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3150 Ind. Eng. Chem. Res.

1993,32, 3150-3161

Calculation of Vapor-Liquid Equilibria from Infinite-Dilution Excess


Enthalpy Data Using the Wilson or NRTL Equation
A r t h u r S.Gow
Department of Chemistry and Chemical Engineering, University of New Haven, 300 Orange Avenue,
West Haven, Connecticut 06516-1999

A study was undertaken to determine the potential for using infinite-dilution excess enthalpy data
with activity coefficient models to predict vapor-liquid equilibria for binary systems. Expressions
for the infinite-dilution reduced excess enthalpies in a binary liquid mixture derived from the
Wilson or NRTL equation with temperature-independent parameters are solved for two unknown
model parameters given limiting values of reduced excess enthalpy (partial molar excess enthalpy)
H E / x 1 x 2 . The Wilson equation is modified using the van der Waals covolume b in place of the
pure-liquid molar volume, and an average value of the nonrandomness factor is chosen to obtain
a two-parameter NRTL equation. Vapor-liquid equilibria were predicted for 19 isothermal and
8 isobaric binary systems. Good results are generally obtained for nearly ideal systems using either
model; however, the Wilson equation is superior for moderately nonideal systems. The temperature-
independent Wilson model fails to accurately describe vapor-liquid equilibria for strongly nonideal
mixtures with highly unsymmetric excess enthalpy profiles. The proposed method appears to be
particularly well suited for estimating phase behavior of environmentally safe refrigerant mixtures.

Introduction composition range have been advanced. Hanks and co-


Phase equilibria are essential for chemical separation workers (Hanks et al., l971,1978a,b; Tan et al., 1977,1978;
process design. Experimental data are frequently un- Garcia Calzon et al., 1986) developed local composition
available over the range of conditions of interest; hence, schemes to predict VLE for a wide variety of nonideal
the required data must be estimated using one of a variety binary systems. In many cases, the NRTL equation with
of approaches. Among the most popular techniques is temperature-independent parameters provided a simple
the so-called “phi-gamma” approach in which activity HE versus composition function. Parameters were ob-
coefficients are estimated by the UNIFAC (Fredenslund tained from HE data, and VLE predictions were made for
et al., l975,1977a,b) or ASOG (Kojima and Tochigi, 1979) totally miscible binary hydrocarbon-hydrocarbon mix-
group contribution methods, and vapor-phase fugacity tures (Hanks et al., 19711,totally miscible ternary systems
coefficients are calculated from a corresponding-states (Tan et al., 1977, 1978), and partially miscible binary
correlation such as proposed by Prausnitz (Prausnitz, 1969; systems (Tan et al., 1977). Fair to excellent results were
Smith and Van Ness, 1987). A popular alternative obtained for totally miscible binary and ternary systems
approach is to use a cubic equation of state such as Soave’s while the method yielded poor predictions of the binodal
modification of Redlich and Kwong’s equation (Soave, solubility curve for partially miscible systems. The method
1972) or the Peng-Robinson (1976) equation to calculate was also successful in predicting phase equilibria for 10
species fugacity coefficients in all phases. A major binary hydrocarbon mixtures at higher temperatures than
drawback of this “phi-phi” approach is the necessity of at which HE data were available (Hanks et al., 1978b).
knowing binary interaction constants for each pair of Garcia Calzon et al. (1986) investigated the prediction
species present in the mixture. These parameters are not of VLE from HE data in nearly ideal mixtures of n-hexane
available “a priori” and must be found by correlating some and n-octane with the hexane isomers. They were fairly
experimental equilibrium data for the system of interest. successful using various models for GE considering the
Generally, experimental data which describe the nature magnification of errors in HE data for mixtures exhibiting
of molecular interactions must be known for each binary only minor deviations from Raoult’s law. Others have
system, regardless of the approach employed. The fun- also investigated VLE-HE cross-prediction using local
damental questions are “what data” and “how much” are composition models. Duran and Kaliaquine (1971) and
needed? Tai et al. (1972) successfully used the Wilson equation to
Group contribution methods such as UNIFAC and simultaneously correlate VLE and HE data. Vonka et al.
ASOG can be used to calculate phase equilibria for a very (1975) and Hanks and co-workers (1978a) have examined
large number of multicomponent mixtures from data for the limitations of applying the Wilson and NRTL equa-
a relatively small number of functional groups. Another tions to prediction of phase equilibria from excess enthalpy
type of approach uses minimal experimental data for a data. Bradley (1976)presents an excellent review of early
binary system at extremes of composition to predict phase work.
equilibria over the entire composition range. Infinite- The approach presented in this paper parallels the use
dilution activity coefficients have been quite successfully of infinite-dilution activity coefficients with local com-
used in this endeavor (Renon and Prausnitz, 1969;Eckert position models developed by Eckert and colleagues
and Schreiber, 1971; Nicolaides and Eckert, 1978a). The (Eckert and Schreiber, 1971;Nicolaides and Eckert, 1978a).
success of this approach and the capability to accurately
determine dilute solution calorimetric data suggest that Approach
calculation of vapor-liquid equilibria (VLE) from infinite-
dilution excess enthalpy data should also be investigated. Liquid mixture models for description of low to moder-
Several approaches based on the Wilson or NRTL ate pressure phase equilibria are generally formulated in
equation using excess enthalpy data over the entire terms of the excess Gibbs energy. The rigorous property
0888-5885/93/2632-3150$04.00/0 0 1993 American Chemical Society
Ind. Eng. Chem. Res., Vol. 32, No. 12,1993 3151
relation for the excess Gibbs energy is
nGE
d(m) =
n p
m nHE
dP- - d T = x l n y i dni
RP
(1)

from which the partial differential equations

Substitution of eqs lOand 11into eqs 12 and 13respectively


followed by differentiation according to eq 3 (assuming
constant a12 and u21) leads to
(3)
and [gIxl4
= b l ) exp( 2) (14)
+ (& a12 a21

(4)
= u2, + ul,( %)exp( 2) (15)
are obtained. Equations 3 and 4 are useful for predicting Equations 14 and 15 express the infinite-dilution reduced
low to moderate pressure phase equilibria, where pressure
excess enthalpy (limiting partial molar excess enthalpy)
has a negligible effect on excess Gibbs energy. These of components 1 and 2 respectively in a binary mixture
equations may be applied to any GE model to provide
relations for the liquid excess enthalpy and species activity provided the binary constants a12 and a21 are temperature-
coefficients. independent. Similar expressions may be obtained using
Wilson (1964) proposed an expression for the excess other models for the excess Gibbs energy of a binary
Gibbs energy based on “local composition” in a liquid mixture.
Renon and Prausnitz (1968) introduced a local com-
mixture. Amodified form of Wilson’s equation was chosen
for the present study. Wilson’s expression for the excess position model based on the “two-liquid” theory. The
Gibbs energy of a binary mixture is
NRTL equation for the excess Gibbs energy is
GE
= -xl ln(x, + x,A,,) - x , ln(x, + xlA2,) (5)
with modified binary parameters given here by where

