Fluid Phase Equilibria, 65 (1991) 19-39 19

Elsevier Science Publishers B.V., Amsterdam

Correlation of binary liquid-liquid equilibrium data

over a wide temperature range using UNIQUAC
and extended UNIQUAC models

Isamu Nagata a, Thomas Meyer b and Jtirgen Gmehling b

a Department of Chemistry and Chemical Engineering, Division of Physical Sciences,
Fwa University, Kodatsuno 2-40-20, Kanarawa 920 (Japan)
Vniversitiit Oldenburg, Technische Chemie (FB9), Postfach 2503, D-2900 Oldenburg (Germany)
(Received October 3, 1990; accepted in final form January 24, 1991)

ABSTRACT

Nagata, I., Meyer, T. and Gmehling, J., 1991. Correlation of binary liquid-liquid equilibrium
data over a wide temperature range using UNIQUAC and extended UNIQUAC models.
Fluid Phase Equilibria, 65: 19-39.

The temperature effect on mutual solubility data for 81 binary systems has been studied
by means of UNIQUAC and extended UNIQUAC models. The energy parameters of the
models are expressed by a quadratic function of temperature. Among the systems studied 61
systems have an upper critical point, 14 systems have a closed partial miscibility and in six
systems the mutual solubihty increases with decreasing temperature. The extended UN-
IQUAC model shows significant improvement for some systems and therefore slightly better
results, on average, than the original UNIQUAC model.

INTRODUCTION

From theoretical and practical points of view it is very important to

obtain good representation of binary liquid-liquid equilibrium data over a
wide temperature range. A non-thermodynamic approach was developed to
express the two-phase equilibria in binary mixtures not only in the critical
region, but over the whole range of coexistence (Vnuk, 1983a,b). Models for
the excess Gibbs energy can be applied for this purpose using a temperature
dependence of the model parameters. A method was developed to calculate
the three binary closed-loop coexistence curves of liquid-liquid equilibria in
terms of lattice decoration and the UNIQUAC model (Kim and Kim, 1988).
The model reproduced fairly well temperature-composition diagrams, which
are asymmetric and closed in a loop or have lower consolute points. De

0378-3812/91/$03SO 0 1991 Elsevier Science Publishers B.V.

20

Pablo and Prausnitz (1990) have used a revised-scaling context, where

transformation to non-classical coordinates is asymmetric with respect to the
critical points for binary and ternary liquid mixtures whose properties are
represented by a conventional activity coefficient model. Detailed descrip-
tion on the present problem and pertinent references have been given
together with two figures to show the ability of local composition models for
the tetrahydrofuran-water and cyclohexane-methanol systems (Novak et
al., 1987).
In this paper we study the effect of temperature on binary liquid-liquid
equilibria for non-electrolyte solutions using the original UNIQUAC
(Abrams and Prausnitz, 1975) and the extended UNIQUAC models (Nagata,
1982).

SOLUTION MODELS

In this work two models for the excess Gibbs energy of non-electrolyte
solutions are used to represent the temperature dependence of the mutual
solubility. The activity coefficients of two components based on UNIQUAC
and extended UNIQUAC models are given below:
UNIQ UA C model
41% + 42x2721
lny,=l--Vi+lnV,- : q1 l--$+ln$ -4i ln
(Ii 1 1 i ( 41x1+ q2x2 i

721 712
+ q1q2x2 0)
i 41x1+ q2x2721 - %X1712 + q2x2 1

41X1?, + 42x2
In y2 = 1 - V, + In V, - 3 q2 l-:+1,2
0 i 2 2 1 - q2 In
i 41x1 + q2x2 i
712 721
+ q1qzx1
i 41x1712 + q2x2 - 41x1+ q2x2721 i
(2)
where the segment fraction per mole fraction V, the surface fraction per
mole fraction F and the binary parameter T are defined as
Vi = ri v2 = r2
‘1% + ‘2X2
(3)
r1x1+ r2x2

F, = ” F2 = q2
(4)
41x1 + 42x2 41x1+ q2x2

7 i2=exp -$ 721= exp - + (5)

( ) ( 1
Molecular structural parameters r and q depend on molecular size and
shape of each pure component.
 21

Extended UNIQ UAC model

41% + qzx2721
lny,=ln1/,+1-Vi- 3 q1 ln%+I-g - qi In
()( 1 1 i ( 41% + q2x2 i

+ qlq2x2 [ 4; ( 721 -1 1 A i 712 -1 11 (6)

ig 41x, + q&7*1 42 %X17-12 + q2x2

q2x2 + q1x1712
lny2=lnV2+1-V,- i q2 lng+l-: - q; In
0 i 2 2 i i 41% -t 42x2 i

+ q2qlxl [ 42
4; i
q2x2
-$XIT~, -1 1 -6
41
i
41% +
721
q2x2721
-1 11(7)
q’ is an interaction correction factor and is empirically assigned to each
component to get good agreement between calculated results and experi-
mental data. If q’ = q, the extended UNIQUAC model reduces to the
UNIQUAC model.
In order to fit the model parameters to experimental mutual solubility
data over a wide range of temperature, we have assumed that the energy
parameters are given by a quadratic function of temperature, because the
linear temperature dependence of the energy parameters did not yield
quantitative agreement with experimental data (Sorensen et al., 1979). The
quadratic temperature dependence of the energy parameters was found to
represent well the mutual solubilities for four systems (Malanowski et al.,
1981) and was used successfully in the simultaneous correlation of excess
Gibbs free energy and excess enthalpy data for 29 strongly non-ideal
mixtures (Nagata and Gmehling, 1991).
al2 = A,, + B,,T + C,,T2 (8)
a21 = A,, + B21T + C2,T2 (9)
Liquid-liquid equilibrium calculations were performed on the basis of the
equality of activities of components in the conjugated phases.

a;= (x,yJ=uf= (X,Yi)8 (10)

a; = (X2y2)a= al = (x2yz)B (11)

CALCULATION PROCEDURE

A general program has been developed for the evaluation of model

parameters from binary experimental liquid-liquid equilibrium data. Mod-
els for activity coefficients are included in form of subprograms and differ-
22

l-BUTANOL (1)
(4 WATER (2) (b) UNIQUAC
= A.. + BijT + CijT2
HILL (1926) aij 1J
600.
z
-4 400.
c?
a 200.
9
N 0.
CT

-200.

