Ionic solutes ternary systems

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... 

Two activity coefficient models have been developed for vapor-liquid equilibrium of electrolyte systems. The first model is an extension of the Pitzer equation and is applicable to aqueous electrolyte systems containing any number of molecular and ionic solutes. The validity of the model has been shown by data correlation studies on three aqueous electrolyte systems of industrial interest. The second model is based on the local composition concept and is designed to be applicable to all kinds of electrolyte systems. Preliminary data correlation results on many binary and ternary electrolyte systems suggest the validity of the local composition model. 

The behaviour of ternary systems consisting of two polymers and a solvent depends largely on the nature of interactions between components (1-4). Two types of limiting behaviour can be observed. The first one occurs in non-polar systems, where polymer-polymer interactions are very low. In such systems a liquid-liquid phase separation is usually observed each liquid phase contains almost the total quantity of one polymer species. The second type of behaviour often occurs in aqueous polymer solutions. The polar or ionic water-soluble polymers can interact to form macromolecular aggregates, occasionally insoluble, called "polymer complexes". Examples are polyanion-polycation couples stabilized through electrostatic interactions, or polyacid-polybase couples stabilized through hydrogen bonds. 

Two different methods have been presented in this contribution for correlation and/or prediction of phase equilibria in ternary or mul> ticomponent systems. The first method, the clinogonial projection, has one disadvantage it is not based on concrete concepts of the system but assumes, to a certain extent, additivity of the properties of individiial components and attempts to express deviations from additivity of the properties of individual components and attempts to express deviations from additivity by using geometrical constructions. Hence this method, although simple and quick, needs not necessarily yield correct results in all the cases. For this reason, the other method based on the thermodynamic description of phase equilibria, reliably describes the behaviour of the system. Of cource, the theory of concentrated ionic solutions does not permit a priori calculation of the behaviour of the system from the thermodynamic properties of pure components however, if a satisfactory equation is obtained from the theory and is modified to express concrete systems by using few adjustable parameters, the results thus obtained are still substantially more reliable than results correlated merely on the basis of geometric similarity. Both of the methods shown here can be easily adapted for the description of multicomponent systems. 

While the early work on molten NH4CI gave only some qualitative hints that the effective critical behavior of ionic fluids may be different from that of nonionic fluids, the possibility of apparent mean-field behavior has been substantiated in precise studies of two- and multicomponent ionic fluids. Crossover to mean-field criticality far away from Tc seems now well-established for several systems. Examples are liquid-liquid demixings in binary systems such as Bu4NPic + alcohols and Na + NH3, liquid-liquid demixings in ternary systems of the type salt + water + organic solvent, and liquid-vapor transitions in aqueous solutions of NaCl. On the other hand, Pitzer s conjecture that the asymptotic behavior itself might be mean-field-like has not been confirmed. 

In our laboratories, extensive use has been made of vapor pressure (14-18) and membrane methods ( 2, 3, 19, 20) to Infer thermodynamic results for ternary aqueous systems containing an ionic or a nonionic surfactant and an organic solute. The most precise solubilization measurements ever reported have been obtained with an automated vapor pressure apparatus for volatile hydrocarbon solutes such as cyclohexane and benzene, dissolved In aqueous solutions of sodium octylsulfate and other Ionic surfactants (15, 16). A manual vapor pressure apparatus has been employed to obtain somewhat less precise results for solutes of lower volatility (17, 18). Recently, semi-equilibrium dialysis (19, 20) and MEUF (2) methods have been used to investigate solute-surfactant systems in which the organic solubilizates are too involatile to study by ordinary vapor pressure methods. 

Ternary ionic systems contain four kinds of ions, which can be constituted in three different ways (A+, B+, C+/X ), (A+ZX", Y , Z ), or (A" ", B+/X , Y ). The first two arrangements are additive ternary systems (the former one is a system with a common anion, the latter one is a system with a common cation), while the last one is a ternary reciprocal system. Having in mind the restriction of electro-neutrality, there are only three independent salt components, from which the solution could be built up. 