Aij = (2) 2)exp(


and
GI, = exp(-arlz) and G,, = exp(-arzl) (17)

aij is an interaction parameter which is assumed here to


be independent of temperature and composition, and bi
and bj are the van der Waals excluded volumes for
r12= m bl,
and r,, = -
b21
RT (18)
components i and j , respectively, which are expressed in The activity coefficients are given by
terms of fluid critical temperature Tcjand critical pressure
Pi as
(7)
Wilson’s (1964) original formulation of eq 6 uses pure-
fluid molar volumes at an arbitrary temperature. The
use of hi's provides a good estimate of the relative size Evaluation of eq 19 for x 1 = 0, xz = 1 and eq 20 for x 2 =
ratio of molecules Vi/Vj while being completely indepen- 0, XI = 1yields expressions for the infinite-dilution activity
dent of temperature. The van der Waals constant bj is coefficients of components 1and 2 which when differen-
readily computed from critical constants (eq 7). tiated with respect to temperature according to eq 3
Expressions for the activity coefficients of components (assuming blz and bzl are temperature-independent) lead
1and 2 in a binary liquid mixture (obtained by applying to the following expressions for the infinite-dilution
eq 4 to eq 5) are reduced excess enthalpies:

In y1 = -ln(z, + x2h12)+ x2( x1+


4 2
XZA12
-
xz + X l A Z l
(8)
[3, = b,, + (b,, - s)2)
exp( (21)

= b,, + (b,, - g) m)
exp( - 4 1 (22)

At infinite dilution of component i in component j , eqs 8 Equations 14 and 15 or 21 and 22 may be solved for the
and 9 become respectively two binary parameters in either the Wilson or NRTL
In 7,- = -In A12 + 1- Azl (10) equation given the two infinite-dilution reduced excess
enthalpies HIE”and HzE“for a binary liquid mixture at
In y2- = -In A,, + 1- A,, a particular temperature, the pure-component critical
(11) constants for the approach using Wilson’s equation, and
However, by definition a value of the nonrandomness factor a for the NRTL
3152 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993

Table I. van der Waals Constants, Infinite Dilution Reduced Excess EnthalDies. and Calculated Binarv Parameters.