-400.
250. 300. 350. 400.

T (K)

Fig. 1. Calculated and experimental results for l-butanol/water; *, experimental; -

calculated with the UNIQUAC model. a, coexistence curve; b, temperature-dependence 0;
energy parameters.

ent types of temperature dependence of the parameters can be taken into

account.
Any type of experimental liquid-liquid equilibrium data can be taken.
For fitting temperature dependent parameters the miscibility gap should be
described well enough by the experimental data, but it is not necessary that
both phase compositions are known for a given temperature. In case of
many experimental data, the number of data is reduced to ten points over
the whole temperature range to keep the calculation time in reasonable
limits. The parameters are evaluated in three steps as shown schematically in
Fig. 1.
In the first part of the program, constant parameters ui2 and u2i are
calculated for each temperature. Missing concentrations on one or the other
side of the miscibility gap are estimated by linear interpolation. The simplex
algorithm modified by Nelder and Mead (1965) is used for this optimization.
The objective function to be minimized is the absolute sum of activity
differences for the two components:

s, = c 1Xi&Y; - &pYF 1< E i=l,2 02)

whereby Xi are the mole fractions in the two liquid phases (Yand p and yj
the corresponding activity coefficients. To obtain reliable results c had to be
set to c = lo-lo.
The result is a set of parameters for each given experimental temperature.
To this set of data the desired temperature dependence is fitted, for example
 23

aI2 = A,, + B,,T -t C12T2 and vice versa for u2i. This is done in the second
part of the program by least square minimization, again with the simplex
Nelder-Mead algorithm (see Fig. 1).
The parameters obtained are finally used in the last part as initial values
for the Marquardt method (1963). Now with all parameters, six parameters
in case of the mentioned example of quadratic temperature dependence, the
difference between experimental and calculated concentrations in the two
phases are minimized. Phase compositions are calculated iteratively with
given model parameters by application of a Newton-type algorithm on the
above mentioned isoactivity criterion:

(13)
The objective function used for the Marquardt algorithm is then the square
sum of the difference between experimental and calculated concentrations of
component 1 in the two phases:

S, = c (xLp - G&al)’ + c (d,exp - &,)* (14)

i j
The summation is carried out for all original experimental data. The above
estimated phase compositions are not used here. Throughout all calculations
the local derivatives needed for the ,Marquardt and Newton algorithms are
evaluated numerically.

SYSTEMS STUDIED

In this work, we studied 81 binary systems. I, 61 systems with an upper

critical solution temperature and mutual solubility increasing as system
temperature goes up; II, 14 systems with a closed curve of partial miscibility
and upper and lower critical solution temperatures; III, 6 systems where the
mutual solubility increases with decreasing temperature and a lower critical
solution temperature is observed.
All experimental data were collected from the literature (Sorensen and
Arlt, 1979; Spinolo, 1978; Vani et al., 1986; Macedo and Rasmussen, 1987)
are stored in the Dortmund Data Bank (DDB). Some experimental results
used in this work were measured 60-90 years ago.

CALCULATED RESULTS

Table 1 shows values of the molecular structural parameters r and q,

taken from the Dortmund Data Bank, and q’. q’ is an empirical constant
24

TABLE 1
Molecular structural parameters for pure components

Component r 4 4’
Acetic anhydride 2.0570 1.6500 q”.2
0.2
Acetone 2.5735 2.3360 4
Acetonitrile 1.8701 1.7240 1.2
Acetophenone 4.6941 3.6080 9o.2
Acrolein 2.3434 2.1240 9o.2
Benzaldehyde 4.0198 3.0800 9o.2
Benzene 3.1878 2.4000 9o.2
Benzylethylamine 5.8042 4.4440 9o.2
1,3-Butanediol 3.7560 3.3200 9o.2
1-Butanol 3.4543 3.0520 0.88
2-Butanol 3.4535 3.0480 1.0
2-Butanone 3.2479 2.8760 1.1
2-Butoxy-ethanol 5.0470 4.3720 1.1
Carbon disulfide 2.0570 1.6500 9o.2
Cyclohexane 4.0464 3.2400 9o.2
Cyclopentane 3.3720 2.7000 9o.2
Decane 7.1974 6.0160 go.2
1,2-Dicyanoethane 3.2868 2.8320 9o.2
Dimethoxymethane 2.9644 2.7160 go.2
2,6_Dimethylpyridine 4.4693 3.2490 9o.2
Dimethylsulfoxide 2.8266 2.4720 9o.2
Dipropylamine 5.0324 4.2520 2.0
Docosane 15.2902 12.4960 12.496
Ethanol 2.1055 1.9720 0.92
Ethylbutylamine 5.0324 4.2520 2.0
1-Ethyl-3-isopropyl-glycerol-ether 6.6381 5.6800 3.0
Formic acid 1.5280 1.5320 9o.2
Furfuraf 3.1680 2.4840 9o.2
Glutaronitrile 3.9612 3.3720 9o.2
Guaiacol 4.5306 3.4880 9o.2
Glycerol 3.5857 3.0600 9o.2
Heptane 5.1742 4.3960 9o.2
Hexadecane 11.2438 9.2560 9.2560
Hexane 4.4998 3.8560 9o.2
1-Hexanol 4.8031 4.1320 1.78
2-Isobutoxy-ethanol 5.0462 4.3680 9o.2
Methanol 1.4311 1.4320 1.0
2-Methoxy-ethanol 3.0238 2.7520 9o.2
m-Methylanilin 4.4515 3.3840 9o.2
o-Methylanilin 4.4515 3.3840 9o.2
3-Methyl-1-butanol 4.1279 3.5880 1.15
Methylcyclohexane 4.7200 3.7760 9o.2
Methylcyclopentane 4.0456 3.2360 9o.2
S-Methylfurfural 3.9030 3.0520 9o.2
Methylisopropyl ketone 3.9215 3.4120 9o.2
2-Methylpentane 4.4990 3.8520 9o.2
2-Methylphenol 4.2867 3.2480 9o.2
2-Methylpiperidine 4.5782 3.6320 1.2
 25