Viscosity studies of ionic polysoaps in pure aqueous solution usually suffer from the polyelectrolyte behaviour experienced at low concentrations [46, 49, 52, 75, 78, 98, 99, 126, 130,193, 219, 229, 338]. Indeed, as the dissociation of the ionic groups varies with the concentration, meaningful concentration dependent studies become difficult. The problem was frequently overcome by addition of salt (Fig. 19). But ternary systems are created, making the systems even more complex, and many ionic polysoaps tend to precipitate in brine [50, 54, 299], These problems can be avoided by zwitterionic polysoaps, facilitating the interpretation of concentration dependence [78]. 

According to Menger a simple nucleophilic catalysis is considered to occur in methanolysis of tetrachlorophthalic anhydride ia the presence of pyridine, and charge-transfer complex formation has been confirmed neither by kinetic studies nor by spectrometry. Also, the conductivity of a binary solution anhydride-tertiary amine is much lower than that of the ternary system containing an epoxide and does not change with time. Antoon and Koenig also reject the formation of zwitterions. Hence, the first modification of Fischer s mechanism performed by Tanaka and Kakiuchi is not appropriate, which was later admitted by the authors The formation of ionic species probably proceeds by the anionic mechanism... 

A typical phase diagram of a ternary system of water, ionic surfactant and long-chain alcohol (co-surfactant) is shown in Figure 15.5. The aqueous micellar solution A solubilizes some alcohol (spherical normal micelles), whereas the alcohol solution dissolves huge amounts of water, forming inverse micelles, B. These two phases are not in equilibrium, but are separated by a third region, namely the lamellar liquid crystalline phase. These lamellar structures and their equilibrium with the aqueous micellar solution (A) and the inverse micellar solution (B) are the essential elements for both microemulsion and emulsion stability [3]. 

Edwards et al. (1975, 1978A, B) established a molecular-thermodynamic correlation for calculating vapor-liquid equilibria in aqueous solutions containing one or more volatile electrolytes, with special attention to the ternary systems, ammonia-carbon dioxide-water and ammonia-hydrogen sulfide-water. Their 1978 correlation was shown to give results in satisfactory agreement with the limited data then available for temperatures from 0° to 170°C (32° to 338° F) and ionic strengths of about 6 molal (equivalent to total concentrations of the electrolytes between 10 and 20 molal). 

About the same time Beutier and Renon (11) also proposed a similar model for the representation of the equilibria in aqueous solutions of weak electrolytes. The vapor was assumed to be an ideal gas and < >a was set equal to unity. Pitzer s method was used for the estimation of the activity coefficients, but, in contrast to Edwards et al. (j)), two ternary parameters in the activity coefficient expression were employed. These were obtained from data on the two-solute systems It was found that the equilibria in the systems NH3+ H2S+H20, NH3+C02+H20 and NH3+S02+H20 could be represented very well up to high concentrations of the ionic species. However, the model was unreliable at high concentrations of undissociated ammonia. Edwards et al. (1 2) have recently proposed a new expression for the representation of the activity coefficients in the NH3+H20 system, over the complete concentration range from pure water to pure NH3. it appears that this area will assume increasing importance and that one must be able to represent activity coefficients in the region of high concentrations of molecular species as well as in dilute solutions. Cruz and Renon (13) have proposed an expression which combines the equations for electrolytes with the non-random two-liquid (NRTL) model for non-electrolytes in order to represent the complete composition range. In a later publication, Cruz and Renon (J4J, this model was applied to the acetic acid-water system. 

From a global assessment of these results, it seems inescapable to conclude that mean-field behavior does not remain valid asymptotically close to the critical point. Rather, ionic systems seem to show Ising-to-mean-field crossover. Such a crossover has been a recurring result observed near liquid-liquid consolute points in Coulombic electrolyte solutions, in ternary aqueous electrolyte solutions containing an organic cosolvent, and in binary aqueous solutions of NaCl near the liquid-vapor critical line. 

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