system
benzene (1)-n-heptane (2) 298.15 119.46 204.89 3220 4916 2720 3360 3750 1920
benzene (1)-n-hexadecane (2) 298.15 119.46 525.33 5707 9474 5610 6910 8630 5 830
benzene (1)-isooctane (2) 298.15 119.46 220.52 3482 5420 3040 3770 4180 2 240
benzene (l)-octene-l (2) 298.15 119.46 224.40 2 155 3783 1670 2180 3110 824
benzene (l)-cyclohexane (2) 298.15 119.46 141.31 3159 3513 2; 3 2440 2350 1890
benzene (l)-decalin (2) 298.15 119.46 229.97 2793 4003 2320 2250 2990 1460
benzene (1)-tetralin (2) 298.15 119.46 212.54 518 800 442 142 1190 -358
cyclohexane (1)-n-heptane (2) 298.15 141.31 204.89 832 1400 395 912 1660 -250
cyclohexane (1)-n-hexadecane (2) 298.15 141.31 525.33 1935 3287 1940 -9.47 2750 622
cyclohexane (l)-isooctane(2) 298.15 141.31 220.52 594 784 512 134 954 -163
cyclohexane (l)-octene-1(2) 298.15 141.31 224.40 816 1482 413 927 1830 -321
cyclohexane (1)-rn-xylene (2) 298.15 141.31 180.83 2039 2875 1350 1870 2 220 799
cyclohexane (l)-decalin (2) 298.15 141.31 229.97 240 -112 2030 -1570 -1 300 1980
cyclohexane (1)-tetralin (2) 298.15 141.31 212.54 1696 2482 1170 1380 2 040 498
n-heptane (1)-n-hexadecane (2) 298.15 204.89 525.33 379 387 1920 -1880 250 142
n-heptane (1)-octene-1 (2) 298.15 204.89 224.40 150 175 -1.55 177 423 -235
n-heptane (Wtoluene (2) 298.15 204.89 149.62 2 682 1980 1600 1370 781 2 040
n-heptene (1)-rn-xylene (2) 298.15 204.89 180.83 1811 1537 1090 916 608 1 280
n-heptane (ll-decalin (2) 298.15 204.89 229.97 401 271 774 -365 -436 880
n-heptane (1)-tetralin (2) 298.15 204.89 212.54 2 156 1 994 1 460 1150 1030 1360
isooctane (1)-n-hexadecane (2) 298.15 220.52 525.33 896 1040 1400 -856 842 208
octene-1 (1)-n-hexadecane (2) 298.15 224.40 525.33 595 695 1370 -1 150 674 20.7
toluene (1)-n-hexadecane (2) 298.15 149.62 525.33 2 447 4 967 2 200 1790 4 090 1190
decalin (1)-n-hexadecane (2) 298.15 229.97 525.33 762 1268 773 -24.4 1580 -290
tetralin (1)-n-hexadecane (2) 298.15 212.54 525.33 2 334 4 026 1980 1820 3 250 1000
isooctane (l)-n-octane (2) 298.15 220.52 238.36 102 102 143 -43.5 63.7 38.7
methylcyclohexane (1)-n-heptane (2) 298.15 171.09 204.89 103 169 -201 431 835 -580
1-chlorobutane (1)-carbon tetrachloride (2) 313.15 152.74 126.80 26.1 -24.9 682 -461 -787 956
1,2-dichloroethane (l)-carbon tetrachloride (2) 313.15 108.57 126.80 2 649 2 829 1 880 1750 1780 1 500
1,2-dichloroethane (1)-1-chlorobutane (2) 313.15 108.57 152.74 853 1785 263 1450 2 260 -434
cyclopentane (1)-tetrachloroethylene (2) 298.15 117.93 144.54 931 979 688 340 622 393
cyclohexane (1)-aniline (2) 308.15 141.31 136.83 9 717 15 352 9 670 15 100 16 500 11 900
323.15 9 641 15 114 9 580 14 900 16 100 11 800
acetone (l)-ethanol(2) 298.15 112.35 84.08 4 517 5 070 3 530 4 430 3 740 3 220
323.15 5 273 5 294 4 170 4 630 3 870 3 850
acetonitrile (1)-benzene (2) 318.15 117.89 119.46 1666 2 700 726 2 140 2380 3410
acetonitrile (1)-n-heptane (2) 318.15 117.89 204.89 11343 13 433 11300 13 200 14900 13200
methyl acetate (1)-benzene (2) 298.15 112.28 119.46 1789 1 767 1160 994 976 1020
308.15 1492 2 023 722 1440 1670 390
methyl acetate (1)-cyclohexane 298.15 112.28 141.31 8 938 8000 8 660 7 670 8240 8920
308.15 8 806 7 975 8 490 7 590 8000 8600
318.15 8 896 9 281 8 650 8 870 9380 9090
methanol (l)-ethyl acetate (2) 298.15 65.77 141.98 6 412 3 632 5 990 2 480 2580 5110
308.15 6 142 4 833 5 730 3 510 3630 4780
ethanol (l)-ethyl acetate (2) 298.15 84.08 141.98 8 046 5 486 7 640 4 890 5020 6970
308.15 8 395 7 296 8 100 6 720 7040 7850
n-propanol (1)-ethyl acetate (2) 298.15 107.95 141.98 8 197 7 181 7 860 6 750 6980 7730
308.15 7 819 6 289 7 350 5 740 5680 6840
318.15 8 317 7 106 7900 6 580 6640 7540
2-propanol (l)-ethyl acetate (2) 298.15 110.93 141.98 8 199 7 673 7 890 7 250 7550 7930
308.15 9 037 7 574 8 700 7 200 7630 8700
methanol (1)-benzene (2) 298.15 65.77 119.46 15 700 1512 15 300 1450 3380 14400
308.15 16 608 1 768 16 100 1710 3780 15300
318.15 17 538 2 175 17 000 2 130 4330 16200
methanol (1)-toluene (2) 298.15 65.77 149.62 16 515 1791 16 100 1 740 3820 15200
308.15 17 212 2 186 16 800 2 130 4320 15900
318.15 17 887 2 605 17 500 2 550 4840 16600
methanol (1)-ethyl benzene (2) 298.15 65.77 177.81 17 096 2 373 16 800 2 320 4520 15900
308.15 17 910 2 768 17 600 2 720 5040 16800
318.15 18 608 3 233 18 300 3 180 5610 17500
ethanol (1)-benzene (2) 298.15 84.08 119.46 15 933 1570 15 400 1 530 3490 14600
308.15 16 864 1942 16 200 1900 4010 15500
318.15 17 910 2 384 17 200 2 350 4620 16600
ethanol (Wtoluene (2) 298.15 84.08 149.62 16 631 1 500 16 200 1460 3550 15300
308.15 17 096 2000 16 600 1950 4110 15800
318.15 17 492 2 547 16 900 2 500 4710 16200
ethanol (l)-ethylbenzene (2) 298.15 84.08 177.81 17 678 1919 17 300 1 880 4 140 16400
308.15 18 375 2 431 17 900 2 400 4750 17200
318.15 19 073 3 012 18 600 2 980 5440 18000
2-propanol (1)-benzene (2) 298.15 110.93 119.46 16 864 3 826 16 100 3 800 6000 16100
308.15 17 352 4 454 16 700 4 430 6710 16700
318.15 17 608 5 094 16 900 5 060 7400 17100
2-propanol (1)-toluene (2) 298.15 110.93 149.62 17 678 3 745 17 100 3 720 6030 16900
308.15 18 027 4 454 17 400 4 430 6810 17400
318.15 18306 5706 17800 5 680 8140 18000
Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993 3163
Table I. (Continued)
bi b2 Hi' HzE" a12 aai biz b21
system T (K) (cm3/mol) (cm3/mol) (J/mol) (J/mol) (J/mol) (J/mol) (J/mol) (J/mol)
2-propanol (l)-ethylbenzene (2) 298.15 110.93 177.81 17 492 4 059 17 OOO 4 030 6 330 16 800
308.15 17 887 4 815 17 400 4 780 7 170 17 400
318.15 18 306 5 489 17 900 5 460 7 920 18 OOO
n-propanol (1)-benzene (2) 298.15 107.95 119.46 17 096 2 105 16 300 2 080 4 240 15 900
308.15 17 096 2 524 16 200 2 490 4 650 15 900
318.15 17 096 3 035 16 200 3000 5 140 15 900
n-propanol (1)-toluene (2) 298.15 107.95 149.62 16 980 1942 16 300 1910 4 060 15 700
308.15 17 236 2 477 16 600 2 440 4 620 16 OOO
318.15 17 445 3 047 16 700 3 010 5 220 16 300
n-propanol (1)-ethylbenzene (2) 298.15 107.95 177.81 18 027 2 198 17 500 2 170 4 470 16 800
308.15 18 189 2 768 17 600 2 740 5 080 17 100
318.15 16 306 3 408 17 700 3 370 5 740 17 300
n-butanol (1)-benzene (2) 298.15 132.43 119.46 18 027 2 291 17 OOO 2 270 4 570 16 900
308.15 18 027 2 721 17 OOO 2 700 5 010 16 900
318.15 18 207 3 187 17 OOO 3 160 5 470 16 900
n-butanol (1)-toluene (2) 298.15 132.43 149.62 17 608 2000 16 800 1980 4 210 16 400
308.15 17 608 2 512 16 800 2 480 4 720 16 400
318.15 17 608 3 128 16 800 3 090 5 330 16 500
n-butanol (Wethylbenzene (2) 298.15 132.43 177.81 18 748 2 268 18 100 2 250 4 630 17 600
308.15 18 748 2 814 18 OOO 2 790 5 200 17 600
318.15 18 748 3 431 18 OOO 3 400 5 830 17 700
n-amylalcohol (1)-benzene (2) 298.15 154.13 119.46 18 027 2 442 16 900 2 430 4 730 16 900
308.15 18 027 2 814 16 800 2 800 5 100 16 900
318.15 18 027 3 222 16 800 3 200 5 510 16 900
n-amyl alcohol (1)-toluene (2) 298.15 154.13 149.62 16 980 1965 16 100 1940 4 080 15 700
308.15 16 980 2 466 16 OOO 2 440 4 570 15 700
318.15 16 980 2 966 16 OOO 2 930 5 040 15 800
n-amyl alcohol-ethylbenzene (2) 298.15 154.13 177.81 17 608 2 163 16 800 2 140 4 380 16 400
308.15 17 608 2 687 16 800 2 660 4900 16 400
318.15 17 608 3 256 16 800 3 222 5 470 16 500
acetone (1)-water (2) 278.15 112.35 30.51 -12 487 3 947 -12 500 755 OOO 169 OOO -12 500
288.15 -11 338 4 144 -11 300 354 OOO 118 OOO -11 300
298.15 -10 193 4 105 -10 200 173 OOO 81 500 -10 200
308.15 -8 903 4 533 -8 900 82 600 32 900 -6 940
318.15 -6 960 5 860 -6 960 32 100 17 500 -4 570
323.15 -7 225 4 881 -7 230 33 800 17 600 -4 820
a Data sources for He values. All 27 hydrocarbon (1)-hydrocarbon (2) systems: Lundberg (1964). Chlorobutane (1)-carbon tetrachloride
(2), 1,2-dichloroethane(1)-carbon tetrachloride (2), and 1,2-dichloroethane(l)-chlorobutane (2): Munoz Embid et al. (1990). Cyclopentane
(1)-tetrachloroethylene (2): Polak et al. (1970). Cyclohexane (1)-aniline (2) and acetone (1)-ethanol (2): Nicolaides and Eckert (1978b).
Acetonitrile (1)-benzene (2) and acetonitrile (l)-n-heptane (2): Palmer and Smith (1972). Methyl acetate(1)-benzene (2) and methyl acetate
(1)-cyclohexane (2): Nagata et al. (1973). All four alcohol (Wethy1 acetate systems: Nagata et al. (1975). All 18 alcohol (1)-hydrocarbon
(2) systems: Mrazek and Van Ness (1961). Acetone (1)-water (2): French (1989).
0.70 0.80 0.90 Application of the Proposed Approach