TABLE 1 (continued)

Component r 4 4’
3-Methylpiperidine 4.5782 3.6320 1.05
N-methylpiperidine 4.5585 3.6400 9o.2
2-Methyl-1-propanol 3.4535 3.0480 0.88
3-Methylpyridine 3.7343 2.6810 9o.2
N-methylpyrrolidone 3.9810 3.2000 9o.2
Nicotine 6.4898 4.6210 2.3
3-Nitrobenzylaldehyde 4.9083 3.7220 9o.2
Nitroethane 2.6829 2.4080 2.4080
Nitromethane 2.0086 1.8680 9o.z
Nonane 6.5230 5.4760 9o.2
Octane 5.8486 4.9360 go.*
Pentaerythritol perfluorobutyrate 20.6331 18.5600 9o.2
2,4-Pentanedione 4.0192 3.5160 9o.2
1-Pentanol 4.1287 3.5920 1.15
Phenol 3.5517 2.6800 9o.2
1,2-Propanediol 3.2824 2.7840 9o.2
Propionic aldehyde 2.5735 2.3360 9o.2
Propionitrile 2.5445 2.2640 9o.2
2-Propoxy-1-propanol 5.0462 4.3680 3.5
1-Propoxy-2-propanol 5.0462 4.3680 1.15
Salicylaldehyde 4.3836 3.3480 9o.2
Tetrahydrofuran 2.9415 2.7200 9o.2
Toluene 3.9228 2.9680 9o.2
Triethylamine 5.0118 4.2560 2.0
2,2,5_Trimethylhexane 6.5207 5.5480 9o.2
Water 0.9200 1.4000 1.0
p-Xylene 4.6578 3.5360 9o.2
2,2,4_Trimethylpentane 5.8463 5.0080 9o.2

for each component. Generally q’ = q”.2 is used for most of the components
but for several components specific values of q’ instead of q”.2 are used in
order to improve fitting the extended UNIQUAC model to experimental
results.
Table 2 indicates calculated results for 81 systems. Figures 2-4 compare
the calculated results from the extended UNIQUAC with the experimental
data for the selected systems. The coexistence curves with various degrees of
asymmetry can be satisfactorily described by the model. The highest devia-
tion is obtained for the triethylamine-water system. As shown in Fig. 4B,
the scattered experimental data mainly cause this high deviation. The total
average deviation between the calculated and experimental compositions is
3.17 mol% for the original UNIQUAC model and 2.65 mol% for the
extended UNIQUAC model. Better correlation of the energy parameters
TABLE 2
Calculated results for mutual solubility data

No. Type a System(l/2) Temp. Average absolute Parameters

range ( o C) deviation (molW)
UNI- Extended UNIQUAC Extended UNIQUAC
QUAC UNI- /, B 12 c 12 A 12 B,, Cl2
QUAC A12
21 B21 c,, &.
A,, _.
B,,
_-
G, -_

11 Acetone/ 9.5-95.7 1.25 1.41 310.650 - 0.1318 - 0.0005 33.832 5.3991 - 0.0109
glycerol - 627.015 4.9061 - 0.0077 - 1095.848 10.4531 -0.0171
21 Acetonitrile/ 24.8-144.0 0.13 0.13 882.030 - 4.2222 0.0050 762.514 - 3.1277 0.0034
hexadecane - 776.370 8.7554 - 0.0139 - 945 445 11.3106 -0.0179
31 Acrolein/ - 8.0-88.0 0.06 0.07 656.862 0.1752 - 0.0043 907.498 0.4498 - 0.0064
water - 591.003 3.4973 - 0.0042 - 1196.956 8.2754 - 0.0117
41 1,3-Butanediol/ 34.1-98.5 0.26 0.25 - 677.936 3.3160 -0.0040 - 4751.743 31.5743 - 0.0487
toluene 855.551 2.7891 - 0.0119 10236.553 43.7803 0.0476
51 1,3-Butanediol/ 36.8-l 14.5 0.01 0.03 1747.470 - 10.5204 0.0157 495.423 0.4842 - 0.0026
p-xylene - 2469.021 19.5432 - 0.0327 - 2901.197 29.4692 - 0.0534
61 1-Butanol/ - 18.0-124.8 0.39 0.11 914.950 - 4.7457 0.0051 - 308.358 4.0368 - 0.0081
water - 2445.374 15.7420 - 0.0215 - 6102.997 38.7838 -0.0534
71 2-Butanone/ - 11.4-142.6 3.93 6.24 925.098 - 2.5499 0.0017 1114.587 - 3.2399 0.0029
water - 951.871 5.1036 - 0.0062 - 3164.002 18.8964 - 0.0257
81 Carbon disulfide/
acetic 0.7-29.9 1.64 1.28 - 268.306 4.4466 - 0.0105 - 3201.901 29.4889 - 0.0586
anhydride - 4079.777 30.4301 - 0.0539 - 6920.392 53.4880 - 0.0969
91 Cyclohexane/ 3.4-76.6 0.04 0.02 - 1448.029 16.0100 -0.0303 1458.151 0.0225 - 0.0064
acetonitrile 647.115 - 3.4466 0.0047 - 1293.291 12.4450 - 0.0232
10 I Cyclopentane/
pentaerythritol 50.8-80.8 4.88 3.70 20076.945 - 115.6199 0.1659 77956.892 - 442.2833 0.6276
perfluorobutyrate -28817.928 168.8981 -0.2453 - 18799.565 114.2459 - 0.1695
11 I 1,2-Dicyanoethane/ 38.5-86.5 6.00 4.89 - 3693.098 22.3650 - 0.0336 - 5857.905 40.4514 - 0.0643
l-pentanol 8185.782 - 44.1089 0.0615 11371.830 - 57.3962 0.0763

