13-20 DISTILLATION

exceed values of approximately 7.5, the van Laar equation erro-

neously predicts phase splitting.
Tables 13-1, 13-2, and 13-4 include data on formic acid and acetic
acid, two substances that tend to dimerize in the vapor phase accord-
ing to the chemical-equilibrium expression
KD = PD /PM2 = 10A + B/T (13-5)
where KD is the chemical-equilibrium constant for dimerization, PD
and PM are partial pressures of dimer and monomer respectively in
torr, and T is in K. Values of A and B for the first four normal aliphatic
acids are:

A B
Formic acid −10.743 3083
Acetic acid −10.421 3166
n-Propionic acid −10.843 3316
n-Butyric acid −10.100 3040

As shown by Marek and Standart [Collect. Czech. Chem. Commun.,

19, 1074 (1954)], it is preferable to correlate and utilize liquid-phase
activity coefficients for the dimerizing component by considering sep-
arately the partial pressures of the monomer and dimer. For example,
for a binary system of components 1 and 2, when only compound 1
dimerizes in the vapor phase, the following equations apply if an ideal
gas is assumed:
P1 = PD + PM (13-6)
y1 = (PM + 2PD)/P (13-7)
These equations when combined with Eq. (13-5) lead to the following
equations for liquid-phase activity coefficients in terms of measurable
quantities:

γ1 = !
Py1
!
!!!
1 + (1 + 4KDP1sat)0.5
P1 x1 1 + [1 + 4KDPy1(2 − y1)]0.5
sat " (13-8)

FIG. 13-19 Liquid-phase activity coefficients for an n-heptane-toluene sys-

# $
Py1 2{1 − y1 + [1 + 4KDPy1(2 − y1)]0.5}
tem at 101.3 kPa (1 atm). [Henley and Seader, Equilibrium-Stage Separation γ2 = ! !!!! (13-9)
Operations in Chemical Engineering, Wiley, New York, 1981; data of Yerazunis P2 x2 (2 − y1){1 + [1 + 4KDPy1(2 − y1)]0.5}
sat

et al., Am. Inst. Chem. Eng. J., 10, 660 (1964).]

Detailed procedures, including computer programs for evaluating
binary-interaction parameters from experimental data and then utiliz-

TABLE 13-2 Binary-Interaction Parameters*

Margules van Laar Wilson (cal/mol)
System %
A12 %21
A A12 A21 (λ12 − λ11) (λ21 − λ22)
Acetone (1), chloroform (2) −0.8404 −0.5610 −0.8643 −0.5899 116.1171 −506.8519
Acetone (1), methanol (2) 0.6184 0.5788 0.6184 0.5797 −114.4047 545.2942
Acetone (1), water (2) 2.0400 1.5461 2.1041 1.5555 344.3346 1482.2133
Carbon tetrachloride (1), benzene (2) 0.0948 0.0922 0.0951 0.0911 7.0459 59.6233
Chloroform (1), methanol (2) 0.8320 1.7365 0.9356 1.8860 −361.7944 1694.0241
Ethanol (1), benzene (2) 1.8362 1.4717 1.8570 1.4785 1264.4318 266.6118
Ethanol (1), water (2) 1.6022 0.7947 1.6798 0.9227 325.0757 953.2792
Ethyl acetate (1), ethanol (2) 0.8557 0.7476 0.8552 0.7526 58.8869 570.0439
n-Hexane (1), ethanol (2) 1.9398 2.7054 1.9195 2.8463 320.3611 2189.2896
Methanol (1), benzene (2) 2.1411 1.7905 2.1623 1.7925 1666.4410 227.2126
Methanol (1), ethyl acetate (2) 1.0016 1.0517 1.0017 1.0524 982.2689 −172.9317
Methanol (1), water (2) 0.7923 0.5434 0.8041 0.5619 82.9876 520.6458
Methyl acetate (1), methanol (2) 0.9605 1.0120 0.9614 1.0126 −93.8900 847.4348
1-Propanol (1), water (2) 2.7070 0.7172 2.9095 1.1572 906.5256 1396.6398
2-Propanol (1), water (2) 2.3319 0.8976 2.4702 1.0938 659.5473 1230.2080
Tetrahydrofuran (1), water (2) 2.8258 1.9450 3.0216 1.9436 1475.2583 1844.7926
Water (1), acetic acid (2) 0.4178 0.9533 0.4973 1.0623 705.5876 111.6579
Water (1), 1-butanol (2) 0.8608 3.2051 1.0996 4.1760 1549.6600 2050.2569
Water (1), formic acid (2) −0.2966 −0.2715 −0.2935 −0.2757 −310.1060 1180.8040
*Abstracted from Gmehling and Onken, Vapor-Liquid Equilibrium Data Collection, DECHEMA Chemistry Data ser., vol. 1 (parts 1–10), Frankfurt, 1977.

