Salting out effects

Effects of electrolytes on the solubility of organic compounds in aqueous solutions were established empirically more than 100 years ago by Setschenow (1889). He found that the presence of dissolved inorganic salts in an aqueous solution decreases the aqueous solubility of nonpolar and weak polar organic compounds. This effect, known as the salting-out effect, is expressed by the empirical Setschenow formula 

Dror et al. (2000a, 2000b) report an experiment dealing with the effect of type and concentration of electrolytes, in an artificial soil aqueous solution, on the 

Salt Benzene Toulene o-Xylene m-Xylene p-Xylene Napthalene 

It is interesting to note that smaller ions (e.g., Na, Mg, Ca, Cl ) form hydration shells larger than bigger ions, which tend to bind water molecules only very weakly. In a simple way, the salting out of nonpolar and weakly polar compounds was explained by Schwarzenbach et al. (2003) by imagining that the dissolved ions compete successfully with the organic compound for solvent molecules. The freedom of some water molecules to solvate an organic molecule depends on the type and concentration of salts. 

A simple correlation was determined for estimating the Setschenow constants for a variety of organic solntes in seawater, which yields an overall reduction in solnbility by a factor 1.36 (Xie et al. 1997). The hydrophobicity of organic solutes increases by this factor, but the salting-out effect must be quantified when comparing the behavior of specific organic contaminants in fresh water and in subsnrface aqueous solutions. 

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In the isolation of organic compounds from aqueous solutions, use is frequently made of the fact that the solubility of many organic substances in water is considerably decreased by the presence of dissolved inorganic salts (sodium chloride, calcium chloride, ammonium sulphate, etc.). This is the so-called salting-out effect. A further advantage is that the solubility of partially miscible organic solvents, such as ether, is considerably less in the salt solution, thus reducing the loss of solvent in extractions. 

The extent of extraction can be increased by a salting out effect. The selectivity of TBP is very poor compared with HDEHP and it is only useful for light rare-earth separation however, organic phase loadings or REO higher than 100 g/L can easily be achieved. There are a large number of TBP manufacturers in Japan, the United States, and Europe. 

S ts can be used to precipitate proteins by salting out effects. The effectiveness of various salts is determined by the Hofmeister series, with anions being effective in the order citrate > PO4" > SO4" > CH3COO > Cl > NO3 , and cations according to NH4 > > Na ... 

The situation under discussion is very similar to the familiar salting-out effect in liquids, where a salt added to an aqueous solution serves to precipitate one or more organic solutes. Here we are considering the case where a... 

Divalent and trivalent ions can precipitate PAA, and this phenomenon is related to the loss of a hydration region. Such precipitation is to be distinguished from salting-out effects which occur with high concentrations of monovalent ions. 

The effect of dissolved hydrophilic electrolytes on the interaction between organic solutes and water can be described by the salting-in and salting-out effects. Dissolved electrolytes usually increase the internal pressure in water, through a volume-reducing process that... 

Similarly, concepts of solvation must be employed in the measurement of equilibrium quantities to explain some anomalies, primarily the salting-out effect. Addition of an electrolyte to an aqueous solution of a non-electrolyte results in transfer of part of the water to the hydration sheath of the ion, decreasing the amount of free solvent, and the solubility of the nonelectrolyte decreases. This effect depends, however, on the electrolyte selected. In addition, the activity coefficient values (obtained, for example, by measuring the freezing point) can indicate the magnitude of hydration numbers. Exchange of the open structure of pure water for the more compact structure of the hydration sheath is the cause of lower compressibility of the electrolyte solution compared to pure water and of lower apparent volumes of the ions in solution in comparison with their effective volumes in the crystals. Again, this method yields the overall hydration number. 

Thus, a suitable refinement of the Debye-Huckel theory must provide a theoretical interpretation of the term CL Originally this term was qualitatively interpreted as a salting-out effect during solvation the ions... 

Bouvier, C. Cote, G. Cierpiszewski, R. Szymanowski, J. Influence of salting-out effects temperature and the chemical structure of the extractant on the rate of copper(II) extraction from chloride media with dialkyl pyridine dicarboxylates. Solvent Extr. Ion Exch. 1998, 16, 1465-1492. 

Alkali ions (salts) influence the formation of the precursor gel for most of the synthetic zeolites (3,34,39,40). Na+ ions were shown to enhance in various ways the nucleation process (structure-directing role) (40-42), the subsequent precipitation and crystallization of the zeolite (salting-out effect) (JO and the final size and morphology of the crystallites (34,43). Informations on the various roles played by the inorganic (alkali) cations in synthesis of ZSM-5, such as reported in some recent publications (7,8,10,14,17,29,30,44,45) remain fragmentary, sometines contradictory and essentially qualitative. 