._ .-_ _.._-_ _ _ _ _
12 I 1,2-Dicyanoethane/ 18.5-55.0 0.24 0.28 - 8841.637 62.3081 - 0.1073 - 8363.493 61.8210 -0.1096
water 5609.282 - 35.8473 0.0582 7113.074 - 43.5640 0.0686
13 I Dimethylsulfoxide/ 25.0-120.0 0.93 0.95 - 817.059 5.9904 - 0.0107 - 1562.573 11.979 - 0.0198
triethylamine - 1189.409 8.0798 - 0.0093 - 3080.606 21.366 - 0.0284
14 I Dimethoxymethane/ 43.0-160.3 6.20 3.29 - 1066.455 9.5186 - 0.0154 19.710 4.2119 - 0.0077
water 545.538 - 3.7292 0.0064 - 1420.722 7.8087 - 0.0092
15 I Ethanol/ 25.0-52.1 2.62 0.32 3913.166 - 25.5707 0.0413 150.013 -0.2903 0.0000
hexadecane - 12979.476 88.6825 -0.1466 - 112184.737 737.0385 - 1.1964
16 I Formic acid/ 3.8-73.4 0.13 0.11 497.839 - 2.1917 0.0033 182.376 2.1787 - 0.0048
benzene - 1855.331 15.8279 - 0.0279 - 2535.926 22.6594 - 0.0402
17 I Furfural/ 14.8-104.4 0.76 0.63 281.838 - 1.9422 0.0030 623.935 1.4007 - 0.0067
2,2,5_trimethylhexane 222.303 3.1597 - 0.0078 705.489 2.9324 - 0.0085
18 I Furfural/ 10.2-67.3 0.11 0.37 887.782 - 4.7796 0.0065 - 47.798 3.2691 - 0.0073
methylcyclopentane - 3120.436 22.4107 - 0.0364 - 5017.975 38.7373 - 0.0656
19 I Furfural/ 20.0-93.7 0.28 0.13 115.2183 - 0.6539 0.0008 - 92.849 5.0783 0.0116
heptane 22.9805 4.0073 - 0.0089 165.773 5.5870 -0.0118
20 I Furfural/ 16.3-66.3 0.10 0.08 1263.609 - 7.4689 0.0110 687.039 0.0197 - 0.0037
cyclohexane - 3106.073 23.4900 - 0.0394 - 4408.518 35.3618 - 0.0604
21 I Furfural/ 13.9-73.2 0.34 1.84 1590.675 - 9.9864 0.0157 2233.464 - 11.4051 0.0169
methylcyclohexane - 1441.512 13.4918 -0.0246 - 766.157 16.2386 -0.0358
22 I Furfural/ 27.9-120.8 0.47 0.64 498.859 1.9392 - 0.0094 693.836 0.8797 - 0.0074
water 501.654 - 5.2600 0.0124 - 459.142 2.6020 - 0.0012
23 I Furfural/ 25.6-126.9 5.05 5.56 1274.886 - 6.9322 0.0090 1006.111 - 5.0207 0.0063
hexadacane - 1562.976 11.9487 - 0.0179 - 1844.182 14.9489 - 0.0228
24 I Furfural/ 43.2-144.3 0.48 0.29 - 537.864 3.4738 - 0.0057 66.963 0.7264 - 0.0020
docosane 2712.593 - 12.3080 0.0161 4779.680 - 21.9046 0.0288
25 I Glutaronitrile/ 5.6-68.3 1.88 1.96 - 1056.659 8.3428 - 0.0140 - 5249.082 39.3689 - 0.0689
water 2378.847 - 12.6633 0.0167 8865.690 - 52.9561 0.0799
26 I Glycerol/ 90.5-185.5 1.88 1.65 209.263 0.3572 - 0.0010 -401.195 8.5959 - 0.0141
acetophenone - 438.868 4.5260 - 0.0072 - 786.690 12.0489 - 0.0198
TABLE 2 (continued) g

