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ELSEVIER FluidPhaseEquilibria109 (1995)83-98

Isothermal vapor-liquid equilibria for mixtures of ethanol, acetone,


and diisopropyl ether
M.-J. Lee *, C.-H. Hu
Department of Chemical Engineering, National Taiwan Institute of Technology, Taipei, 106, Taiwan
Received20 October 1994; accepted31 January 1995

Abstract

A static apparatus was installed for measuringisothermalvapor-liquid equilibrium(VLE) data for the binary and ternary
mixtures composed of ethanol, acetone, and diisopropyl ether in a temperature range of 343-363 K. Maximum pressure
azeotropes appeared in the binary systems containing diisopropyl ether. All the binary data passed the point, area, and
infinite dilution thermodynamicconsistency tests. Furthermore,the Wilson, NRTL and UNIQUAC models correlated the
binary data well. The UNIQUAC model yielded the best prediction for the ternary system.

Keywords: Experiments;Data; Excess functions;VLE low pressure; Polar; Azeotropes

1. I n t r o d u c t i o n

Vapor-liquid equilibrium data are fundamentally important for separation process design. A static
apparatus was installed in the present study to measure isothermal VLE data. This article reports the
experimental results of the binary and ternary mixtures containing ethanol, acetone, and diisopropyl
ether at 343-363 K over the entire composition range. Of these investigated systems, several isobaric
(1.013 bar) and isothermal (288-328 K) VLE data for acetone/ethanol are available in the
DECHEMA collection (Gmehling et al., 1982). Campbell et al. (1987) also reported the isothermal
data of acetone/ethanol system at 372-422 K. Additionally, Horsley (1973) tabulated the azeotropic
temperature and composition for both ethanol/diisopropyl ether and acetone/diisopropyl ether at
atmospheric pressure. Each set of isothermal binary data obtained in this work is examined by
thermodynamic consistency test and correlated by the Wilson (Wilson, 1964), NRTL (Renon and
Prausnitz, 1968), and UNIQUAC (Abrams and Prausnitz, 1975) models, respectively. By using the
determined binary parameters, these models are employed to predict the bubble points of
acetone/ethanol/diisopropyl ether system.

* Corresponding author.

0378-3812/95/$09.50 © 1995 ElsevierScienceB.V. All rightsreserved


SSDI 0378-3812(95)02705-X
84 M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

2. Experimental section
Fig. 1 illustrates the schematic diagram of the static VLE apparatus. The round-bottom bottle (1)
serves as a degassing unit which connects to the circulation pump (2) and the equilibrium cell (3). The
cell (approximately 60 cm 3) is placed in a thermostated bath (Model HT-250, Neslab, USA,
stability = + 0.03 K) (4) and the bath temperature is measured by a Microtherm (Model-1506, Hart
Scientific, USA) with a platinum RTD probe (5) accurate to 0.02 K. A pressure transducer (Model
PDCR-330, 0-500 kPa, Druck, UK) with a digital indicator (Model DPI 262, Druck, UK) (6)
measures the equilibrium pressure accurate to _ 1%.
In the liquid circulating loop, a four-port liquid-sampling valve (Model 7410, Rheodyne, USA)
with a 1 /.d loop disc (7) is used for trapping the liquid sample and a preheater (8) is utilized to reheat
the returned liquid. The circulated liquid bypasses the sampling valve when no liquid sample is taken.
The vapor sample is trapped by a six-port vapor-sampling valve (Model 7010, Rheodyne, USA) with
a 10 /.d sample loop (9), which is connected to an opening on the top of the cell.
Vapor and liquid samples are analyzed by a thermal conductivity detector (TCD) gas chromatogra-
phy (Model-8700, China Chromatography Co., Taiwan) with a stainless steel column (10% Carbowax
on Chromosorb W-HP 80/100, 20m X 1/8") and using helium (99.99% purity) as a carrier gas.
Calibrations are made with gravimetrically prepared samples over the entire composition range for
each binary system. The responses are reproduced within __+1%.
The equilibrium system is evacuated before starting a new measurement. A prepared solution is
sucked into the degassing bottle through V1 (10). Some dissolved gases liberate from the solution and
to be confined over the liquid surface. A heat-gun heats the degassing unit to enhance liberation of the

to GC (
12
to vac.(

1~ ...)to vac.

