Solubility nonaqueous

Solubility can often be decreased by using a nonaqueous solvent. A precipitate s solubility is generally greater in aqueous solutions because of the ability of water molecules to stabilize ions through solvation. The poorer solvating ability of nonaqueous solvents, even those that are polar, leads to a smaller solubility product. For example, PbS04 has a Ks of 1.6 X 10 in H2O, whereas in a 50 50 mixture of H20/ethanol the Ks at 2.6 X 10 is four orders of magnitude smaller. 

Electrolytic Solvent. The use of DMAC as a nonaqueous electrolytic solvent is promising because salts are modesdy soluble ia DMAC and appear to be completely dissociated ia dilute solutions (18). 

Tetiafluoioethylene—peifluoiopiopyl vinyl ethei copolymeis [26655-00-5] aie made in aqueous (1,2) oi nonaqueous media (3). In aqueous copolymerizations water-soluble initiators and a perfluorinated emulsifying agent are used. Molecular weight and molecular weight distribution are controlled by a chain-transfer agent. Sometimes a second phase is added to the reaction medium to improve the distribution of the vinyl ether in the poljmier (11) a buffer is also added. 

In nonaqueous copolymerization, fluorinated acyl peroxides are used as initiators that are soluble in the medium (12) a chain-transfer agent may be added for molecular weight control. 

The solubihty of potassium permanganate in aqueous potassium hydroxide (108) is shown in Figure 7. Permanganates are soluble in certain nonaqueous solvents such as hquid NH, but not in hquid SO2. Organic solvents such as glacial acetic acid, acetone, acetonitrile, tert-huty alcohol. 

Chemical Grafting. Polymer chains which are soluble in the suspending Hquid may be grafted to the particle surface to provide steric stabilization. The most common technique is the reaction of an organic silyl chloride or an organic titanate with surface hydroxyl groups in a nonaqueous solvent. For typical interparticle potentials and a particle diameter of 10 p.m, steric stabilization can be provided by a soluble polymer layer having a thickness of - 10 nm. This can be provided by a polymer tail with a molar mass of 10 kg/mol (25) (see Dispersants). 

Table 3. Solubilities of the Hydrox ybenzoic Acids in Nonaqueous Solvents, Wt % ...

Table 1. Solubility of Sodium Nitrite in Nonaqueous Solvents ...

Surface activity is not limited to aqueous systems, however. AH of the combiaations of aqueous and nonaqueous phases are known to occur, but because water is present as the solvent phase in the overwhelming proportion of commercially important surfactant systems, its presence is assumed in much of the common terminology of industry. Thus, the water-soluble amphipathic groups are often referred to as solubilizing groups. 

Micellar properties are affected by changes in the environment, eg, temperature, solvents, electrolytes, and solubilized components. These changes include compHcated phase changes, viscosity effects, gel formation, and Hquefication of Hquid crystals. Of the simpler changes, high concentrations of water-soluble alcohols in aqueous solution often dissolve micelles and in nonaqueous solvents addition of water frequendy causes a sharp increase in micellar size. 

Hydrophobic substances are soluble in nonpolar solvents, whereas their solubiUty in water is very limited. Many of these substances are also soluble in fats and Hpids and are also called hpophile compounds. Such substances have a tendency to avoid contact with water and to associate with a nonpolar, nonaqueous environment, such as a surface, eg, an organic particle, a particle containing organic material, or the lipid-containing biomass of an organism. 

Although the ethyleneamines ate water soluble, soHd amine hydrates may form at certain concentrations that may plug processing equipment, vent lines, and safety devices. Hydrate formation usually can be avoided by insulating and heat tracing equipment to maintain a temperature of at least 50°C. Water cleanup of ethyleneamine equipment can result in hydrate formation even in areas where routine processing is nonaqueous. Use of warm water can reduce the extent of the problem. 

Flocculation and sedimentation arc two processes used to separate waste streams that contain both a liquid and a solid phase. Both are well-developed, highly competitive processes, which arc oflcii used in the complete treatment of waste streams. They may also be used instead of, or in addition to, filtration. Some applications include the removal of suspended solid particles and soluble heavy metals from aqueous streams. Many industries use both processes in the rcmowal of pollutants from their wastewaters. These processes work best when the waste stream contains a low concentration of the contaminating solids. Although they are applicable to a wide variety of aqueous waste streams, these processes arc not generally used to treat nonaqueous or semisolid waste streams such as sludges and slurries. 

However, solubility, depending as it does on the rather small difference between solvation energy and lattice energy (both large quantities which themselves increase as cation size decreases) and on entropy effects, cannot be simply related to cation radius. No consistent trends are apparent in aqueous, or for that matter nonaqueous, solutions but an empirical distinction can often be made between the lighter cerium lanthanides and the heavier yttrium lanthanides. Thus oxalates, double sulfates and double nitrates of the former are rather less soluble and basic nitrates more soluble than those of the latter. The differences are by no means sharp, but classical separation procedures depended on them. 

