Solubilization electrolyte effect

Conversely, the addition of some other ions can promote solubility by the indifferent electrolyte effect. The use of hydrophilic molecules such as the hydroxyacids (e.g. citrate, tartaric) or aromatic carboxylic acids (e.g. benzoic) can create cavities in the water structure thereby promoting solubilization. Many salt formers increase drug solubility by this type of mechaiusm. Citrate buffers and sodium benzoate, the latter often used in formulations as an antimicrobial preservative, are known to enhance the solubility of a number of drugs. 

The effect of surfactant structure on cmc is discussed in Section 6.6. The complex relationship between surface tension and cmc depends on the hydrophobe and the hydrophile, including the counterion, of the surfactant. An increase in the chain length of the hydrophobe decreases cmc branching of the carbon chain increases cmc. Fluorination of the hydrophobe lowers cmc considerably. In addition to the chemical structure of the surfactant, cmc depends on external factors, including electrolyte effects, temperature, and other dissolved or solubilized organic components. 

The covalent character of mercury compounds and the corresponding abiUty to complex with various organic compounds explains the unusually wide solubihty characteristics. Mercury compounds are soluble in alcohols, ethyl ether, benzene, and other organic solvents. Moreover, small amounts of chemicals such as amines, ammonia (qv), and ammonium acetate can have a profound solubilizing effect (see COORDINATION COMPOUNDS). The solubihty of mercury and a wide variety of mercury salts and complexes in water and aqueous electrolyte solutions has been well outlined (5). 

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. 

Foam low high Alkali stab Electrolyte stab Acid stab Chlorine stab Surface tension Detergent effect Hydrotropic effect Solubilizing effect Biodegrad- ability... 

Electrolytes are obviously solubilized only in the aqueous micellar core. Adding electrolytes in water-containing AOT-reversed micelles has an effect that is opposite to that observed for direct micelles, i.e., a decrease in the micellar radius and in the intermicellar attractive interactions is observed. This has been attributed to the stabilization of AOT ions at the water/surfactant interface [128]. 

Zhong et al. (2003) studied the apparent solubility of trichloroethylene in aqueous solutions, where the experimental variables were surfactant type and cosolvent concentration. The surfactants used in the experiment were sodium dihexyl sulfo-succinte (MA-80), sodium dodecyl sulfate (SDS), polyoxyethylene 20 (POE 20), sorbitan monooleate (Tween 80), and a mixture of Surfonic- PE2597 and Witconol-NPIOO. Isopropanol was used as the alcohol cosolvent. Eigure 8.20 shows the results of a batch experiment studying the effects of type and concentration of surfactant on solubilization of trichloroethylene in aqueous solutions. A correlation between surfactant chain length and solubilization rate may explain this behavior. However, the solubilization rate constants decrease with surfactant concentration. Addition of the cosolvent isopropanol to MA-80 increased the solubility of isopropanol at each surfactant concentration but did not demonstrate any particular trend in solubilization rate of isopropanol for the other surfactants tested. In the case of anionic surfactants (MA-80 and SDS), the solubility and solubilization rate increase with increasing electrolyte concentration for all surfactant concentrations. 

Other molecular thermodynamic models for protein-reverse micelle complexes have also emerged. Bratko et al. [171] presented a model for phase transfer of proteins in RMs. The shell and core model was combined with the Poisson-Boltzmann approximation for the protein-RM complex and for the protein-free RM. The increase in entropy of counterions released from RMs on solubilization of a protein was the main contribution to the decrease in free energy of com-plexation. Good agreement was found with SANS results of Sheu et al. [151] for cytochrome C solubilization and the effect of electrolytes on it. However, this model assumes that filled and empty RMs are of the same size, independent of salt strength and pH, which is not true according to experimental evidence available since then. 

For a given surfactant, the ability to form a single-phase w/o microemulsion is a function of the type of oil, nature of the electrolyte, solution composition, and temperature (54-58). When microemulsions are used as reaction media, the added reactants and the reaction products can also influence the phase stability. Figure 2.2.4 illustrates the effects of temperature and ammonia concentration on the phase behavior of the NP-5/cyclohexane/water system (27). In the absence of ammonia, the central region bounded by the two curves represents the single-phase microemulsion region. Above the upper curve (the solubilization limit), a water-in-oil microemulsion coexists with an aqueous phase, while below the lower curve (the solubility limit), an oil-in-water water microemulsion coexists with an oil phase. It can be seen that introducing ammonia into the system results in a shift of the solubilization... 

However, it may also be possible that the buffer negatively influences the solubility of the drug and other excipients. Buffer salts can either increase or decrease the solubility of organic compounds in water. The effect depends on a combination of the polarity of the solute and of the salt. Nonpolar solutes are solubilized (salted in) by less polar organic salts and are desolubilized (salted out) by polar salts. Conversely, polar solutes are salted in by polar salts and salted out by organic salts. It was shown that for a semipolar solute such as ampicillin, strong electrolytes... 

Numerous methods have been explored to recover at least some of this vast resource. Injection of oil-miscible fluids, gases under high pressure, and steam —either separately or in combination — have all been tried with various degrees of success. This is where microemulsions enter the picture. Under optimum conditions an aqueous surfactant solution — which may also contain cosurfactants, electrolytes, polymers, and so on —injected into an oil reservoir has the potential to solubilize the oil, effectively dispersing it as a microemulsion. 

Shihab et al. (1979) determined the effects of electrolytes on the solubility of furosemide in 5% polysorbate 80 solutions. It was found that the CMC of the surfactant decreased and the micellar volume increased in the presence of electrolytes (Table 12.6). All the electrolytes used increased the solubilizing power of the surfactant at the concentrations employed. 

In the study of nonaqueous electrolytes, the ion-pair effect is a sevae factor affecting ion conduction. The degree of association of salts in nonaqueous solvents (or the solubilizing ability of the different solvents toward the salt) is often estimated by comparing the Walden product, that is, Arf. Justify this method and explain what hypothesis is included and how it holds. (Xu)... 

The stability of emulsion and foam films have also been found dependent upon the micellar microstructure within the film. Electrolyte concentration, and surfactant type and concentration have been shown to directly influence this microstructure stabilizing mechanism. The effect of oil solubilization has also been discussed. The preceding stabilizing/destabilizing mechanisms for three phase foam systems have been shown to predict the effectiveness of aqueous foam systems for displacing oil in enhanced oil recovery experiments in Berea Sandstone cores. 

A HE SEARCH FOR PLASTIC, solvent-free electrolytes for use in solid-state batteries is being actively pursued in several laboratories (1-4). A number of reports have stressed the need for facile motion of the macromolecular chain in order to promote the ion conduction process in the polymer matrix, because this process occurs primarily via a free-volume mechanism (1-4). Comblike polymers with oligooxyethylene side chains constitute effective media for ion conduction of solubilized alkali salts (5-8). The low glass transition temperature (Tg) of poly(dimethylsiloxane) suggests that polysi-loxane could serve as a suitable backbone for such a comb polymer, and recent studies (9-J2) indicate this to be the case indeed. 

Ultrasound-assisted electrolytic reduction of emulsions of activated unsaturated systems provides a method for hydrogenation of water-insoluble materials in an aqueous environment [284]. The effect of ultrasound on electrochemical reactions in emulsions may vary depending on the reaction in some cases solubilization of an insoluble reaction product is furthered, whereas in other cases the heterogeneous rate constant is influenced [284]. 

Gadalla MAP, Saleh AM, Motawi MM. Effect of electrolytes on the solubility and solubilization of chlorocresol. Pharmazie 1974 29 105-107. 

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