Nonelectrolytes

Table 1 indicates that the enthalpy of mixing in the liquid phase is not important when calculating enthalpies of vaporization, even though for this system, the enthalpy of mixing is large (Brown, 1964) when compared to other enthalpies of mixing for typical mixtures of nonelectrolytes. 

For dilute solutions, solute-solute interactions are unimportant (i.e., Henry s law will hold), and the variation of surface tension with concentration will be linear (at least for nonelectrolytes). Thus... 

The variation of the integral capacity with E is illustrated in Fig. V-12, as determined both by surface tension and by direct capacitance measurements the agreement confrrms the general correctness of the thermodynamic relationships. The differential capacity C shows a general decrease as E is made more negative but may include maxima and minima the case of nonelectrolytes is mentioned in the next subsection. 

Still another situation is that of a supersaturated or supercooled solution, and straightforward modifications can be made in the preceding equations. Thus in Eq. IX-2, x now denotes the ratio of the actual solute activity to that of the saturated solution. In the case of a nonelectrolyte, x - S/Sq, where S denotes the concentration. Equation IX-13 now contains AH, the molar heat of solution. 

A logical division is made for the adsorption of nonelectrolytes according to whether they are in dilute or concentrated solution. In dilute solutions, the treatment is very similar to that for gas adsorption, whereas in concentrated binary mixtures the role of the solvent becomes more explicit. An important class of adsorbed materials, self-assembling monolayers, are briefly reviewed along with an overview of the essential features of polymer adsorption. The adsorption of electrolytes is treated briefly, mainly in terms of the exchange of components in an electrical double layer. 

The adsorption of nonelectrolytes at the solid-solution interface may be viewed in terms of two somewhat different physical pictures. In the first, the adsorption is confined to a monolayer next to the surface, with the implication that succeeding layers are virtually normal bulk solution. The picture is similar to that for the chemisorption of gases (see Chapter XVIII) and arises under the assumption that solute-solid interactions decay very rapidly with distance. Unlike the chemisorption of gases, however, the heat of adsorption from solution is usually small it is more comparable with heats of solution than with chemical bond energies. 

Figure A2.5.18. Body-centred cubic arrangement of (3-brass (CiiZn) at low temperature showing two interpenetrating simple cubic superlattices, one all Cu, the other all Zn, and a single lattice of randomly distributed atoms at high temperature. Reproduced from Hildebrand J H and Scott R L 1950 The Solubility of Nonelectrolytes 3rd edn (New York Reinliold) p 342.

A series of studies has been made by Yalkowsky and co-workers. The so-called general solubility equation was used for estimating the solubility of solid nonelectrolytes [17, 18]. The solubility log S (logarithm of solubility expressed as mol/L) was formulated with log P logarithm of octanol/water partition coefficient), and the melting point (MP) as shown in Eq. (11). This equation generally... 

Osmotic pressure experiments provide absolute values for Neither a model nor independent calibration is required to use this method. Experimental errors can arise, of course, and we note particularly the effect of impurities. Polymers which dissociate into ions can also be confusing. We shall return to this topic in Sec. 8.13 for now we assume that the polymers under consideration are nonelectrolytes. 

Nonelectrolytic plant producing chlorine and potassium nitrate. 

A survey of nonelectrolytic routes for CI2 production was conducted by Argonne National Laboratory the economics of these processes were examined in detail (76). One route identified as energy efficient and economically attractive is the conversion of waste NH Cl to CI2. 

The use of UNIFAC for estimating activity coefficients in binary and multicomponent organic and organic—water systems is recommended for those systems composed of nonelectrolyte, nonpolymer substances for which only stmctural information is known. UNIFAC is not recommended for systems for which some reUable experimental data are available. The method, including revisions through 1987 (39), is available in commercial software packages such as AspenPlus (174). 

McGraw-HiU, New York, 1987. Sandler, S.I., Chemical and Engineeiing Thermodynamics, 2d ed., Wiley, New York, 1989. Smith, J.M., H.C. Van Ness, and M.M. Abbott, Introduction to Chemical Engineeiing Theimodynamics, 5th ed., McGraw-Hill, New York, 1996. Van Ness, H.C., and M.M. Abbott, Classical Theimodynamics of Nonelectrolyte Solutions With Applications to Phase Equi-lihiia, McGraw-Hill, New York, 1982. 

The N equations represented by Eq. (4-282) in conjunction with Eq. (4-284) may be used to solve for N unspecified phase-equilibrium variables. For a multicomponent system the calculation is formidable, but well suited to computer solution. The types of problems encountered for nonelectrolyte systems at low to moderate pressures (well below the critical pressure) are discussed by Smith, Van Ness, and Abbott (Introduction to Chemical Engineering Thermodynamics, 5th ed., McGraw-Hill, New York, 1996). 

Dilute Binary Mixtures of Nonelectrolytes with Water as the... 

Dilute Binary Nonelectrolytes General Mixtures These correlations are outlined in Table 5-18. 

TABLE 5-18 Correlations for Diffusivities of Dilute/ Binary Mixtures of Nonelectrolytes in Liquids... 

Dilute Binary Mixtures of a Nonelectrolyte in Water The correlations that were suggested previously for general mixtures, unless specified otherwise, may also be applied to diffusion of miscellaneous solutes in water. The following correlations are restricted to the present case, however. 

Hayduk-Laudie They presented a simple correlation for the infinite dilution diffusion coefficients of nonelectrolytes in water. It has about the same accuracy as the Wilke-Chang equation (about 5.9 percent). There is no explicit temperature dependence, but the 1.14 exponent on I compensates for the absence of T in the numerator. That exponent was misprinted (as 1.4) in the original article and has been reproduced elsewhere erroneously. 

Concentrated, Binary Mixtures of Nonelectrolytes Several correlations that predict the composition dependence of Dab. re summarized in Table 5-19. Most are based on known values of D°g and Dba- In fact, a rule of thumb states that, for many binary systems, D°g and Dba bound the Dab vs. Xa cuiwe. CuUinan s equation predicts dif-fusivities even in hen of values at infinite dilution, but requires accurate density, viscosity, and activity coefficient data. 

TABLE 5-19 Correlations of Diffusivities for Concentrated/ Binary Mixtures of Nonelectrolyte Liquids... 

---