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258 Fugacities in Liquid Mixtures: Excess Functions Chapter 6 6.11 Wilson, NRTL, and UNIQUAC Equations Many equations have been proposed for the relation between activity coefficients and mole fractions and new ones appear every year.” Some, but not all, of these can be derived from Wohl’s general method. In particular, three equations that are useful for many practical calculations cannot be obtained by Wohl’s formulation. Wilson Equation. Based on molecular considerations, Wilson (1964) presented the following expression for the excess Gibbs energy of a binary solution: =a In(xy + Aq9X2)— x2 In(xy + AQ}24) (6-104) ‘The activity coefficients derived from this equation are lnyy ==In(ay + Ayax2)+ of te -A (6-105) Mt Ayxy Agia, + xp Ay Aa ] (6-106) Inyo =-noa Aas) In Eq. (6-104) the excess Gibbs energy is defined with reference to an ideal solu- tion in the sense of Raoult’s law; Eq. (6-104) obeys the boundary condition that g@ vanishes as either x, or x» becomes zero. Wilson's equation has two adjustable parameters, A, and Aj). In Wilson’s deri- vation, these are related to the pure-component molar volumes and to characteristic energy differences by A= Shox{ Aan) (6-107) 0 (6-108) ” See, for example, E. Hala, J, Pick, V. Fried and O. Vilim, 1967, Vapor-Liguid Equilibrium, 2” Ed., rans, 6. ndast, Part 1, (Oxford: Pergamon Press); C. Black, 1959, AIChE J. 5: 249; M, Hiranuma and K. Honma, 1975, Ind. Eng. Chem. Process Des. Dev., 14: 221. A particularly simple but unusual equation has been proposed by H. Mauser, 1958, Z Elekirochem., 62: 895, There are many, many others, too many to list here 6.11 Wilson, NATL, and UNIQUAC Equations 261 Wilson's equation has two disadvantages that are not serious for many applica- tions. First, Eqs. (6-105) and (6-106) are not useful for systems where the logarithms of the activity 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 for a binary system (see next section), no parameters Ay2 and Az; can be found that indicate the existence of two stable liquid phases." Wilson'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- liquid) 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 E So yy (tua, _ tr _ (6-109) RT My tHG | +E where an- 82 g1-8u1 ty, = 2128, = S21 6-110) 12 RT 21 RT ( ) Giz = expl-aygt12) Gay = exp-042721) (111) similar to that of Ay in Wilson's equation; gy is an energy parameter characteristic of the i-j interaction. Parameter a2 is related to the nonrandomness in the mixture; when 42 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 a2 varies from about 0.20 to 0.47; when experimental data are scarce, the value of cy can often be set arbitrarily; a typical choice is 043 0.3. From Eq. (6-109), the activity coefficients are ‘The significance of gy is °' For panially miscible systems, Wilson (1964) suggested that the right-hand side of Eig, (6-104) be multiplied by 4 constant greater than unity, This suggestion not only introduces a third parameter but, more important, creates difficulties when the equation is applied to ternary (or higher) systems (see Sec. 6.15). 262 Fugacities in Liquid Mixtures: Excess Functions Chapter 6 G; TG ny, =| a1) ,__ ta Pea e2Oa) ” Ca + aiGia? (6-112) 2 G TG; Inyy = 22] t19 12 4 Ga Pe eMC) (x +x2G21)* (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- ethane/isooctane 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 (219 ~ 22) and (89) ~ g11) appear to be linear functions of temperature, showing no discontinuities in the 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-LIQUID DATA + Uiuid-Liauio oaTa ,,+0.20 6000} T EXPERIMENTAL ERROR e 4 é (93922 JE = 4000 EE -E-EEI t 4 lie Le cayTcat sp4gTION fe TEMPERATURE oly 4 a a TEMPERATURE , Figure 6-18 Parameters in NRTL equation for the nitroethane (1)/isooctane (2) sys- tem calculated from vapor-liquid and liquid-liquid