Stokes and Isothermal heat of mixing data were obtained at various


&rfitt temperatures for 60 binary systems exhibiting a wide range
16 of liquid solution behavior. Infinite-dilution reduced
excess enthalpies, HxE"and Hz"", were determined for
each binary system. Most data sources provided corre-
lations for HEIx1x2 versus XI which facilitated calculation
14 of the limiting values. In other cases, the experimental
heat of mixing data were plotted as H E I x 1 x 2 versus x1 and
fit to a polynomial to obtain [ H E / X I X ~ I ~ ~and. + [HE/
~ 1 ~ 2 l X ~ ~ l .
12 This graphical estimation procedure is illustrated in
Van Ness Figure 1for the system ethanol (1)-benzene (2) at 298.15
(1961)
K for which detailed heat of mixing data in both dilute
10 -1000 regions have been measured (Stokes and Burfitt, 1973).
0.00 0.01 0.02 0.03 0.04 0.05 HE/x1x2 changes rapidly in the hydrocarbon-rich region
for alcohol-hydrocarbon mixtures; thus, such systems
xl provide a particularly stringent test of the ability to
Figure 1. Reduced excess enthalpy versus mole fraction of ethanol precisely determine infinite-dilution reduced excess en-
for ethanol (1)-benzene (2) mixtures at 298.15 K. The solid curves thalpies. The plots in Figure 1 yield infinite-dilution
were regressed to experimental data (open circles) and yielded values reduced excess enthalpies of 15 700 and 1560 J/mol for
for HIE" andH2E' nearly identical to those reported in another study components 1 and 2, respectively. These values are in
(solid circles). excellent agreement with the values of HI""and &E"
(15 933 and 1570J/mol, respectively) reported by Mrazek
equation. In either case, two nonlinear equations are and Van Ness (1961) from a correlation of data over the
solved by successive substitution for two unknown pa- full range of composition. Similar good results were
rameters. observed for other systems.
3154 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993

Table 11. Summary of Results for Calculation of Isothermal Binary VLE for Selected Systems.
TVLE TPARM &exp- -
W e x p Kcad/ ZI(psxp -
system (K) model (K) N ~ca~cllN KexpIIN PdIWN
benzene (l)-octene-l (2) 283.15 Raoult’s law 8 0.104
283.15 Wilson eq 298.15 8 0.185
283.15 NRTL eq 298.15 8 0.274
283.15 UNIFAC 8 0.024
303.15 Raoult’s law 8 0.087
303.15 Wilson eq 298.15 8 0.180
303.15 NRTL eq 298.15 8 0.263
303.15 UNIFAC 8 0.014
323.15 Raoult’s law 8 0.075
323.15 Wilson eq 298.15 8 0.172
323.15 NRTL eq 298.15 8 0.251
323.15 UNIFAC 8 0.008
chlorobutane (l)-carbon tetrachloride (2) 313.15 Raoult’s law 22 0.009 0.029 0.038
313.15 Wilson eq 313.15 22 0.008 0.028 0.035
313.15 NRTL eq 313.15 22 0.007 0.022 0.030
313.15 UNIFAC 22 0.006 0.020 0.029
1,2-dichloroethane(1)-carbon tetrachloride (2) 313.15 Raoult’s law 22 0.044 0.134 0.116
313.15 Wilson eq 313.15 22 0.052 0.158 0.116
313.15 NRTL eq 313.15 22 0.051 0.157 0.113
313.15 UNIFAC 22 0.003 0.007 0.017
1,2-dichloroethane(1)-chlorobutane (2) 313.15 Raoult’s law 22 0.018 0.053 0.060
313.15 Wilson eq 313.15 22 0.014 0.039 0.026
313.15 NRTL eq 313.15 22 0.025 0.071 0.054
313.15 UNIFAC 22 0.009 0.025 0.013
cyclopentane (1)-tetrachloroethylene (2) 298.15 Raoult’s law 15 0.011 0.014 0.084
298.15 Wilson eq 298.15 15 0.005 0.007 0.020
298.15 NRTL eq 298.15 15 0.006 0.007 0.029
298.15 UNIFAC 15 0.008 0.010 0.039
cyclohexane (1)-aniline (2) 308.15 Wilson eq 308.15 14 0.001 0.001 0.124
308.15 NRTL eq 308.15 14 0.004 0.004 0.525
308.15 UNIFAC 14 0.001 0.001 0.110
323.15 Wilson eq 323.15 15 0.003 0.003 0.247
323.15 NRTL eq 323.15 15 0.008 0.008 1.003
323.15 UNIFAC 15 0.002 0.002 0.096
acetonitrile (l)-benzene (2) 318.15 Wilson eq 318.15 11 0.007 0.047 0.032
318.15 NRTL eq 318.15 11 0.077 0.272 0.185
318.15 UNIFAC 11 0.010 0.030 0.008
acetonitrile (1)-n-heptane (2) 318.15 Wilson eq 318.15 9 0.080 0.120 0.161
318.15 NRTL eq 318.15 9 0.392 0.582 2.199
318.15 UNIFAC 9 0.019 0.032 0.024
benzene (1)-n-heptane (2) 318.15 Raoult’s law 15 0.036 0.090 0.093
318.15 Wilson eq 298.15 15 0.092 0.249 0.352
318.15 NRTL eq 298.15 15 0.111 0.300 0.373
318.15 UNIFAC 15 0.003 0.007 0.005
methyl acetate (1)-benzene (2) 303.15 Wilson eq 298.15 16 0.039 0.110 0.081
303.15 NRTL eq 298.15 16 0.038 0.105 0.076
303.15 UNIFAC 16 0.004 0.012 0.022
323.15 Wilson eq 308.15 12 0.028 0.064 0.068
323.15 NRTL eq 308.15 12 0.028 0.064 0.068
323.15 UNIFAC 12 0.002 0.005 0.027
methyl acetate (l)-cyclohexane (2) 308.15 Wilson eq 308.15 8 0.099 0.154 0.353
308.15 NRTL eq 308.15 8 0.212 0.319 0.961
308.15 UNIFAC 8 0.007 0.010 0.045
313.15 Wilson eq 318.15 9 0.156 0.437 0.516
313.15 NRTL eq 318.15 9 0.285 0.723 1.504
313.15 UNIFAC 9 0.011 0.025 0.034
methanol (l)-ethyl acetate (2) 328.15 Wilson eq 308.15 11 0.094 0.257 0.313
328.15 NRTL eq 308.15 11 0.137 0.388 0.429
328.15 UNIFAC 11 0.004 0.010 0.005
ethanol (l)-ethyl acetate (2) 328.15 Wilson eq 308.15 11 0.153 0.378 0.565
328.15 NRTL eq 308.15 11 0.255 0.647 1.138
328.15 UNIFAC 11 0.011 0.021 0.016
n-propanol (l)-ethyl acetate (2) 328.15 Wilson eq 318.15 12 0.106 0.819 0.525
328.15 NRTL eq 318.15 12 0.179 1.515 0.971
328.15 UNIFAC 12 0.009 0.033 0.011
2-propanol (1)-ethyl acetate (2) 328.15 Wilson eq 308.15 12 0.155 0.570 0.647
328.15 NRTL eq 308.15 12 0.253 0.987 1.306
328.16 UNIFAC 12 0.016 0.036 0.036
methanol (1)-benzene (2) 308.15 Wilson eq 308.15 9 0.068 0.202 0.160
308.15 NRTL eq 308.15 9 0.210 0.589 1.491
308.15 UNIFAC 9 0.012 0.027 0.012
ethanol (1)-benzene (2) 328.15 Wilson eq 318.15 9 0.065 0.164 0.179
328.15 NRTL eq 318.15 9 0.166 0.453 0.686
328.15 UNIFAC 9 0.014 0.034 0.011
Ind. Eng. Chem. Res., Vol. 32, No. 12,1993 3155
Table XI. (Continued)
TVLE TPARM UYeIP - Z I ( K q - KmdI El(P- -
system (K) model (K) N YdCW K 4 N PdIWN
ethanol (1)-toluene (2) 308.15 Wilson eq 308.15 10 0.062 0.120 0.200
308.15 NRTL eq 308.15 10 0.165 0.318 1.465
308.15 UNIFAC 10 0.021 0.041 0.036
328.15 Wilson eq 318.15 10 0.064 0.110 0.219
328.15 NRTL eq 318.15 10 0.142 0.242 1.035
328.15 UNIFAC 10 0.011 0.019 0.012
acetone (1)-water (2) 373.15 Wilson eq 323.15 22 0.134 0.329 0.249
373.15 NRTL eq 323.15 22 0.158 0.371 0.253
373.15 UNIFAC 22 0.018 0.059 0.024
473.15 Wilson eq 323.15 25 0.076 0.233 0.099
473.15 NRTL eq 323.15 25 0.099 0.292 0.123
473.15 UNIFAC 25 0.056 0.165 0.104
0 Data sources for isothermal VLE. Benzene (l)-octene-1 (2): Vera and Prausnitz (1971). Chlorobutane (l)-carbon tetrachloride (2),
1,2-dichloroethane (l)-carbon tetrachloride (2), and 1,2-dichloroethane (l)-chlorobutane (2): Munoz Embid et al. (1990). Cyclopentane
(1)-tetrachloroethylene (2): Polak et al. (1970). Cyclohexane (1)-aniline (2): Abello et al. (1968). Acetonitrile (1)-benzene (2), acetonitrile-
n-heptane (2), and benzene (1)-n-heptane (2): Palmer and Smith (1972). Methyl acetate (1)-benzene (2) and methyl acetate (l)-cyclohexane
(2): Nagata et al. (1973). All four alcohol (l)-ethyl acetate (2) systems: Nagata et al. (1975). Methanol (1)-benzene (2): Scatchard et al. (1946).
Ethanol (1)-benzene (2): Ho and Lu, (1963). Ethanol (1)-toluene (2): Kretachmer and Wiebe (1949). Acetone (1)-water (2): Griewold and
Wong (1952).
Table 111. Summary of Results for Calculation of Isobaric Binary VLE for Selected Systems at 760 m m H p