No. Type ’ System(l/Z) Temp. Average absolute Parameters

range ( o C) deviation (mol%)
UNI- Extended UNIQUAC Extended UNIQUAC
QUAC UNI- /,
B 12 C,, A 12 B 12 Cl2
QUAC _,ft B21 c21 c2,
A21 B 21
27 I Glycerol/ 37.5-164.5 1.26 1.14 - 1648.623 10.9014 - 0.0158 - 2581.222 18.9442 - 0.2733
2-butanone 1052.458 - 5.1337 0.0075 235.518 2.0727 - 0.2643
28 I Glycerol/ 67.5-160.7 3.16 3.44 - 1430.851 8.4516 -0.0112 - 909.638 10.3490 - 0.0165
benzaldehyde 3809.697 - 16.3002 -0.0182 7005.221 - 27.3776 0.0286
29 I Glycerol/ 18.0-136.0 0.15 0.21 - 9.831 1.0017 -0.0005 - 165.903 5.5561 - 0.0094
1-hexanol - 437.211 3.6525 - 0.0066 - 473.020 5.7486 - 0.0101
30 I Glycerol/
f-methyl- 12.5-74.2 3.25 2.51 - 802.746 6.7744 - 0.0110 - 1853.707 22.6885 - 0.0447
I-butanol 344.907 - 1.1684 0.0007 - 485.884 6.7610 - 0.0125
31 I Glycerol/ 99.2-154.4 4.41 3.72 - 6969.684 35.9583 - 0.0456 - 11334.227 61.2756 - 0.0791
o-methylanilin 5398.845 - 25.2134 0.0307 3190.158 - 10.5631 0.0103
32 I Glycerol/ 91.5-176.6 3.91 3.76 3332.217 - 15.5129 0.0188 3851.505 - 13.8634 0.0143
sahcylaldehyde - 3498.969 19.9540 - 0.0264 - 3814.868 26.2340 - 0.0370
33 I Methanol/
carbon - 100.3-34.5 1.67 0.34 898.648 - 6.1495 0.0116 643.346 - 1.3392 0.0011
disulfide - 3926.115 41.7140 -0.0898 - 6349.806 69.0673 - 0.1490
34 I Methanol/ 29.2-45.1 0.18 0.31 1025.967 - 5.9504 0.0085 - 3826.197 28.8756 - 0.0501
cyclohexane - 15668.007 109.1543 -0.1829 - 27466.335 191.2676 -0.3192
35 I Methanol/ 18.0-50.0 0.02 0.03 169.299 - 0.8516 0.0010 - 1025.408 10.2178 -0.0181
heptane - 1246.057 16.2683 - 0.0330 -2116.153 27.8990 - 0.0541
36 I Methanol/ 24.8-139.8 4.51 1.59 108.240 - 0.3274 0.0002 23.412 0.7463 -0.0015
hexadecane 2173.481 - 5.3052 0.0032 3174.373 - 7.4104 0.0046
37 I 2-Methoxy-
ethanol/ 25.5-105.0 1.12 0.75 949.459 - 6.0902 0.0095 374.353 - 1.5236 0.0018
hexadecane - 849.099 9.9256 - 0.0188 - 1059.382 15.2945 - 0.0302
38 I 5-Methyl-
furfural/ - 5.5-160.3 0.09 0.08 120.672 2.7215 - 0.0083 - 73.696 4.5144 - 0.0108
water - 181.590 - 0.1587 0.0036 - 1412.824 8.0182 - 0.0082
39 I N-methyl-
pyrrolidone/ 24.9-93.8 1.16 0.57 - 3161.254 19.0984 - 0.0292 - 1269.244 8.3801 - 0.0132
hexadecane 6293.406 - 35.0924 0.0512 10852.063 - 59.6378 0.0861
40 I Methylisopropylketone/ - 8.0-180.0 2.41 2.38 1627.490 - 4.6995 0.0019 1026.444 0.6886 - 0.0062
water - 2173.245 11.2401 -0.0123 - 3244.379 17.2887 - 0.0193
41 I 2-Methyl- 25.0-162.8 0.11 0.13 - 1216.666 7.2874 - 0.0125 - 1493.509 9.4482 - 0.0150
phenol/water 1699.721 - 9.0355 0.0156 1977.718 - 9.5471 0.0145
42 I 2-Methyl-
I-propanol/ - 14.7-132.9 0.25 0.15 1153.801 - 4.8778 0.0043 - 73.099 3.0303 - 0.0067
water - 1535.559 8.8272 - 0.0102 - 3907.934 25.4452 - 0.0343
43 I 3_Nitrobenzaldehyde/ 40.5-211.8 2.62 1.02 - 1466.780 13.2806 - 0.0225 1560.440 3.9801 - 0.0160
water 7765.908 - 37.7926 0.0468 10745.234 - 57.3262 0.0757
441 Nitromethane/ 23.5-133.0 0.21 0.15 - 736.566 4.5849 - 0.0066 - 1808.879 14.0847 - 0.0214
glycerol 3025.998 - 9.5759 0.0079 3938.050 - 11.1683 0.0085
45 I Nitromethane/ 22.9-120.6 0.09 0.23 297.799 -0.8900 0.0004 499.650 4.8217 - 0.0132
nonane 269.700 3.4800 - 0.0081 497.386 6.6623 - 0.0155
461 Nitromethane/ 34.0-114.5 0.54 0.35 1531.635 - 7.6532 0.0097 4358.153 - 17.3090 0.0186
octane 154.811 4.3492 - 0.0097 1657.960 0.1825 - 0.0846
47 I Nitromethane/ 16.4-108.3 6.41 4.33 - 1186.215 8.0767 - 0.0130 - 1802.375 17.0911 - 0.0301
heptane 9004.269 - 46.7272 0.0634 12756.075 - 63.7872 0.0846
48 I Nitromethane/ 11.0-93.7 0.76 1.11 2464.063 - 14.1615 0.0208 1255.832 - 1.6656 - 0.0022
cyclohexane - 1938.718 19.2070 - 0.0356 503.306 9.5015 - 0.0251
49 I Nitromethane/
carbon 18.5-63.5 4.29 3.85 2038.868 - 12.1955 0.0208 - 1111.059 10.9014 - 0.0177
disulfide - 6325.370 46.3795 - 0.0804 - 10221.742 78.1112 -0.1380
50 I Nitroethane/ 2.9-29.3 0.11 1.37 1421.935 - 2.6598 - 0.0010 - 9182.357 67.7505 - 0.1241
water - 70.552 1.1730 -0.0011 4533.651 -27.9512 0.0460
51 I Nitroethane/ - 0.4-26.7 0.44 0.36 - 1098.432 7.1673 - 0.0117 - 3284.321 21.9600 - 0.0366
2-methylpentane - 653.765 11.0285 - 0.0266 - 448.936 9.2983 - 0.0231
TABLE 2 (continued)