equilibrium data. ” See App. E 6.11 Wilson, NRTL, and UNIQUAC Equations 263 UNIQUAC Equation. A critical examination of the derivation of the NRTL equation shows that this equation, like those obtained from Wohl’s expansion, is more suitable for AF than g® (Renon and Prausnitz, 1969). Further, because experimental data for typical binary mixtures are usually not sufficiently plentiful or precise to yield three meaningful binary parameters, attempts were made (Abrams, 1975; Maurer, 1978; Anderson, 1978; Kemeny and Rasmussen, 1981) to derive a two-parameter equation for g¥ that retains at least some of the advantages of the equation of Wilson without restriction to completely miscible mixtures. Abrams derived an equation that, in a sense, extends the quasichemical theory of Guggenheim (see Sec. 7.6) for nonran- dom mixtures to solutions containing molecules of different size. This extension was therefore called the universal quasi-chemical theory or, in short, UNIQUAC. As dis- cussed in Sec. 7.7, the UNIQUAC equation for g® consists of two parts, a combinato- rial part that attempts to describe the dominant entropic contribution, and a residual part that is due primarily to intermolecular forces that are responsible for the enthalpy of mixing. The combinatorial part is determined only by the composition and by the sizes and shapes of the molecules; it requires only pure-component data. The residual part, however, depends also on intermolecular forces; the two adjustable binary pa- rameters, therefore, appear only in the residual part. The UNIQUAC equation is E (gf e £-(5] (5) us combinatorial residual For a binary mixture, - } =x inthe xin 22s S{oa nL, soning] (6-115) ar ‘combinatorial “1 *2 o @) 91 IN(0} +0921) ~ x993 In(B} +0)7)2) (6-116) where the coordination number z is set equal to 10, Segment fraction, *, and area fractions, @ and @', are given by =—M_ 3 = (6-117) ain +n xn th 6, =—11_ 6) = 222 (6-118) xa +292 ain +242 6.11 Wilson, NRTL, and UNIQUAC Equations Table 6-9 Some structural parameters for UNIQUAG equation.* en mcenneneee ete mine Component Carbon tetrachloride Chloroform Formic acid Methanol Acetonitrile Acetic acid Nitroethane Ethanol Acetone Ethyl acetate Methyl ethyl ketone Diethytamine Benzene Methyleyclopentane Methyl isobutyl ketone n-Hexane Toluene n-Heptane n-Octane Water Component q' Water 1.00 CH,OH 0.96 CH,OH 0.92 Cyalcohols 0.89 r q 333 2.82 2.70 2.34 154 1.48 1.43 143 1.87 1? 1.90 1.80 2.68 241 241 197 257 2.34 3.48 3.12 3.25 2.88 3.68 3.17 319 2.40 3.97 3.01 4.60 4.03 4.50 3.86 3.92 2.97 SAT 4.40 585 4.94 0.92 1.40 Component gt Cyaleohols 0.88 Cyaleohols 1.15 Cealcohols 1.78 Cyalcohols 2.71 * These parameters are dimensionless because they are (arbitrar= ily) taken relative to the size and surface area of a—CH— unit in 4 high-molecular-weight paraffin. where h= Se-a—G-d 5(2-a)-(2-D) 265 (6-124) (6-125) The UNIQUAC equation is applicable to a wide variety of nonelectrolyte liquid mix- ures containing nonpolar or polar fluids such as hydrocarbons, alcohols, nitriles, ketones, 264 Fugacities in Liquid Mixtures: Excess Functions Chapter 6 x t__ p= (6-119) 1d + ¥242 191 + 2292 gi 6% Parameters r, q, and q' are pure-component molecular-structure constants de- pending on molecular size and external surface areas. In the original formulation, q = q’. To obtain better agreement for systems containing water or lower alcohols, g' values for water and alcohols were adjusted empirically by Anderson (1978) to give an opti- mum fit to a variety of systems containing these components. For alcohols, the surface of interaction q’ is smaller than the geometric external surface q, suggesting that inter- molecular attraction is dominated by the OH group (hydrogen bonding). Table 6-9 pre- sents a few values of these structural parameters. For fluids other than water or lower alcohols, q = 4’. For each binary