benzene (l)-cyclohexane (2) 353.25,353.89 Raoult’s law 9 0.027 0.076 0.007


Wilson eq 298.15 9 0.079 0.188 0.020
NRTL eq 298.15 9 0.078 0.187 0.019
UNIFAC 9 0.005 0.016 0.000
acetonitrile (1)-benzene (2) 354.93,353.25 Wilson eq 318.15 5 0.013 0.041 0.003
NRTL eq 318.15 5 0.074 0.206 0.016
UNIFAC 5 0.004 0.007 0.001
acetonitrile (1)-n-heptane (2) 354.93,371.58 Wilson eq 318.15 8 0.078 0.135 0.016
NRTL eq 318.15 8 0.314 0.509 0.070
UNIFAC 8 0.065 0.109 0.011
benzene (1)-n-heptane (2) 353.25,371.58 Raoult‘s law 5 0.028 0.061 0.006
Wilson eq 298.15 5 0.088 0.248 0.022
NRTL eq 298.15 5 0.109 0.319 0.026
UNIFAC 5 0.007 0.022 0,001
methyl acetate (1)-benzene (2) 330.76,353.25 Wilson eq 308.15 12 0.037 0.115 0.006
NRTL eq 308.15 12 0.037 0.115 0.006
UNIFAC 12 0.007 0.013 0.002
methanol (l)-ethyl acetate (2) 337.90,349.87 Wilson eq 308.15 14 0.079 0.127 0.022
NRTL eq 308.15 14 0.115 0.189 0.028
UNIFAC 14 0.013 0.025 0.000
ethanol (l)-ethyl acetate (2) 351.48,349.87 Wilson eq 308.15 11 0.164 0.540 0.035
NRTL eq 308.15 11 0.276 0.924 0.057
UNIFAC 11 0.014 0.026 0.003
methanol (1)-benzene (2) 337.91,353.25 Wilson eq 318.15 15 0.038 0.067 0.008
NRTL eq 318.15 15 0.155 0.285 0.040
UNIFAC 15 0.040 0.074 0.004
a Data sources for isobaric VLE. Benzene (l)-cyclohexane (2): Thornton and Garner (1951). Acetonitrile (1)-benzene (2), acetonitrile
(1)-n-heptane (2), and benzene (1)-heptane (2): Tripathi and Asselineau (1975). Methyl acetate (1)-benzene (2): Nagata (1962). Methanol
(l)-ethyl acetate (2) and ethanol (l)-ethyl acetate (2): Zandijcke and Verhoeye (1974). Methanol (1)-benzene (2): Williams et al. (1948).

Equations 14 and 15 were next solved for the Wilson surprising, since it has been suggested by several workers
parameters a12 and a21 and eqs 21 and 22 were solved with (Duran and Kaliaquinene, 1971;Nagata and Yamada, 1974;
a = 0.30 for the NRTL parameters b12 and bzl for each of Vonka et al., 1975; Prausnitz et al., 1986) that these
the systems studied. Table I summarizes the infinite- parameters should be considered to be functions of
dilution reduced excess enthalpies and binary parameters temperature. Nonetheless, it is useful to examine for what
for both the Wilson and NRTL equations at several types of systems eqs 14 and 15 or 21 and 22 are
temperatures for all 60 systems. The van der Waals approximately valid. It should be emphasized that these
constants b for each of the pure components are also listed. equations in their given form cannot be derived with
The data in Table I clearly demonstrate that the temperature-dependent parameters.
parameters are not truly temperature-independent for Isothermal VLE for 19 systems a t several temperatures
either the Wilson or NRTL equation. For example, the were calculated using four bubble-point temperature
Wilson parameters a12 and a21 vary up to 2000 J/mol over schemes (i.e., Raoult’s law, Wilson-Prausnitz, NRTL-
a temperature range of 20 K (Le., from 298.15 to 318.15 Prausnitz, and UNIFAC-Prausnitz). Similar schemes
K) for 18 binary alcohol-aromatic hydrocarbon systems. were used to calculate the bubble-point temperature and
This constitutes a considerable percentage change, espe- vapor composition for eight isobaric binary systems. The
cially for the parameter a21. Similar trends are observed vapor phase model Prausnitz refers to the simple corre-
for other systems for which heat of mixing data are sponding-states correlation (Prausnitz, 1969; Smith and
available a t multiple temperatures. This finding is not Van Ness, 1987)for the vapor-phase fugacity coefficients.
3156 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993