No. Type a System(l/2) Temp. Average absolute Parameters

range ( o C) deviation (mol’%)
UNI- Extended UNIQUAC Extended UNIQUAC
QUAC UNI- A B 12 C A 12 B C
QUAC AZ B 21 d: A21 4: 4:

52 I Nitroethane/ 4.2-41.3 0.03 0.08 - 2702.704 19.1093 - 0.0339 - 11178.052 79.0060 - 0.1400
octane 4417.681 - 26.5919 0.0432 7073.671 - 45.2007 0.0758
53 I Nitroethane/ 1.8-29.5 1.17 0.97 755.666 - 5.3251 0.0091 2588.016 - 18.1585 0.0309
2,2,4_trimethypentane - 3834.162 31.3532 -0.0587 - 3847.625 31.3920 -0.0586
54 I Nitroethane/ 2.3-52.6 0.12 0.43 441.549 - 2.3041 0.0026 244.374 3.9272 -0.0158
decane - 182.659 4.8958 - 0.0105 851.189 - 3.0964 0.0045
55 I Nitroethane/ 2.9-29.3 0.13 0.14 - 2997.879 22.1848 - 0.0407 - 9182.357 67.7505 - 0.1241
hexane 3697.603 - 22.2453 0.0363 4533.651 - 27.9512 0.0460
56 I 2,4-Pentanedione/ 21.7-82.3 0.37 0.20 - 9447.203 64.0175 - 0.1030 - 11771.548 80.8185 -0.1311
water 3708.518 - 23.1917 0.0357 6196.666 - 37.3129 0.0562
57 I Phenol/ 19.7-48.4 1.30 0.78 12767.462 - 84.4709 0.1392 20024.002 - 129.3223 0.2106
octane - 19193.772 130.4088 -0.2179 - 21492.913 149.2408 - 0.2520
58 I Phenol/ 1.3-65.0 0.13 0.13 368.486 - 2.6341 0.0016 62.913 0.0824 - 0.0030
water - 2549.370 18.0831 - 0.0256 - 3937.780 27.5391 - 0.0397
59 I 1,2-Propanediol/ 32.1-107.1 0.00 0.00 1044.066 - 6.6673 0.0107 - 169.147 4.0871 - 0.0072
toluene 244.946 5.4413 -0.0143 1745.969 3.2403 - 0.0167
60 I 1,2-Propanediol/ 20.0-79.8 0.35 0.15 9491.540 - 58.5959 0.0901 3863.346 - 20.6219 0.0299
benzene - 25932.333 165.9041 -0.2597 - 41481.239 267.8231 -0.4213
61 I Propionitrile/ 4.5-113.2 0.16 0.14 1238.906 - 3.5354 0.0011 1640.287 - 4.2190 0.0009
water - 553.422 3.4077 - 0.0036 - 928.313 7.1379 - 0.0099
62 II 2-ButanoI/ - 16.5-113.7 9.83 10.09 514.152 - 2.4120 0.0019 - 1698.092 11.6495 -0.0189
water - 2492.030 14.9396 - 0.0195 - 1483.266 8.0298 - 0.0056
63 II 2-Butoxyethanol/ 49.1-128.0 1.10 0.22 185.289 - 3.1616 0.0058 -4957.200 27.5848 - 0.0385
water - 1661.299 13.2820 - 0.0209 2747.737 - 13.4031 0.0221
64 II 2,6_Dimethylpyridine/ 45.3-164.9 1.13 1.36 - 2609.723 13.0094 -0.0185 - 3198.395 16.3345 - 0.0225
water 5010.975 - 25.1167 0.0353 7885.543 - 39.3786 0.0534
65 II Glycerol/ 6.7-120.5 6.54 6.38 - 3064.338 19.0071 - 0.0280 - 6205.348 39.2171 - 0.0571
m-methylaniline 1042.653 - 5.9834 0.0097 - 1546.279 10.3835 - 0.0132
66 II Glycerol/ 39.5-83.5 4.01 4.36 - 10450.073 62.8255 - 0.0934 - 17623.196 106.915 - 0.1582
guaiacol 7069.381 - 41.8394 0.0630 2455.265 - 13.538 0.0220
67 II Glycerol/ 50.0-281.0 34.30 22.71 410.792 - 0.4631 - 0.0003 - 2036.985 11.8623 - 0.0126
benzylethylamine - 1324.537 5.6620 - 0.0050 - 4227.543 21.6162 - 0.0231
68 II 2-Isobutoxyethanol/ 24.6-150.2 0.15 0.10 - 4947.929 27.5768 - 0.0390 - 5253.863 29.7938 - 0.0416
water 5882.995 - 32.2591 0.0463 5810.647 31.2949 0.0458
69 II 2_Methylpiperidine/ 79.3-227.0 22.18 23.29 - 6992.940 31.8547 - 0.0376 - 6795.150 31.4864 - 0.0367
water 13167.218 - 59.0614 0.0689 19462.904 - 87.3078 0.1010
70 II 3_Methylpiperidine/ 56.9-235.0 5.77 1.37 - 3113.930 13.0387 -0.0147 - 2271.496 9.8072 - 0.0105
water 3977.556 - 14.2107 0.0144 2335.319 - 4.1682 - 0.0000
71 II 3-Methylpyridine/ 49.4-152.5 2.04 1.84 - 1851.892 8.7568 - 0.0129 - 2246.941 11.2720 - 0.0163
water 3505.934 - 16.0606 0.0230 6533.775 - 32.9536 0.0482
72 II Nicotine/ 61.5-233.0 0.47 0.32 1158.408 - 7.6438 0.0103 - 1089.493 3.4783 - 0.0035
water - 5369.508 - 29.2141 - 0.0373 - 6032.971 34.5386 - 0.0446
73 II 2-Propoxy-
I-propanol/ 42.8-162.0 0.55 0.46 - 7107.046 38.2764 - 0.0516 - 8591.858 46.3394 - 0.0623
water 7482.227 - 39.7605 0.0542 7982.579 - 42.3618 0.0578
74 II 1-Propoxy-
2-propanol/ 34.5-171.0 0.99 1.34 - 5892.471 31.7822 - 0.0429 - 5908.745 32.5685 - 0.0435
water 5840.240 - 30.8944 0.0424 5400.387 - 28.6652 0.0407
75 II Tetrahydrofuran,’ 71.8-137.1 2.31 0.50 - 8186.185 45.0604 -0.0613 - 5109.747 29.4071 - 0.0405
water 4604.761 - 25.2887 0.0361 - 4223.928 21.4889 - 0.0245
76 III Dipropylamine/ - 4.8-74.8 1.33 0.46 - 3254.218 16.6071 - 0.0194 - 2485.433 10.8245 - 0.0079
water 6282.381 - 37.8590 0.0589 7525.696 46.8982 0.0771
77 III Ethylbutylamine,’ 10.0-40.0 0.88 1.02 4157.627 - 34.5690 0.0669 3906.890 - 34.1662 0.0694
water - 3541.238 33.2541 - 0.0665 - 2465.967 29.4541 - 0.0644
78 III 1-Ethyl-3-isopropyl-
glycerolether/ 34.1-78.40 0.38 0.37 - 30960.804 188.7339 - 0.2852 - 42305.948 257.9845 - 0.3903
water 11807.560 - 72.8259 0.1119 16974.528 - 105.0433 0.1623
TABLE 2 (continued)