Intercalation from solutions in nonaqueous solvents (S21). This method may suffer from the drawback that final stoichiometries may not correspond to equilibrium conditions, because of partial leaching out of metal halide. For this reason, some chlorides can be intercalated only from solvents in which they have limited solubility iLS). It has often been the practice to wash intercalates with solvents to remove the excess of intercalant this may lead to stoichiometries lower than the original ones. The two-ampoule method may, therefore, be preferable (H24). 

Nonaqueous Systems In nonaqueous (nonpolar) solvent systems, nitrosatlon also proceeds. In these solvents, alpha-tocopherol acts as a lipid soluble blocking agent in much the same fashion as ascorbic acid functions in the aqueous phase. Alpha-tocopherol reacts with a nitrosating agent and reduces it to nitric oxide. At the same time, alpha-tocopherol is oxidized to tocoquinone, which is the first oxidation product of vitamin E and also a normal metabolite in vivo. 

It is possible to carry out experiments with immobilized cells in essentially nonaqueous media (Rothenburger and Atlas 1993), and this could prove an attractive strategy for compounds with limited water solubility, provided that solvents can be found that are compatible with the solubility of the substrate and the sensitivity of the cells to organic solvents. 

Reactions involving organic substances have some special features. Many of these substances are poorly soluble in aqueous solutions. Sometimes their solubilities can be raised by adding to the solution the salts of aromatic sulfonic acids with cations of the type [NHJ or alkali metal ions. These salts have a salting-in effect on poorly soluble organic substances. In many cases solutions in mixed or nonaque-ous solvents (e.g., methanol) are used. Suspensions of the organic substances in aqueous solutions are also useful for electrosynthesis. 

The strategy of using two phases, one of which is an aqueous phase, has now been extended to fluorous . systems where perfluorinated solvents are used which are immiscible with many organic reactants nonaqueous ionic liquids have also been considered. Thus, toluene and fluorosolvents form two phases at room temperature but are soluble at 64 °C, and therefore,. solvent separation becomes easy (Klement et ai, 1997). For hydrogenation and oxo reactions, however, these systems are unlikely to compete with two-phase systems involving an aqueous pha.se. Recent work of Richier et al. (2000) refers to high rates of hydrogenation of alkenes with fluoro versions of Wilkinson s catalyst. De Wolf et al. (1999) have discussed the application and potential of fluorous phase separation techniques for soluble catalysts. 

In Ref. 11, IT voltammograms of NH4 and N03 were obtained when a 0-pipette was exposed to vapors of ammonia and nitric acid, and linear dependence of the voltam-metric response on concentration of vapor-generating solution has been demonstrated. The surface liquid layer in all pipettes used in that work was aqueous, and only the detection of water-soluble gases was discussed. However, the detection of organic compounds in the gas phase may also be possible using a 0-pipette with a nonaqueous sensing film. 

Most small organic molecules are soluble in mixed organic-aqueous solvents and can be easily analyzed using RPLC. However, there are some polar compounds which are not soluble in typical RPLC solvent systems or are unstable in an aqueous mobile phase system. These compounds can be analyzed on an RPLC column with a nonaqueous solvent system. This technique is called "nonaqueous reversed phase chromatography" (NARP).20-21 The NARP technique is primarily used for the separation of lipophilic compounds having low to medium polarity and a molecular weight larger than... 

The single most important consideration in nonaqueous GPC is sample solubility. Although adsorption is not an infrequent problem, finding a solvent for a polymer is usually the hard step in analysis. The most common solvents for nonaqueous GPC are toluene, tetrahydrofuran, chloroform, and DMF. A number of potentially useful solvents are toxic, corrosive, or expensive,... 

Applications High-temperature liquid chromatography with packed-capillary columns, nonaqueous mobile phases, and ELSD and ICP-MS detection, has been developed specifically as a robust analytical tool for the analysis of high-MW polymer additives [731,738]. Dissolving such moderately polar, heavy compounds with low water solubility at ambient temperature usually... 

Drug solubility can be increased by the use of solubilizing agents, such as those listed in Table 2, and by nonaqueous solvents or mixed solvent systems, to be... 

A nonaqueous solvent or a mixed aqueous/nonaqu-eous solvent system may be necessary to stabilize drugs, such as the barbiturates, that are readily hydrolyzed by water, or to improve solubility (e.g., di-gitoxin). Nonaqueous solvents must be carefully screened and tested to ensure that they exhibit no pharmacological action, are nontoxic and nonirritating, and are compatible and stable with all ingredients of a formulation. 

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