to vat.~ ~ I~

1 degassing unit 8 preheater


2 circulation pump 9 vapor sampling valve
3 equilibrium cell 10 valve (V1)
4 thermostated bath 11 valve (V2)
5 thermometer 12 valve (V3)
6 pressure transducer 13 valve (V4)
7 liquid sampling valve
Fig. 1. Schematicdiagram of the new VLE apparatus.
M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98 85

Table 1
Properties of pure substances a
compound Tc Pc Vc tO t~ ZRA Vpa b Vp b Vpc l/pd
K kPa cm 3 mol "1 Debye

cyclohexane 553.5 4070 308.0 0.212 0.3 0.2729 -6.96009 1.31328 -2.75683 -2.45491
benzene 562.2 4890 259.0 0.212 0.0 0.2696 -6.98273 1.33213 -2.62863 -3.33399
ethanol 513.9 6140 167.1 0.644 1.7 0.2520 -8.51838 0.34163 -5.73683 8.32581
acetone 508.1 4700 209.0 0.304 2.9 0.2470 - 7.45514 1.20200 -2.43926 - 3.35590
diisopropylether 500.3 2880 386.0 0.331 1.2 0.2615 c -7.62613 1.29308 -2.90101 -6.14467

a Taken from Reid et al. (1987); b l n ( p S / P c ) = ( 1 - O ) - I (VPa+VP b ol5--I-Vec 03--]-Ved 0 6 ) with O = I - ( T / T c ) ;


c Estimated from ZRA = 0.29056 -- 0.08775 tO.

dissolved gases and elevate the pressure difference between degassing unit and equilibrium cell. The
degassed solution is charged into the equilibrium cell through V1, V2 (11), and V3 (12). The charging
process is ended before the liquid level in the degassing bottle lower than the bottom of feeding tube
to prevent the non-condensable gases from intruding into the equilibrium system. Subsequently, close
V1 and circulate the liquid-phase mixture by the liquid-pump (2) to promote equilibration. While
system attains to the equilibrium state, pressure reading approaches a constant. Then, take the liquid
and vapor samples from the sampling valves, respectively, and analyze the equilibrium phase
compositions by the gas chromatography. It is notice that V4 (13) should be opened slowly enough to
avoid interrupting the equilibration during taking the vapor samples. Four to five samples are
replicated. The averaged area fraction converts into mole fraction via the calibration correlation.
Diisopropyl ether (99 + %), benzene (99 + %), and ethanol (99.8%) were supplied by Ferak,
Germany. Cyclohexane (99 + %) and acetone (99 + %) were purchased from Aldrich, USA. No
impurity peak was detected by the chromatographic analysis. Those chemicals were used without
further purification. Table 1 lists the properties of these substances (Reid et al., 1987).

3. Experimental results
The literature VLE data of cyclohexane/benzene at 343.13 K (Gmehling et al., 1980), which have
been passed the thermodynamic consistency test by Kojima et al. (1990), were used here for checking
the validity of the new VLE apparatus. Table 2 Table 3 compares the measured values of this work
with those of the literature. The agreement is satisfactory for phase compositions as shown in Fig. 2
and the differences of equilibrium pressures are within + 1 kPa. These new data also passed the point,
area, and infinite dilution consistency tests.
The new apparatus is subsequently employed to determine the isothermal VLE data of ethanol/di-
isopropyl ether, acetone/diisopropyl ether, and acetone/ethanol at 343 K, 353 K, and 363 K. The
results are reported in Table 4 Table 5Table 6, where the entries of the activity coefficient (Yi) are
calculated from the following equation:

yi =
xi PiS~b~exp
[(p_p?)viL
YieJPi

(RT) ] (1)

The experimental T, P, xi, and Yi are introduced in Eq. (1), while the vapor pressure is calculated
from the Wagner equation as given in Table 1. Meanwhile, the modified Rackett model (Spencer and
86 M.d. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