Raoult’s law was used as a basis of comparison for mixtures 1.oo


containing only nonpolar and/or slightly polar species, and
the UNIFAC method provided a benchmark for Wilson
or NRTL model performance for moderately and strongly 0.80
nonideal systems.
VLE prediction results for the 20 selected systems are
0.60
presented in Tables I1 and 111. Table I1 summarizes the
results for isothermal systems. The table lists the tem- 7
x
perature at which isothermal VLE were calculated, T ~ E ;
0.40
the model used (i.e., Raoult’s law, Wilson-Prausnitz,
NRTL-Pruasnitz, or UNIFAC-Prausnitz); the temper-
ature at which parameters were obtained, T p m ~the ;
number of mixture experimental data points N,the average 0.20
error in vapor-phase mole fraction per point, Clyexp -ycalcl/
N, the average percent error in component 1distribution
coefficient per point, CI(K1exp - K1 calc)/K1exp)l and the 0.00 ’
0.00 0.20 0.40 0.60 0.80 1.00
I

average percent error in absolute total pressure per point,


p l / ~ .I11gives similar information
~ l ( P ~ x ~ - P ~ ~ c ) / P e xTable xl
for the isobaric systems studied. Results for four repre-
sentative systems are now examined in detail, and various
issues including effects of system type and the method of I
VLE data representation on model performance are
addressed. 0 (1970)
The system cyclopentane (1)-tetrachloroethylene (21,
for which isothermal VLE and heat of mixing data were
available at 298.15 K (Polak et al., 19701, illustrates the
degree to which the proposed approach works for simple
nonpolar mixtures using three conventional means of
representing isothermal binary VLE. Wilson and NRTL
parameters were determined from the limiting partial
molar excess enthalpies HIEmand H2E”, and isothermal
VLE were predicted at 298.15 K using each of the four
schemes described above. Figure 2 presents the experi-
mental VLE and predictions using the Wilson-Prausnitz
bubble-point pressure routine. The results for Raoult’s
law are also shown for comparison. 0.00 0.20 0.40 0.60 0.80 1.00

Figure 2a depicts the vapor-liquid composition ( y l - x l ) XI. Y l


diagram. Description of y1 versus x 1 is excellent for the
Wilson-Prausnitz method. Average errors in vapor mole
fraction per point range from 0.005 for Wilson-Prausnitz
to 0.011 for Raoult’s law. The major improvement over
Raoult’s law is evident in the description of the bubble-
point curve shown in Figure 2b (about 3% average error
in P versus x1 for the Wilson or NRTL equations as
0.80

0.40
/c
c
\
compared to 8.4 % error for Raoult’s law). Figure 2c shows
equilibrium K values (Ki= yi/xi) plotted against system
total pressure. Ki versus P is a standard representation
of isothermal VLE for simple relatively nonpolar mixtures
such as hydrocarbon mixtures. Again, the deficiency of 1
-0.40 K2 ’\ - Wilson
Raoult’s law is clearly apparent.
Mixtures containing moderately polar species are often
fairly well described by the Wilson model but are generally -0.80 1 \
poorly described by the NRTL model. Heat of mixing
and VLE for the acetonitrile (1)-benzene (2) system at
318.15 K were obtained by Palmer and Smith (1972).HIE“
-1.20 ’0 60 120 180 240 300
I

and H2E” were determined and used to predict isothermal


VLE for this system at 318.15 K. A comparison of the P (mm Hg)
performance of the Wilson and NRTL BUBLP approaches Figure 2. Experimental and calculated isothermal VLE for the
is given in Figures 3. Results from the UNIFAC method cyclopentane (1)-tetrachloroethylene (2) system at 298.15 K: (a)
are also shown for comparison. yl-xl diagram;(b) P-xl,yl diagram;(c)K-Pdiagram. Results for the
Wilson-Prausnitz approach are superior to Raoult’s law in all three
The yl-xl diagram for this system is presented in Figure plots for this simple mixture.
3a. The Wilson-Prausnitz and UNIFAC-Prausnitz meth-
ods yield comparable results in this case (0.010 versus 0.007 of the NRTL model is much more pronounced in de-
average deviation in vapor mole fraction for 11data points scription of the P-x1,y1 diagram (Figure 3b). The system
for the Wilson and UNIFAC methods, respectively); total pressure is only slightly underestimated using the
however, results for the NRTL-Prausnitz method with a Wilson-Prausnitz routine. In contrast, the NRTL-
= 0.30 are considerably less satisfactory (0.077 average Prausnitz routine significantly overestimates the total
deviation in vapor mole fraction). The poor performance pressure (2.7 % average error in P for Wilson’s equation
Ind. Eng. Chem. Res., Vol. 32, No. 12,1993 3157
1.00 I
a
0.80 .

0.60 0.60 *
r r
x
r ' -
A

>,
Scatchard et
0.40 0.40
81. (1946)
Wilson

0.20
VJIFAC

n nn
W."W W.W"

0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

X I xi

d.2" 350
' 8 %I&

.
snd
b ,*-
C--------_.

I
I / \\
\
0 -,smith (1972) b
I'
I \
/' I
I \
\
\
\\ 300
I I
I I \
I I \\
I II \
1
300. / II \
1
II I 1
I

Ea m Scatchard et -
250 o al. (1946)

