Organics, solubility regular solution theory

If the mutual solubilities of the solvents A and B are small, and the systems are dilute in C, the ratio ni can be estimated from the activity coefficients at infinite dilution. The infinite dilution activity coefficients of many organic systems have been correlated in terms of stmctural contributions (24), a method recommended by others (5). In the more general case of nondilute systems where there is significant mutual solubiUty between the two solvents, regular solution theory must be appHed. Several methods of correlation and prediction have been reviewed (23). The universal quasichemical (UNIQUAC) equation has been recommended (25), which uses binary parameters to predict multicomponent equihbria (see Eengineering, chemical DATA correlation). 

There already exists a substantial literature devoted to the estimation of various material properties with the help of additive structual increments (Reid et. al, 1987, Van Krevelen, 1990). The regular solution theory in combination with additive structural increments has a wide application for estimating the relative solubilities of organic substances in polymers and the solubility of polymers in various solvents (Barton, 1983) and will be described later in this chapter. When estimating partition coefficient values, one is quickly confronted with this method s application limits, particularly with polar and non-polar structures, for example the partitioning of substances between polyolefins and alcohol (Baner and Piringer, 1991). 

Additional approaches to understand and predict solubilities in mixed solvents are based on estimation of the activity coefficient, logy, in Eq. (1). Martin, Chertkoff, and Restaino investigated the use of regular solution theory, as developed by Hildebrand and Scott, to predict the solubilities of organic solutes in various solvent mixtures ... 

Azizian, S. Pour, A. H. Solubility of 2-naphthol in organic nonelectrolyte solvents. Comparison of observed versus predicted values based upon mobile order and regular solution theories./. Chem. Res.-S. 2003, 7, 402-404. 

Barton"" " provides empirical methods based on solubility parameters for ternary solvent systems. All these methods provide only a qualitative idea on miscibility. The combination of regular solution theory and solubility parameters has been employed for predicting the partition coefficients of organic compounds between water and polystyrene and between alcohols and polyolefins. The results are useful to a first approximation. 

Figure 2.4 demonstrates the linear correlation between log Kd/(83 - and 8 for the distribution of some P-diketone. Advantages of the regular solution theory are that there is no adjustable parameter in the calculation and that the effect of organic solvents is fairly explained by the solubility parameter that is experimentally determined independently from the vaporization energy and molar volume (Table 2.1). 

Fortunately, most organic solvents are nonpolar and therefore their intermolecular forces are weak London or dispersion forces. Hildebrand used the term "regular solutions" to describe solutions of nonelectrolytes and their nonpolar solvents. Additional theories on the solubility of polymers were developed by Flory ( ) and Huggins O). Probably the most important publications leading to the practical use of solubility theories by polymer scientists were those published by Burrell in 1955 ( ) and 1966 ( ). Modifications in the Hildebrand solubility parameter concept for regular solutions to account for larger intermolecular forces were made by Liebermann ( ), Crowley (.7), Hansen and Beerbower ( ) and Nelson et al. (9). 

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