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 THERMODYNAMIC DATA 13-21

TABLE 13-3 Activity-Coefficient Equations in Binary Form for Use with Parameters and Constants
in Tables 13-2 and 13-4
Type of equation Adjustable parameters Equations in binary form
Margules %12
A %12 + 2(A
ln γ1 = [A %21 − A
%12)x1]x 22
%21
A %21 + 2(A
ln γ2 = [A %12 − A
%21)x2]x 12

# $
2
A21x2
van Laar A12 ln γ1 = A12 !!
A12 x1 + A21 x2

# $
2
A12x1
A21 ln γ2 = A21 !!
A12 x1 + A21 x2

# $
Λ12 Λ21
Wilson λ12 − λ11 ln γ1 = −ln (x1 + Λ12 x2) + x2 !! − !!
x1 + Λ12 x2 Λ21 x1 + x2

# $
Λ12 Λ21
λ 21 − λ22 ln γ2 = −ln (x2 + Λ21 x1) − x1 !! − !!
x1 + Λ12 x2 Λ21 x1 + x2

# $ # $
L L
v 2 λ12 − λ11 v 1 λ 21 − λ 22
where Λ12 = ! exp − ! Λ21 = ! exp − !
v1L RT v L2 RT
vLi = molar volume of pure-liquid component i
λ ij = interaction energy between components i and j, λ ij = λ ji

ing these parameters to predict K values and phase equilibria, are
given in terms of the UNIQUAC equation by Prausnitz et al. (Com-
puter Calculations for Multicomponent Vapor-Liquid and Liquid-
Liquid Equilibria, Prentice-Hall, Englewood Cliffs, N.J., 1980) and in
terms of the UNIFAC group contribution method by Fredenslund,
Gmehling, and Rasmussen (Vapor-Liquid Equilibria Using UNIFAC,
Elsevier, Amsterdam, 1980). Both use the method of Hayden and
O’Connell [Ind. Eng. Chem. Process Des. Dev., 14, 209 (1975)] to
compute Φ̂iV in Eq. (13-4). When the system temperature is greater
than the critical temperature of one or more components in the mix-
ture, Prausnitz et al. utilize a Henry’s-law constant Hi,M in place of the
product γ iL ΦiL in Eq. (13-4). Otherwise ΦiL is evaluated from vapor-
pressure data with a Poynting saturated-vapor fugacity correction.
When the total pressure is less than about 202.6 kPa (2 atm) and all
components in the mixture have a critical temperature that is greater
than the system temperature, then ΦiL = Pisat/P and Φ̂iV = 1.0. Equation
(13-4) then reduces to
Ki = γ iLPisat/P (13-10)
which is referred to as a modified Raoult’s-law K value. If, further-
more, the liquid phase is ideal, then γ iL = 1.0 and
K i = Pisat/P (13-11)
which is referred to as a Raoult’s-law K value that is dependent solely
on the vapor pressure Pisat of the component in the mixture. The
UNIFAC method is being periodically updated with new group
contributions, with a recent article being that of Hansen et al. [Ind.
Eng. Chem. Res., 30, 2352 (1991)].

TABLE 13-4 Antoine Vapor-Pressure Constants and Liquid Molar Volume*

Antoine constants† Applicable vL, liquid molar

temperature volume, cm3/
Species A B C region, °C g⋅mol
Acetic acid 8.02100 1936.010 258.451 18–118 57.54
Acetone 7.11714 1210.595 229.664 (−13)–55 74.05
Benzene 6.87987 1196.760 219.161 8–80 89.41
1-Butanol 7.36366 1305.198 173.427 89–126 91.97
Carbon tetrachloride 6.84083 1177.910 220.576 (−20)–77 97.09

Chloroform 6.95465 1170.966 226.232 (−10)–60 80.67

Ethanol 7.58670 1281.590 193.768 78–203 58.68
Ethanol 8.11220 1592.864 226.184 20–93 58.68
Ethyl acetate 7.10179 1244.951 217.881 16–76 98.49
Formic acid 6.94459 1295.260 218.000 36–108 37.91

n-Hexane 6.91058 1189.640 226.280 (−30)–170 131.61

Methanol 8.08097 1582.271 239.726 15–84 40.73
Methyl acetate 7.06524 1157.630 219.726 2–56 79.84
1-Propanol 8.37895 1788.020 227.438 (−15)–98 75.14
2-Propanol 8.87829 2010.320 252.636 (−26)–83 76.92

Tetrahydrofuran 6.99515 1202.290 226.254 23–100 81.55

Water 8.07131 1730.630 233.426 1–100 18.07
*Abstracted from Gmehling and Onken, Vapor-Liquid Equilibrium Data Collection, DECHEMA Chemistry Data ser., vol. 1 (parts 1–10), Frankfurt, 1977.
†Antoine equation is log Psat = A − B/(T + C) with Psat in torr and T in °C.
NOTE: To convert degrees Celsius to degrees Fahrenheit, °F = 1.8°C + 32. To convert cubic centimeters per gram-mole to cubic feet per pound-mole, multiply by
0.016.

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