150
...... UJIFAC

200 100
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

XI. yl XI. yl

Figure 3. Experimental and calculated isothermal VLE for the Figure 4. Experimental and calculated isothermal VLE for the
acetonitrile (1)-benzene (2) system at 318.15 K. (a) yl-xl diagram; methanol (1)-benzene (2) system at 308.15 K (a)yl-rl diagram; (b)
(b) P - z ~ Jdiagram.
~ A good description of the experimentaldata is P-rlyl diagram.The Wilson-Prausnitz approachproduces only fair
achievedusing the Wilson-Prausnitz approach;however the NRTL- results for this strongly nonideal system.
Prausnitz approach fails to produce satisfactory results.
average of 17.5% per point). In contrast, errors for the
versus 19.5% average error in Pfor the NRTL equation). UNIFAC method are only 0.012 in y1 and 1.2% in P. It
The UNIFAC method (average error of 0.8% in P for 11 is also noted that the NRTL-Prausnitz BUBLP approach
points) is only slightly better than the Wilson model in completely fails to describe the phase behavior of this
this case. system (0.210 error in y1 versus X I and 152.7 3'% error in P
Methanol (1)-benzene (2) is representative of a large versus X I ) . Similar results are observed for other alcohol-
class of highly nonideal binary mixtures which contain hydrocarbon systems included in the present study, and
one very polar species such as an alcohol which undergoes an interpretation based on the inability of Wilson pa-
significant hydrogen bonding and a relatively (but not rameters to sufficiently back-calculate excess enthalpy
entirely) inert component such as an aliphatic or simple data for alcohol-hydrocarbon systems is given later in this
aromatic hydrocarbon. Mrazek and Van Ness (1961) paper.
measured isothermal heats of mixing for 18binary alcohol- Isobaric VLE were also calculated for eight systems at
aromatic hydrocarbon systems from 298.15 to 318.15 K atmospheric pressure. HE data correlation and VLE
using a novel isothermal dilution calorimeter. Included prediction were done at the same temperature for each of
in their measurements are excess enthalpy data for the the three previous isothermal systems discussed; hence,
methanol (1)-benzene (2) system at 308.15 K. Scatchard it is useful to examine cases where this is not true (isobaric
et al. (1946)measured isothermal VLE for the same system systems) to try to ascertain the effects of differences
at 308.15 K. These data are presented in Figure 4 along between correlation and prediction temperatures. The
with VLE for this system calculated using the Wilson- isobaric yl-xl diagram for the system methyl acetate
Prausnitz BUBLP routine. Results from the UNIFAC (1)-benzene (2) at 760 mmHg (Nagata, 1962) is shown in
method are shown for comparison. Figure 5a. The Wilson model overcorrects for positive
Wilson model description of the yl-xl diagram for this deviations from Raoult's law (average deviation in y1 is
system (Figure 4a) is fairly good. The average error of 0.037 for the Wilson-Prausnitz routine and 0.007 for the
0.069 in vapor composition is biased by considerable UNIFAC-Prausnitz routine). This overcorrection is more
deviations in the benzene-rich region ( X I < 0.10). Pversus apparent in the temperature-composition diagram (Figure
X I (Figure 4b) shows considerably greater error (Le., an 5b). The average errors of 0.6% and 0.2% reported in
3158 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993
1.oo be better thanPor Tversus x l using either method (Wilson
a or NRTL). The Wilson model produces good-to-excellent
yl-xl diagrams for the four systems discussed earlier;
0.80 however, system pressure- or temperature-composition
profiles for the same systems show greater deviation. The
distribution coefficient for species 1, K1 ( y ~ l x l )is an
0.60 alternative measure of system composition. Errors in K1
r versus x1 (reported in Tables I1 and 111) follow a trend
x 6 Nagata
( 1962)
similar to errors in vapor-phase mole fraction.
0.40 The use of infinite-dilution reduced excess enthalpies
- Wilson
with Wilson's equation generally performs much better
UNIFAC . than with the NRTL equation for most of the systems
0.20 studied. The apparent limitation of the NRTL equation
in this work is that the nonrandomness factor a must be
arbitrarily specified (a = 0.30 here) to obtain a two-
V.W
0.00
~~

0.20 0.40 0.60 0.80 1.00


parameter model. The general failure of the NRTL
equation is quite unfortunate, since the NRTL equation
xl is capable of describing liquid-liquid equilibria whereas
Wilson's equation is not. Perhaps a more systematic
360 I I method for choosing a value of the nonrandomness factor
b Nagata
according to type of binary system would produce better
0 (1962) results using the NRTL-Prausnitz approach.
350
- Wilson . Model predictive performance for a given system should
depend to a large extent on the ability to "back-calculate"
heat of mixing data over the full liquid composition range.

'
+ 340
Such calculations were made with the Wilson model for
the four highlighted systems, and the results are presented
in Figures 6. Description of the excess enthalpy profiles
for cyclopentane (1)-tetrachloroethylene (2) at 298.15 K
and for acetonitrile (1)-benzene (2) at 318.15 K is excellent,
330 I suggesting that the temperature-independent Wilson
model is useful for describing phase behavior of nonpolar
mixtures and nonideal systems with moderately unsym-
320 '
0.00 0.20 0.40 0.60 0.80
I
1.00
metric excess functions. However, only fair agreement
between calculated and experimental heat of mixing data
is observed for the system methyl acetate (1)-benzene (2)
XI. yl
at 308.15 K (Figure 6b), while the results for methanol
(1)-benzene (2) at 308.15 K (Figure 6b) are very poor. The
Figure6. Experimentaland calculated isobaric VLE for the methyl results from Figure 6 are in accord with the results from
acetate (1)-benzene (2) system at 760 mm Hg: (a)yl-rl diagram;(b) Figures 2-5, indicating that the capacity of estimated
T - q y l diagram.A good qualitativedescriptionof the data is produced
using thewilson-Prausnitz approach. parameters to describe heat of mixing data is paramount
in determining VLE predictive performance.
Table I11 for the Wilson and UNIFAC methods respec- One possible reason for the failure in HE representation
tively are artificially low because the temperature range for alcohol-hydrocarbon systems is that there are solutions
for this system is small compared to absolute temperatures. to eqs 14 and 15 which are unattainable by the method of
The VLE system temperatures for this data set vary successive substitution. An alternative explanation is that
from about 330 to 355 K whereas model-parameters were the temperature dependence of (1.12and (1.21 is great enough
determined from heat of mixing data a t 308.15 K. It is to make eqs 14and 15inaccurate for suchsystems. Finally,
likely that the temperature variation has some impact, vapor-phase association must play a role for alcohol-
but it is hard to isolate this effect considering that similar containing systems; however, UNIFAC predictions are so
errors in vapor mole fraction and total pressure are good that no reasonable amount of unaccounted for alcohol
observed for calculation of isothermal VLE for methyl association could offset large Wilson model errors. Nev-
acetate (1)-benzene (2) a t 303.15 K from HE data at 298.15 ertheless, future work should employ a vapor-phase model
K (see Table 11). It is also interesting to note that excellent (Prausnitz et al., 1980) which properly accounts for
results are achieved using the Wilson model to predict association.
isobaric VLE for acetonitrile (1)-benzene (2) at atmo- Some additional insight is available for alcohol-hydro-
spheric pressure (bubble-pointtemperatures in the vicinity carbon mixtures. The Wilson parameters a12 and a21
of 350 K)from isothermal heat of mixing data at 318.15 exhibit strong trends with HIE" and HzE", respectively.
K. The data for the 18 binary alcohol-hydrocarbon systems
The degree to which model parameters can be used to in Table I are plotted as a12 versus H l E mand (1.21 versus
back-calculate HE data appears to be a much better H2E"in Figure 7a and 7b, respectively. A clear linear trend
performance indicator. A comprehensive discussion of is evident in each case with a near perfect linear rela-
this and other important issues is now presented. tionship between a21 and HzE". These plots yield the
relations
Discussion
Some general conclusions can be reached from the results
a12= -217.2 + 0.974H:" (23)
of this study. First, predictions of y1 versus x1 appear to and
Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993 3159
500 19
a ,,B'-QQ
b \

