Selective solvents

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

Tab lei, 4, Sofiness of some selected solvents accordir to the )i-scale . 

Table 1,5, Donor scales (Dg, DN and DNbulk) of some selected solvents, as well as acceptor number (AN) and hydrogen bond donor capacities (a).

The second important influence of the solvent on Lewis acid - Lewis base equilibria concerns the interactions with the Lewis base. Consequently the Lewis addity and, for hard Lewis bases, especially the hydrogen bond donor capacity of tire solvent are important parameters. The electron pair acceptor capacities, quantified by the acceptor number AN, together with the hydrogen bond donor addities. O, of some selected solvents are listed in Table 1.5. Water is among the solvents with the highest AN and, accordingly, interacts strongly witli Lewis bases. This seriously hampers die efficiency of Lewis-acid catalysis in water. 

Table 7.29 Infrared Transmission Characteristics of Selected Solvents...

TABLE 7.29 Infrared Transmission Characteristics of Selected Solvents Transmission below 80%, obtained with a 0.10-mm cell path, is shown as shaded area. 

Several standard methods for the quantitative analysis of food samples are based on measuring the sample s mass following a selective solvent extraction. For example, the crude fat content in chocolate can be determined by extracting with ether for 16 h in a Soxhlet extractor. After the extraction is complete, the ether is allowed to evaporate, and the residue is weighed after drying at 100 °C. This analysis has also been accomplished indirectly by weighing a sample before and after extracting with supercritical GO2. 

The principal direct appHcation of furfural is as a selective solvent. It is used for separating saturated from unsaturated compounds in petroleum refining, for the extractive distillation of butadiene and other hydrocarbons in the manufacture of synthetic mbber and for the production of... 

The choice of separation method to be appHed to a particular system depends largely on the phase relations that can be developed by using various separative agents. Adsorption is usually considered to be a more complex operation than is the use of selective solvents in Hquid—Hquid extraction (see Extraction, liquid-liquid), extractive distillation, or azeotropic distillation (see Distillation, azeotropic and extractive). Consequentiy, adsorption is employed when it achieves higher selectivities than those obtained with solvents. 

Selectivity. Solvent selectivity is intimately linked to the purity of the recovered extract, and obtaining a purer extract can reduce the number and cost of subsequent separation and purification operations. In aqueous extractions pH gives only limited control over selectivity greater control can be exercised using organic solvents. Use of mixed solvents, for example short-chain alcohols admixed with water to give a wide range of compositions, can be beneficial in this respect (6). 

Boron trifluoride catalyst may be recovered by distillation, chemical reactions, or a combination of these methods. Ammonia or amines are frequently added to the spent catalyst to form stable coordination compounds that can be separated from the reaction products. Subsequent treatment with sulfuric acid releases boron trifluoride. An organic compound may be added that forms an adduct more stable than that formed by the desired product and boron trifluoride. In another procedure, a fluoride is added to the reaction products to precipitate the boron trifluoride which is then released by heating. Selective solvents may also be employed in recovery procedures (see Catalysts,regeneration). 

In the wood rosin process, rosin is isolated from aged pine stumps that have been left in fields cleared for farming or lumbering operations. The stumps are cut and shredded to pieces the size of matchsticks. The wood chips are then extracted with an appropriate solvent, eg, aUphatic or aromatic petroleum hydrocarbons or ketones. The extract is fractionally separated into nonvolatile cmde rosin, volatile extractibles, and recovered solvent. The dark rosin is usually refined further to lighter-colored products using selective solvents or absorption. 

Solveat users and formulators may choose to avoid notification requirements for their workplaces and products by selecting solvents that do not contain Proposition 65 substances. As a result. Proposition 65 considerations can also influence the composition of solvents used ia iadustrial processes and solvent-containing products. 

An important characteristic of solvents is rate of evaporation. Rates of solvent loss are controUed by the vapor pressure of the solvent(s) and temperature, partial pressure of the solvent over the surface, and thus the air-flow rate over the surface, and the ratio of surface area to volume. Tables of relative evaporation rates, in which -butyl acetate is the standard, are widely used in selecting solvents. These relative rates are deterrnined experimentally by comparing the times required to evaporate 90% of a weighed amount of solvent from filter paper under standard conditions as compared to the time for -butyl acetate. The rates are dependent on the standard conditions selected (6). Most tables of relative evaporation rates are said to be at 25°C. This, however, means that the air temperature was 25°C, not that the temperature of the evaporating solvent was 25°C. As solvents evaporate, temperature drops and the drop in temperature is greatest for solvents that evaporate most rapidly. 

Acetate fibers are dyed usually with disperse dyes specially synthesized for these fibers. They tend to have lower molecular size (low and medium energy dyes) and contain polar groups presumably to enhance the forces of attraction by hydrogen bonding with the numerous potential sites in the cellulose acetate polymer (see Fibers cellulose esters). Other dyes can be appHed to acetates such as acid dyes with selected solvents, and azoic or ingrain dyes can be apphed especially for black colorants. However thek use is very limited. 