Table 2
Comparison of VLE data from this work with those from the literature for cyclohexane(1)/benzene(2) at 343.13 K
This work literature a difference b
P kPa xI Yl P kPa x1 Yl ziP kPa Ax x ziYa
76.0 0.1189 0.1491 75.7 0.1186 0.1486 0.3 0.0003 0.0005
78.4 0.2421 0.2812 78.0 0.2409 0.2805 0.4 0.0012 0.0007
80.3 0.3764 0.3959 79.5 0.3759 0.3982 0.8 -0.0005 -0.0023
80.7 0.4933 0.4990 80.0 0.4945 0.4975 0.7 -0.0012 0.0015
79.6 0.6191 0.6062 79.9 0.6180 0.6027 - 0.3 0.0011 0.0035
79.5 0.7235 0.6951 79.1 0.7248 0.6962 0.4 -0.0013 -0.0011
77.9 0.8664 0.8319 77.0 0.8659 0.8311 0.9 0.0005 0.0008

Table 3
Thermodynamic consistency tests c
This work literature
6 A Ia 12 6 A Ix 12
2.2 ( + ) d 0.4(+) 20.8(+) 10.1(+) 1.5(+) 0.6(+) 12.5(+) 9.3(+)

a Gmehling et al. (1980); b A P = pexp _ plit, Ax I = x~xP _ x[it, Ay I = y~xp_ y[it; c see Appendix A; d ( + ) : passes the
thermodynamic consistency test.

D a n n e r , 1972) is u s e d for e s t i m a t i n g the l i q u i d m o l a r v o l u m e (Vi L) a n d the t w o - t e r m virial e q u a t i o n


for c a l c u l a t i n g the f u g a c i t y c o e f f i c i e n t s (~b~ a n d tki), i.e.,

In ¢~i = " ~ YiBij -- B m (2)

1.0
oooooGmehling et al. ( 1 9 8 0 ) /
0.8

0.6

:7.
0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Xl
Fig. 2. Comparison of equilibrium phase compositions measured in this work with the literature values for
cyclohexane(1)/benzene(2) at 343.13 K.
M. d. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98 87

Table 4
VLE data for ethanol(1)/diisopropyl ether(2)
T K P kPa x1 Yl lnyl lnY2 GE//(RTxIX2 )
344.17 108.0 0.0 0.0 - - -
126.9 0.104 0.206 1.203 0.0173 1.508
130.2 0.198 0.284 0.896 0.0510 1.374
132.3 0.304 0.333 0.639 0.138 1.372
133.9 0.414 0.369 0.444 0.266 1.402
133.3 0.516 0.403 0.306 0.399 1.406
128.1 0.618 0.442 0.179 0.531 1.328
123.4 0.709 0.490 0.108 0.680 1.330
113.3 0.813 0.569 0.0364 0.874 1.270
99.9 0.906 0.702 0.0149 1.078 1.348
75.4 1.0 1.0 - - -
353.22 142.1 0.0 0.0 - - -
168.5 0.103 0.219 1.186 0.0081 1.401
178.2 0.198 0.294 0.882 0.0710 1.459
179.9 0.304 0.342 0.609 0.154 1.380
178.7 0.413 0.382 0.405 0.256 1.310
178.0 0.516 0.421 0.275 0.382 1.307
174.3 0.618 0.463 0.168 0.523 1.288
166.4 0.709 0.516 0.0950 0.649 1.242
155.3 0.813 0.600 0.0402 0.839 1.247
136.8 0.906 0.734 0.00947 1.008 1.213
109.0 1.0 1.0 - - -
363.20 188.7 0.0 0.0 - - -
227.0 0.103 0.225 1.144 0.010 1.375
240.9 0.198 0.312 0.863 0.0595 1.379
245.8 0.303 0.372 0.632 0.129 1.332
249.2 0.414 0.414 0.439 0.246 1.343
246.7 0.515 0.451 0.295 0.362 1.312
244.1 0.617 0.492 0.190 0.512 1.326
234.9 0.709 0.541 0.109 0.651 1.291
220.6 0.813 0.620 0.0450 0.852 1.289
199.6 0.906 0.741 0.0176 1.072 1.371
158.7 1.0 1.0 - - -

with
c c
em = E E YiYjaij (3)
i=lj=l
where the second virial coefficient (Bij) is estimated by the correlation of Tsonopoulos (1974). By
definition, the excess Gibbs free energy (G E) of the liquid phase is obtained from
C
a E =- RT E Xi In Yi (4)
i=l
Table 7 shows that all the new data passed the point, area, and infinite dilution thermodynamic
consistency tests. The method of consistency tests is similar to that proposed by Kojima et al. (1990).
Appendix A gives the related equations.
88 M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