Role of alkali and NH cations in the crystallization of ZSM-5 Introduced in an aqueous (alumino) silicate gel (sol), the bare alkali cations will behave in various ways firstly, they will interact with water dipoles and increase the (super) saturation of the sol. Secondly, once hydrated, they will interact with the aluminosilicate anions with, as a result, the precipitation of the so formed gel (salting-out effect). Thirdly, if sufficiently small, they also can order the structural subunits precursors to nucleation species of various zeolites (template function-fulfilled by hydrated Na+ in the case of ZSM-5 (11,48)). ... 

This problem was resolved by Nakae et al. [7] using non-polar octadecylsilica as the stationary phase and a solution of 0.1 M of sodium perchlorate in methanol/water (80 20) as the mobile phase. The ternary system (water-alcohol-salt), previously used by Fudano and Konishi [8] as an eluent for the separation of ionic surfactants at higher concentrations, induced the so-called salting out effect . The addition of the organic solvent to the water modified the polarity of the eluent and produced a good separation within a short period of time [9]. It also has the function of dissociating the surfactant micelles in individual molecules that are dissolved in the eluent [8], The presence of the salt (NaC104) in the mobile phase has a considerable influence on... 

It is interesting to note that the molecule-ion interaction contribution in equation (5) is consistent with the well-known Setschenow equation. The Setschenow equation is used to represent the salting-out effect of salts on molecular nonelectrolyte solutes, when the solubilities of the latter are small (Gordon, (15)). The Setschenow equation is... 

A second type of ternary electrolyte systems is solvent -supercritical molecular solute - salt systems. The concentration of supercritical molecular solutes in these systems is generally very low. Therefore, the salting out effects are essentially effects of the presence of salts on the unsymmetric activity coefficient of molecular solutes at infinite dilution. The interaction parameters for NaCl-C02 binary pair and KCI-CO2 binary pair are shown in Table 8. Water-electrolyte binary parameters were obtained from Table 1. Water-carbon dioxide binary parameters were correlated assuming dissociation of carbon dioxide in water is negligible. It is interesting to note that the Setschenow equation fits only approximately these two systems (Yasunishi and Yoshida, (24)). 

The semi-empirical Pitzer equation for modeling equilibrium in aqueous electrolyte systems has been extended in a thermodynamically consistent manner to allow for molecular as well as ionic solutes. Under limiting conditions, the extended model reduces to the well-known Setschenow equation for the salting out effect of molecular solutes. To test the validity of the model, correlations of vapor-liquid equilibrium data were carried out for three systems the hydrochloric acid aqueous solution at 298.15°K and concentrations up to 18 molal the NH3-CO2 aqueous solution studied by van Krevelen, et al. 

Due to very limited experimental data, ion-ion interaction-parameters had to be assumed to be independent of temperature. Ion-molecule interaction parameters 0 iy were estimated from experimental results on salting-out effects, while 0were set equal zero. 

Prediction of salting out effect based on scaled particle theory... 

The addition of an amino acid to mixed solvents at selected temperatures can be a means to compensate even partially for the decrease of dielectric constant due to the solvent addition. Limitations are imposed by the solubility of the amino acid in such mixtures for instance, there is a salting-out effect in methanol-water 50 50 at 25°C when the concentration of glycine is about 0.5 Af (8 20). 

Washing and Cleaning Action. The properties of alkyl ether sulfates, due to the good solubility and the special hydrophilic/hydrophobic properties of the molecule, are of particular practical interest. From the investigations described in sections 2 and 3, it can be concluded that, in addition to the decrease in the Krafft Point, favorable properties for practical applications can be expected as a result of the inclusion of the oxyethylene groups into the hydrophobic part of the molecule. As is true for other anionic surfactants, the electrical double layer will be compressed by the addition of multivalent cations. By this means, the adsorption at the interface is increased, the surface activity is raised, and, furthermore, the critical micelle concentration decreased. In the case of the alkyl ether sulfates, however these effects can be obtained without encountering undesirable salting out effects. 

The effect of the water activity of the aqueous phase, discussed in Chapters 2, 3, and 6, is determined by the total concentration and nature of the salts. Generally, the distribution constant for a neutral metal complex would increase with increasing ionic strength, as Ulnstrated in Fig. 4.25. This salting-out effect is often ascribed to a redaction in free water available for hydration. On the other hand, the salt also breaks down the water structure, which could reduce the energy to form a hole in the phase. 

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