluoride) [9], and later for in several other systems [27,43,44,45], However, the direction of the shift in cloud-point temperature with pressure proved to be system-dependent. In addition, the phase behaviour of mixtures containing random copolymers strongly depends on the exact chemical composition of both copolymers. In the production of reactor blends or copolymers a small variation of the reactor feed or process variables, such as temperature and pressure, may lead to demixing of the copolymer solution (or the blend) in the reactor. Fig. 9.7-1 shows some data collected in a laser-light-scattering autoclave on the blend PMMA/SAN [46],... 

Figure 5. Examples of moment free energy (70) for Flory-Huggins theory of length-polydisperse polymers, with one moment density, p, retained. The parent is of the Schulz form (65), with pf = 0.03, Lu = 100 (hence p = p, /Lv = 3 x 10-4), and a = 2 (hence Lw = 150) the point pt = pj° is marked by the filled circles. In plot (a), the value of x = 0.55 is sufficiently small for the parent to be stable The moment free energy is convex. Plot (b) shows the cloud point, % 0.585, where the parent lies on one endpoint of a double tangent the other endpoint gives the polymer volume fraction p, in the shadow phase. Increasing x further, the parent eventually becomes spinodally unstable [x 0.62, plot (c)]. Note that for better visualization, linear terms have been added to all free energies to make the tangent at the parent coincide with the horizontal axis.

The advantages cited for the described nonionic micellar cloud point extraction schemes include the following (1) ability to concentrate a variety of analytes (with concentration factors of 10-75), (2) safety and cost benefits (i.e. the use of small amounts of nonionic surfactant as an extraction solvent obviates the need to handle the usually large volumes of organic solvent required in traditional liquid-liquid extractions so that the volatility, flammability, and cost are reduced), (3) easy disposal of the nonionic surfactant extraction solvent (i.e. the nonionic surfactant solution is reportedly easily burned in the presence of waste... 

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