mixture, there are two adjustable parameters, ty and tp). These, in turn, are given in terms of characteristic energies Aujz and Auyy, by (6-120) (6-121) For many cases, Eqs. (6-120) and (6-121) give the primary effect of temperature ont} and ty}. Characteristic energies Aujz and Au,y are often only weakly dependent on temperature. Table 6-10 gives some binary parameters a} and a>, Activity coefficients 7, and y are given by Oz Oo ol) A Iny, =In +=qy In—- + @3] - 1; Ya x 3m oF | 4 h 2 } (6-122) 1 = gj In(8} +8591) + 8g} —— qi In(8) + 82721) ia (6-123) 16.15 Wilson, NRTL, and UNIQUAG Equations for Multicomponent Midures 287 6.15 Wilson, NATL, and UNIQUAC Equations for Multicomponent Mixtures ‘The equations discussed in Sec. 6.11 are readily extended to as many components as desired without any additional assumptions and without introducing any constants other than those obtained from binary data, Wilson Equation. For a solution of m components, Wilson’s equation is (6-162) tere (6-163) (6-164) ‘The activity coefficient for any component k is given by Nix, wy Sng} $e ews Eom Equation (6-165) requires only parameters that can be obtained from binary data; for each possible binary pair in the multicomponent solution, two parameters are needed. Orye (1965a) has tested Eq. (6-165) for a variety of ternary systems, using only binary data, and finds that for most cases good results are obtained. For example, Fig. 6-32 compares calculated and observed vapor compositions for the acetone/methyl acetate/methanol system at 50°C. A similar comparison is also shown for calculations based on the van Laar equation. No ternary data were used in either calculation; the binary constants used are given in Table 6-13. For this ternary system, the Wilson equations give a much better prediction than the van Lar equations but, as indicated in Table 6-11, the three-suffix Margules equations (using binary data only) can also give 1 good prediction because no ternary constant is required. Prauswire Sm, BN: Lichter thulen, E.G. cle Aecuelo," molecuion Therma yuemes ot Figd- Phage Eoveibrn', SMe, Premtice Hall C199), 3] von) set egal to 10. Fc any somone, eat oe “Te comin nome we Saingeet Sa -infSon pce es “m ™ yeiy-ap-o-o ers ‘Using UNIGUAC, Tal 6 1 marae ape iat quis predcns for ice well nih experimental prec rte) sed apr pace comportons scidfomie wwe and ssoonsecctoiat, whee expetinetal uncertain Aeneas dn oor es acorn lpn ond tcferalerionfarans Hee sg eons {ondng teens choslor and slebo reser ean eins ow Wey for {hh slebohiofen stan, the acy coef thow nelldeGned eens ‘Besnoeentems at oes bw eprodaced y te UNIQUAC seston se Bi ‘esate sol epesased swe ante ere: The aca ary devon es Corton forte wos iting ues, methanlAorsform ad eanellsorfrm Ie ‘los sge wl with he eerie dat f Severs eat (1958), Forueny tema ie ato coos eae ebay system areca eine! fr he ose atoneablndefneanaeatene, whee he "the resis shoe Tle 6-16 sogest dat UNIQUAC can Be used wih con enc for pia! malicomponnt tens of noel pote ha goede ‘pment nary date ae ral een ce nny puree ee tw UNE Eqns np one htt 616 reat a mcrguet gry en MOU ee tot tose” Toes Peer pa Sen Soe Tyeme Po) pean pores roe asin oasioair0 hseaorre encom, oncooye hocaums ossarme os ousre Seroe fret! seoc200 toa Inge aeso3) 039¢085) ova aca esters acco) erea00) itr ewes, assem nes) EB aninge “erm her segment con and wes acon and 9 ae coe bv = a | x esa wet Foe eee catamaran seri, Pes mt Paton! me pad ee ee us * emote (ebibecton (oe fei be R rary cont) nary cord) tery cnet) miry coat) — 7 > 7 : a own : Nectetythtooe t 4 3 er sn Here ‘ ° 3 ‘ apemcys 8) 0 Bmiow 2 oF Ft st ey ome Some 2 oF og | newt Bem iE + 1), Clrovmcctinie 3 5 i 2 Eo seoiro & ; 3 mt fr Go; ltl veri mt eee en = Bod bk tee Wien ey sce fog ot 4 eee i eh ey Poi SEES Mise Site coalesce = i 3 og Santana Mm i: to: 3 : su VA on = 2 of Gg rigor nhac = Pobodog