6.11 Wilson, NRTL, and UNIQUAC Equations 281 Wilson's equation has two disadvantages that are not serious for many applica- rst, Eqs. (6-105) and (6-106) are not useful for systems where the logarithms ty coefficients, when plotted against x, exhibit maxima or minima. (Van Laar equations are also not useful for this case). Such systems, however, are not com- mon. The second and more serious disadvantage of Wilson’s equation lies in its inabil- ity to predict limited miscibility. When Wilson's equation is substituted into the equa- tions of thermodynamic stability fora binary system (see next section), no parameters ‘Ay and Az; can be found that indicate the existence of two stable liquid phases.” .on’s equation, therefore, should be used only for liquid systems that are com- pletely miscible or else for those limited regions of partially miscible systems where only one liquid phase is present. NRTL Equation. The basic idea in Wilson's derivation of Eq. (6-104) follows from the concept of local composition that is discussed further in Sec. 7.7. This con- cept was also used by Renon (1968) in his derivation of the NRTL (nonrandom, two- quid) equation; however, Renon’s equation, unlike Wilson's, is applicable to partially miscible as well as completely miscible systems. The NRTL equation for the excess Gibbs energy is tions. e # y(t, tS 6.1 oe co where fue : RT (6-110) Gy mexp-ayzty) Gy =exph-a2a1) (itty ‘The significance of gy is similar to that of Ay energy parameter characteristic of the ij interaction. Parameter ap is related to the nonrandomness in the mixture; when «2 is zero, the mixture is completely random and Eq. (6-109) reduces to the two-suffix Margules equation. The NRTL equation contains three parameters, but reduction of experimental data for a large number of binary systems indicates that «jz vaties from about 0.20 to 0.47; when experimental data are scarce, the value of 2 can often be set arbitrarily; atypical choice is ay 0.3. From Eq, (6-109), the activity coefficients are For partially miscible systems, Wilson (1964) suggested thal he righthand side of Eq, (6-10) be multiplied by a constant grater than unity. This suggestion not ony inoduces atid parameter but, more important, creates + tnGe_|| ) f+nGu? | (6-112) (6-113) For moderately nonideal systems, the NRTL equation offers no advantages over the simpler van Laar and three-suffix Margules equations. However, for strongly nonideal mixtures, and especially for partially immiscible systems,” the NRTL equa- tion often provides a good representation of experimental data if care is exercised in data reduction to obtain the adjustable parameters. For example, consider the nitro- cthanefisooctane system studied by Renon; below 30°C, this system has a miscibility gap. Reduction of liquid-liquid equilibrium data below 30°C and vapor-liquid equilib rium data at 25 and 45°C gave the results shown in Fig. 6-18. The parameters (£12 ~ 22) and (201 ~ 811) appear to be linear functions of temperature, showing no discontinuities inthe region of the critical solution temperature. Renon’s and Wilson's equations are readily generalized to multicomponent mix- tures as discussed in Sec. 6.15. X vapoR-Liguio DATA + Ucuro-tiouto oxta 1, +0.20 EXPERIMENTAL eRROR 1 (2%) Jt i ee pe 4 99°9)) —Lecrricat. souurion 1 Temperature 2000) Deo e0 sso 40s sos 00 TEMPERATURE , °C Figure 6-18 Parameters in NATL equation for the nitroethane (1Visooctane (2) sys- tem calculated from vapor-iquid and liquid-liquid equilibrium data * See App.