I Y\
400 //d \
18
I
i
b\

z 300 I
I

.---
0 Palmer and '\
Smith (1972) '\
B u
sj
-
\
-J 17

Y 200
cat;
I Polak et al. 16
100 (1 970)
Calculated

0 15
0.00 0.20 0.40 0.60 0.80 1.00 15 16 17 I8 19 20
(Thousands)
xl HE 1inf (J/mol)

1000 6000
b 0 Mazek an
0 Van Ness
800 0 0
(1961) 5000
0 .--- Calculated
0
0
1
-.
600 Nagata et 4000
-3 0
-
al. (1973)
Calculated
0 -I

y 400
F

% 3000

200 2000

0 1000
0.00 0.20 0.40 0.60 0.80 1.00 1000 2000 3000 4000 5000 6000

xl HE2inf (J/mol)
Figure 6. Back-calculated heat of mixing for the systems: (a) Figure 7. Correlation of Wilson parameters with infinite- dilution
cyclopentane (1)-tetrachloroethylene (2) at 298.15 K (Polak et al., reduced excess enthalpies for binary alcohol-aromatic hydrocarbon
1970) and acetonitrile (1)-benzene (2) at 318.15K (Palmerand Smith, systems: (a) the parameter a12 versus HIE";(b) the parameter (121
1972); (b) methanol (1)-benzene (2) at 308.15 K (Mrazek and Van versus HzE'.
Ness, 1961) and methyl acetate (1)-benzene (2) at 308.15 K (Nagata
et al., 1973). Results are excellent for both systems in (a), fair for potential for CFC substitution. In contrast, it is unlikely
methyl acetate-benzene, and poor for methanol-benzene.
that the proposed approach in its present form will find
any great use for strongly nonideal systems.
= -43.8 + 1.003H,Em
~2~ (24)
where all quantities are expressed in J/mol. Conclusions
These results can be cautiously explained in terms of An approach is presented using the Wilson or NRTL
the vastly different behavior of alcohol-rich versus hy- equation with limiting partial molar excess enthalpies to
drocarbon-rich mixtures. In the infinitely dilute alcohol calculate isothermal or isobaric VLE for several systems
region the value of HIE" is approximately equal to the over limited ranges of temperature. Analysis of several
enthalpy of hydrogen bond formation for the alcohol, factors including the type of mixture, temperature dif-
assuming the hydrocarbon solvent to be inert. Thus, it ference between parameter estimation and VLE calcu-
can be seen from eq 23 that the Wilson parameter 012 is lation, ability to back-calculate heat of mixing, and vapor-
nearly equal to the hydrogen bond energy of the alcohol. phase effects suggests that the Wilson equation may be
However, this physical significance is very imprecise useful in cross-predictingVLE from infinite-dilution excess
considering the poor results in Figure 6b. Of practical enthalpy data for nearly ideal and moderately nonideal
importance is that the correlations given by eqs 23 and 24 systems. However, reasonable estimates of vapor-liquid
can be used to provide rough estimates of the Wilson equilibria are also possible for strongly nonideal systems.
parameters a12 and u21. The proposed modellapproach may be particularly useful
The approach presented in this paper may be useful for in reducing experimental effort in exploratory research
new systems for which few experimental thermodynamic for new mixtures.
data are available. One highly potential application is
the preliminary identification of chlorofluorocarbon (CFC)
alternative mixtures with low ozone depletion potentials. Nomenclature
Results from calorimetric studies in the dilute regions of aij = Wilson binary parameter (J/mol)
such mixtures (likely to consist of various hydrofluoro- bi = van der Waals constant for species i (cms/mol)
carbons) could be used to identify azeotropes with excellent bjj = NRTL binary parameter (J/mol)
3160 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993

GE = excess Gibbs energy (J/mol) Fredenslund, Aa.; Gmehling, G.; Rasmussen. P. Vapor-Liquid
Gij = NRTL binary parameter Equilibria Using UNZFAC.Elsevier, North Holland: Amsterdam,
EIE = excess enthalpy (J/mol) 1977b.
Hpm= infinite-dilution reduced excess enthalpy of species French, H. T. Excess Enthalpies of (Acetone + Water) at 278.15,
288.15,298.15,308.15,318.15, and 323.15 K. J.Chem. Thermodyn.
i (J/mol) 1989,21, 801-809.
Ki = distribution coefficient for species i Garcia Calzon, J. A.; Pando, C.; Renuncio, J. A. R. Simultaneous
n = total moles (mol) Correlation of Vapor-Liquid Equilibrium and Excess Enthalpies
ni = moles of species i (mol) for Binary Mixtures of n-Hexane and n-octane with Hexane
N = number of data points Isomers. Thermochim. Acta 1986,106, 219-231.
P = absolute total pressure (mmHg) Griswold,J.; Wong, S. Y. Phase-Equilibria of the Acetone-Methanol-
PCdc= calculated total pressure (mmHg) Water System from 100 "C Into the Critical Region. Chem. Eng.
Pci = critical pressure of species i (bar) Prog. Symp. Ser. 1952,48 (3), 18-34.
PSI,,= experimental total pressure (mmHg) Hanks, R. W.; Gupte, A. C.; Christensen, J. J. Calculation of
PisAT = vapor pressure of species i (mmHg) Isothermal Vapor-Liquid Equilibrium Data for Binary Mixtures
from Heats of Mixing. Znd. Eng. Chem. Fundam. 1971,10,504-
R = gas constant (J/(mol K)) or (cm3bar/(mol K)) 509.
T = absolute temperature (K) Hanks, R. W.; Tan, R. L.; Christensen, J. J. Limits on the
Tci = critical temperature of species i (K) Simultaneous Correlation of GE and HEdata by the NRTL, LEMF,
TisAT = saturated temperature of species i (K) and Wilson's Equations, Thermochim. Acta 1978a, 23,41-55.
T p m ~= temperature at which H P were determined (K) Hanks, R. W.; Tan, R. L.; Christensen, J. J. The Prediction of High
T ~ = temperature
E at which isothermal VLE were predicted Temperature Vapor-Liquid Equilibria from Lower Temperature
(K) Heat of Mixing Data. Thermochim. Acta 1978b, 27,9-18.
VE = excess volume (cm3/mol) Ho, J. C. K.; Lu, B. C.-Y. Vapor-Liquid Equilibria. Part 11. System
Vi = liquid molar volume of species i (cm3/mol) n-Hexane-Ethanol-Benzene at 55 OC. J. Chem. Eng. Data 1963,
xi = liquid-phase mole fraction of species i 8, 553-558.
y d c = calculated vapor-phase mole fraction of species i Kojima, K.; Tochigi, K. Prediction of Vapor-Liquid Equilibria by
yexp= experimental vapor-phase mole fraction of species i the ASOG Method; Kodansha Ltd.: Tokyo, Elsevier, North
Holland: Amsterdam, 1979.
yi = vapor-phase mole fraction of species i Kretachmer, C. B.; Wiebe, R. Vapor-Liquid Equilibrium of Ethanol-
Greek Letters Toluene Solutions. J. Am. Chem. SOC.1949, 71, 1793-1797.
a = nonrandomness factor in NRTL equation Lundberg, G. W. Thermodynamics of Solutions XI. Heats of Mixing
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