‘The Wilson equation, like the Margules and van Laar equations, contains just two pa- rameters fora binary system (A12 and A\21), and is written: ot OE = ayn + a2Ai2) —xolmee Han) (218) An Au ly = —In(as +280) +0 (AB _At_ 12.1% manmintnnden (aap) Ce (12.198) An dn ~ Wan tartan —n (A - For infinite dilution, these equations become: =I Ayg #1 = Aa Xd 24 must always be positive numbers. ‘The NRTL equation, containing thiee parameters for abit ct Gye ORT Nh +0G (2% Gy ° [Gite tee] ea ; Gn), Gam wras[e(seics) tate] 9 Here, Gras exp(-arya) Gay = exp(—aea1) "26.4. Wilko, J. Chem, So. wo. 86 9127-150, 1968 "HL Reoon JM. Past, AICAE Sy 14, 9.139144, 1966 “4D. S, Abrams and, M. Praia, APOME J, wl 2p. 116-128, 1975 'SUNIQUAC Functional group Activity Coticients: proposed by Aa. Fedeasund. RL Jones, abd J. M.Paus- siz, AICHE, wl 2p. 1086-105, 1973; gen deed retnent inthe monograph: As Frsenund,) Grehling, and Rasmussen, Vip LiguidEquilriom sing UNIFAC, Bevis, Asteria 197,bay RT and m1 na RT ‘where a, by2, and bi, parameters specific to a particular pair of species, are independent of ‘composition and temperature, The infinite-dilution values of the activity coefficients are given by the equations: lay amt memp(—ata) and ny = ra +n ewp-an) ‘The UNIQUAC equation and the UNIFAC method are models of greater complexity and are treated in App. HL ‘The local-composiion models have Kimited exbiiy in dhe fi ta, ut they are adequate for most engineering purposes. Moreover, they are implicitly generalizable to ‘multicomponent systems without the introduction of any parameters beyond those required 0 describe the constituent binary systems. For example, the Wilson equation for multicomponent systems is ~Bae( B83) (1222) ny aa -in( Spasms) (az (Bem) Es, i eee ee eee fret penance acremnednc atta eat ae Mei sine ai vaeer ae vy ay Muar gr | CFD 229 Where Vj and ¥j are the molar volumes at temperature 7 of pure liquids j and i, and ay is ‘constant independent of composition and temperature, Thus the Wilson equation, like all other local-composition models, has built into it an approximate temperature dependence for the parameters, Moreover, all parameters are found from data for binary (in contrast to multi- component) systems. ‘This makes parameter determination for the local-composition models a lask of manageable proportions,‘Table 12.5: Parameter Values for the Wilson and NRTL Equations. Parameters a2, aai, bi2, and bai have units of eal mol~, and Vj and V2 have units of em? mol~!. Values are those recommended by Gmehling et al. Vapor-Liquid Equilibrium Data Collection, Chemistry Data Series, vol. I, parts 1a, 1b, 2¢ and 2c, DECHEMA, Frank- furyMain, 1981-1988, Vi | Wilson equation NRT equation System v2 | an at ba bat a Acetone( |) 7405 | 291.27 144801 | 631.05 1,197.41 0.5343 Water(2) 18.07 ‘Methanol(1) 40.73 | 10738 469.55 | -253.88 845.21 0.2994 ‘Water(2) 18.07 1-Propanol(1) 75.14 | 77548 1,351.90) 500.40 1,636.57 0.5081 Water(2) 18.07 Water(1) 18.07 | 1,696.98 -21939 | 715.96 548.90 0.2920 14Dioxane2) 85.71 ‘Methanol(1) 40.73 | 50431 19675 | 343.70 314.59 0.2981 Acetonitrile2) 66.30 Acetone(1) 74.05 | 161.88 583.11 | 184.70 222.64 0.3084 ‘Methanol(2) 40.73 Methytacctaet!) 79.84 | 31.19 $138) 38146 34654 0.2965 Methanol) 40.73 ‘Methanol(1) 40.73 | 1.73442 183.04] 730.09 1.17541 0.4743 Benzene(2) 89.41 Ethanol(1) 58.68 | 1,556.45 21052] 713.57 1,147.86 0.5292 ‘Toluene(2) 106.85 |