Extractive distillation works by the exploitation of the selective solvent-induced enhancements or moderations of the liquid-phase nonidealities of the components to be separated. The solvent selectively alters the activity coefficients of the components being separated. To do this, a high concentration of solvent is necessaiy. Several features are essential ... 

The optimum conditions of heavy metals extraction from ordinary chernozem in different solvents are selected both at determination of the mobile forms of elements, and at an estimation of their gross contents. It is established, that the stage of elements extraction in the greater measure depends on time of action and intensity of ultrasonic, nature of selected solvents and determinated elements. It is shown, that for all type of soils the time of low frequency ultrasonic action does not exceed 10 minutes, and the intensity ranges in an interval of 3-4 W/cm. ... 

Furfural is a colourless liquid which darkens in air and has a boiling point of 161.7°C at atmospheric pressure. Its principal uses are as a selective solvent used in such operations as the purification of wood resin and in the extraction of butadiene from other refinery gases. It is also used in the manufacture of phenol-furfural resins and as a raw material for the nylons. The material will resinify in the presence of acids but the product has little commercial value. 

Solubility in water, selected solvents Coefficient of thermal expansion Hardness/flexibility... 

GPC has many uses and is a powerful analysis technique for acrylate polymers. With care in selecting solvents and stationary phases, one finds that many polymers can be analyzed successfully. Opportunities always exist to use analytical GPC columns in nonstandard ways (semiprep, HDC, pseudo-ElPLC combined with GPC ) to the benefit of the analyst, but the analyst must always be keenly aware of which mode of operation is dominating when practicing such nonroutine analyses. 

ILs, on the other hand, are uniquely suited for use as solvents for gas separations. Since they are non-volatile, they cannot evaporate to cause contamination of the gas stream. This is important when selective solvents are used in conventional absorbers, or when they are used in supported liquid membranes. For conventional absorbers, the ability to separate one gas from another depends entirely on the relative solubilities (ratio of Henry s law constants) of the gases. In addition, ILs are particularly promising for supported liquid membranes, because they have the potential to be incredibly stable. Supported liquid membranes that incorporate conventional liquids eventually deteriorate because the liquid slowly evaporates. Moreover, this finite evaporation rate limits how thin one can make the membrane. This... 

Removal of diluent by an extraction process To obtain the final stable macroporous structure, the liquid organic diluents and the linear polymer are removed from the crosslinked structure by extraction with a good solvent for the inert diluents and particularly for the linear polymer. Toluene or methylene chloride are usually preferred for the removal of linear polystyrene from the divinylbenzene crosslinked macroporous polystyrene particles [125,128]. The extraction is carried out within a Soxhelet apparatus at the boiling point of the selected solvent over a period usually more than 24 h. 

Generally, the number of the shell chains in a microsphere ranges from a few hundred to a few thousand. The range of the diameter of the core is from 10-100 nm. Such a core-shell structure is very similar to the (AB)n type star block copolymers, which have many arms and spherical polymer micelles of the block or graft copolymers formed in selective solvents that are good for the corona sequence and bad for the core sequence. In fact, many theoretical investigations of the chain con-... 

Solvent extraction may also be used to reduce asphaltenes and metals from heavy fractions and residues before using them in catalytic cracking. The organic solvent separates the resids into demetallized oil with lower metal and asphaltene content than the feed, and asphalt with high metal content. Figure 3-2 shows the IFP deasphalting process and Table 3-2 shows the analysis of feed before and after solvent treatment. Solvent extraction is used extensively in the petroleum refining industry. Each process uses its selective solvent, but, the basic principle is the same as above. 

Methyl ethyl ketone may also he produced hy the catalyzed dehydrogenation of sec-hutanol over zinc oxide or brass at about 500°C. The yield from this process is approximately 95%. MEK is used mainly as a solvent in vinyl and acrylic coatings, in nitrocellulose lacquers, and in adhesives. It is a selective solvent in dewaxing lubricating oils where it dissolves the oil and leaves out the wax. MEK is also used to synthesize various compounds such as methyl ethyl ketone peroxide, a polymerization catalyst used to form acrylic and polyester polymers and methyl pentynol by reacting with acetylene ... 

Solvent extraction is generally employed in analysis to separate a solute (or solutes) of interest from substances which interfere in the ultimate quantitative analysis of the material sometimes the interfering solutes are extracted selectively. Solvent extraction is also used to concentrate a species which in aqueous solution is too dilute to be analysed. 

It would be desirable to make sample prototype tooling and analyze the flow effects on a product that is likely to present a flow problem. In addition to the usual physical testing of the product, the use of photo-stress analysis techniques plus the exposure to selected solvents to check for stress crack characteristics would lead to changes in the product to minimize the effects of the molding on the product performance. As an example there have been cases in the past where piano keys with frozen-in stresses have been released from perspiration, leaving open flow lines (Chapter 5, STRESS ANALYSIS). 

Table 6.5 Transfer Constants (60 °C, bulk) for Selected Solvents and Additives...

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