No. Type a System(l/Z) Temp. Average absolute Parameters

range ( o C) deviation (mol%)
UNI- Extended UNIQUAC Extended UNIQUAC
QUAC UNI-
A 12 42 ‘42 42 B 12 Cl2
QUAC
A 21 B21 c2, A 21 B 21 c2,

79 III N-methylpiperidine/ 48.3-236.0 15.39 3.79 - 2796.010 9.8609 - 0.0067 - 3670.010 15.3258 -0.0141
water 3659.910 - 13.4099 0.0119 4040.300 - 13.9049 0.0121
80 III Propionic
aldehyde/ 15.0-40.0 0.19 0.29 10376.891 - 65.1587 0.1062 23467.425 - 150.2877 0.2464
water - 3671.579 22.0674 - 0.0328 - 5005.530 29.6698 - 0.0424
81 III Triethylamine/ 18.7-69.2 60.30 60.96 - 120777.221 738.6394 - 1.1147 - 159598.559 947.2883 - 1.4656
water 34896.508 - 218.7337 0.3425 32634.806 - 207.5131 0.3311

Total average deviation 3.17 2.65

a I: system has an upper critical solution temperature; II: system has a closed curve of partial miscibility; III: mutual solubility increases
with decreasing temperature.
 33

2-METHOXY-ETHANOL (1)
(4 HEXADECANE (2)
R
120

s 100

e
k 80.

60.

40.

20.

0.
I I I I
0 25. 50 75. 100

Xl is,)

CYCLOHEXANE (1) 5-METHYLFURFURAL (1)

04 ACETONITRILE (2)
(c)
WATER (2)

0 25 50 75 100 0 25 50 75 100

x1 @) Xl (%

Fig. 2. Calculated coexistence curves for systems having an upper critical solution tempera-
ture: l , experimental; -, calculated by the extended UNIQUAC model. a, 2-methoxy-
ethanol-hexadecane; b, cyclohexane-acetonitrile; c, Smethylfurfural-water.

against temperature variation may yield improved representation of the

mutual solubility data of the systems, whose temperature interval of coexis-
tence is more than 100 K.
The physical significance of the energy parameters obtained here are
further corroborated by comparing the estimated and experimental activity
coefficients and excess enthalpies in miscible and infinitely diluted regions
for the four selected systems 1-butanol-water, ethanol-hexadecane, fur-
fural-cyclohexane and methanol-cyclohexane as shown in Figs. 5-8. The
experimental values of the systems were taken from DECHEMA Chemistry
Data Series Books (Christensen et al., 1984; Gmehling et al., 1981, 1988,
1989; Tiegs et al., 1986 and French et al. (1979)).
34

(4 NICOTINE (1)
(b) 2-PR3POXY-i -PROPQTIL ()
WATER (2) WATER (2)

250

120

100

80

60

40
3 25 5c

x1 (XI

GLYCEROL (1) TETRAHYDROFURAN (1)

(4 (d)
M-METHYLANILIN (2) WATER (2)

140. 140

120 130
G 3
; 100 p;- 120

80 110

60 100

40 90

20 80

0 70
0 25 50 75 100 25 5;

x1 (%) ‘1 (%)

Fig. 3. Calculated coexistence curves for systems having a closed curve of partial miscibility:
* , experimental; - calculated by the extended UNIQUAC model. a, nicotine-water; b,
Zpropoxy-l-propanol-dater; c, glycerol-m-methylaniline; d, Tetrahydrofuran-water.

For the l-butanol-water system the extended UNIQUAC model provides

the calculated activity coefficients much closer to the experimental values of
Lyzlova et al. (1979) at 35 o C. Both models give considerably higher values
of excess enthalpy than the experimental results of Goodwin and Newsham
(1971) at 30” C.
In the ethanol-hexadecane system the experimental activity coefficients
and excess enthalpies were directly taken from French et al. (1979). The
calculated activity coefficients obtained from the extended UNIQUAC
model are in good agreement with the experimental results at 25°C. The
estimated excess enthalpies also agree reasonably with the experimental
values at 35°C. On the contrary, the original UNIQUAC model gives
 35

DIPROPYIAMINE (1) TRIETHYLAMINE (1)

(4 lb)
WATER (2) WATER (2)

70

60
G 60 3
e
; 50.
+
40
40.

30
20

20.
0
10.

-20 0.
0 25. 50 75 100 0 25. 50 75 100

x1 m x1 (C

Fig. 4. Calculated coexistence curves for systems, where mutual solubility increases with
decreasing temperature: * , experimental; - , calculated by the extended UNIQUAC
model. a, dipropylamine-water; b, triethylamine-water.

calculated results which deviated greatly from the experimental values of

activity coefficient and excess enthalpy.
For the furfural(l)-cyclohexane(2) system the values of limiting activity
coefficients calculated from the extended UNIQUAC model agree well with
the reported values of ylw at 64.4”C (Thomas et al., 1982) and y? at 30”

Mole fraction of ethanol

Mole fraction of ethanol

Fig. 5. Calculated activity coefficients and excess enthalpies for l-butanol-water: -,

calculated with the extended UNIQUAC model; - - - - - -, calculated with the UNIQUAC
model. Experimental, A, activity coefficient, o, data of Lyzlova et al. (1979) at 35OC; B,
excess enthalpy, o, data of Goodwin and Newsham (1971) at 30 o C.
36

5 1200
A B
/’ \
1 \
1000 -

4
b 800

3 500
L

2
0
0

/ -

1: “. -Y-Y---o
--___ 0 n n?
02 04 06 08
0 0 I *5 0.6 0.7 08 09 I

Mole froctlon of I-butanol Mole fraction of I-butonol

Fig. 6. Calculated activity coefficients and excess enthalpies for ethanol-hexadecane: -

calculated with the extended UNIQUAC model; - - - - - -, calculated with the UNIQUAd
model. Experimental, A, activity coefficient, o, data of French et al. (1979) at 25OC; B,
excess enthalpy, o, data of French et al. (1979) at 35°C.

and 64.4” C (Santacesaria et al., 1979). The two models give estimated values
of excess enthalpy in reasonable agreement with the experimental values of
Battler and Rowley (1985) at 25°C.
In the methanol-cyclohexane system the experimental activity coef-
ficients at 40 ’ C were obtained from P-x data of Goral et al. (1983) using a

2000
t3

0 01 02 06 07 08 09 I 0 02 04 0.6 08

Mole fraction of furfural Mole fraction of furfural

Fig. 7. Calculated activity coefficients and excess enthalpies for furfural(l)-cyclohexane(2):

, calculated with the extended UNIQUAC model; - -----, calculated with the
UNIQUAC model. Experimental, A, activity coefficient, o, yp” of Thomas et al (1982) at
64.4O C, A, yp of Santacesaria et al. (1979) at 30 o and 64.4O C; B, excess enthalpy, o, data of
Battler and Rowley (1985) at 25°C.
 37

r !/
5
A

_____---- -\ \
__---
1250 - ,__--- \
4 \
,

: \
2 I
I
c -,lOOO- ; L
I
3
I
i
5
\
2

0 0.2 0 3 0.7 0.8 0.9 I

Molefraction of methanol Mole fraction of methanol

Fig. 8. Calculated activity coefficients and excess enthalpies for methanol-cyclohexane:

-, calculated with the extended UNIQUAC model; - - - - - -, calculated with the
UNIQUAC model. Experimental, A, activity coefficient, o, data of Goral et al. (1983); A, yim
of Lobien and Prausnitz (1982) at 40’ C; B, excess enthalpy, o, data of Dai and Chao (1985)
at 3O’C.

Legendre polynomial of degree 5 (Fredenslund et al., 1977). The values of

limiting activity coefficients were interpolated from those of Lobien and
Prausnitz (1982). The calculated activity coefficients based on the extended
UNIQUAC model are in excellent agreement with the experimental values
and the calculated excess enthalpies also are in substantial agreement with
the experimental data of Dai and Chao (1985) at 30°C. Again, the original
UNIQUAC model gives less satisfactory results.
We may conclude that the adjusted q’ in the extended UNIQUAC model
shows much better results in some cases and on average a slightly improved
performance compared with the original UNIQUAC model for the descrip-
tion of temperature dependence of mutual solubilities. Moreover, the predic-
ted results of activity coefficients and excess enthalpies in miscible regions
confirm the superiority of the extended UNIQUAC model over the original
UNIQUAC model.

ACKNOWLEDGEMENTS

I. Nagata is grateful to the Deutscher Akademischer Austauschdienst

(DAAD) for its financial support. Furthermore the support of the Deutsche
Forschungsgemeinschaft (DFG) and the Bundesministerium fur Forschung
und Technologie (BMFT) is gratefully acknowledged. K. Miyamoto helped
with the computational work.
38

LIST OF SYMBOLS

aij binary interaction energy parameter related to rij

Ai;> B;;, Cij coefficients related to aij
r;l area fraction per mole fraction for component i
4i
molecular area parameter for pure component i
41 molecular interaction factor for pure component i
5 molecular size parameter for pure component i
R universal gas constant
s,, $7 s, objective functions for calculation procedure
T absolute temperature
vl segment fraction per mole fraction of component i
X, liquid phase mole fraction of component i
Z lattice coordination number, here equal to 10

Greek letters

Yi activity coefficient of component i

VP" activity coefficient of component i at infinite dilution
ff? P liquid phases
‘ij binary parameter as defined by exp( - aij/T)

Subscripts

talc calculated
exp experimental
4-i components

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