Table 5
VLE data for acetone(1)/diisopropyl ether(2)
T (K) P (kPa) xI Yl In ~1 In "/2 GE/(RTxIX2 )
343.26 105.2 0.0 0.0 - - -
125.5 0.0956 0.226 0.660 0.00081 0.738
140.2 0.210 0.383 0.496 0.0179 0.714
147.6 0.286 0.457 0.408 0.0436 0.724
158.6 0.390 0.537 0.324 0.112 0.820
164.1 0.498 0.603 0.223 0.192 0.829
168.2 0.601 0.660 0.151 0.293 0.867
168.7 0.704 0.722 0.0758 0.397 0.820
168.6 0.802 0.791 0.0380 0.522 0.842
164.8 0.908 0.881 - 0.00124 0.707 0.766
159.2 1.0 1.0 - - -
353.27 142.4 0.0 0.0 - - -
169.4 0.0959 0.224 0.654 - 0.00261 0.697
189.8 0.209 0.378 0.492 0.0216 0.725
203.2 0.286 0.451 0.420 0.0639 0.811
211.0 0.398 0.536 0.289 0.109 0.754
219.4 0.496 0.600 0.214 0.180 0.788
226.4 0.601 0.658 0.142 0.288 0.836
226.9 0.703 0.720 0.0750 0.391 0.809
229.6 0.803 0.792 0.0446 0.527 0.883
224.8 0.908 0.885 0.0112 0.688 0.879
216.2 1.0 1.0 - - -
363.29 189.4 0.0 0.0 - - -
226.2 0.0946 0.225 0.686 - 0.00372 0.719
257.1 0.208 0.380 0.527 0.0306 0.813
269.5 0.285 0.453 0.427 0.0552 0.791
284.1 0.391 0.530 0.314 0.116 0.812
294.3 0.496 0.597 0.222 0.191 0.825
301.4 0.603 0.657 0.143 0.293 0.845
306.2 0.704 0.717 0.0850 0.418 0.881
306.0 0.802 0.787 0.0441 0.545 0.903
300.4 0.908 0.879 0.0114 0.742 0.942
286.6 1.0 1.0 - - -

Figs. 3, 4 a n d 5 illustrate the p r e s s u r e - c o m p o s i t i o n d i a g r a m s for e t h a n o l / d i i s o p r o p y l ether,


a c e t o n e / d i i s o p r o p y l ether, a n d a c e t o n e / e t h a n o l at 353 K, r e s p e c t i v e l y . A l l these three b i n a r y s y s t e m s
s h o w p o s i t i v e d e v i a t i o n s f r o m R a o u l t ' s l a w a n d m a x i m u m a z e o t r o p e s exist in the m i x t u r e s c o n t a i n i n g
d i i s o p r o p y l ether. T h e a z e o t r o p i c p o i n t for each i s o t h e r m is d e t e r m i n e d b y f i n d i n g the m a x i m u m
p r e s s u r e ( d P / d x I = 0) o n the s m o o t h e d P - x 1 c u r v e a n d r e p o r t e d in T a b l e 8. T h e a z e o t r o p i c m o l e
f r a c t i o n o f d i i s o p r o p y l ether d e c r e a s e s w i t h t e m p e r a t u r e i n e t h a n o l / d i i s o p r o p y l ether m i x t u r e s , w h i l e
that i n c r e a s e s w i t h t e m p e r a t u r e i n a c e t o n e / d i i s o p r o p y l ether m i x t u r e s . F u r t h e r m o r e , Fig. 6 illustrates
that the a z e o t r o p i c c o m p o s i t i o n s ( x az) c o u l d b e c o r r e l a t e d w i t h the a z e o t r o p i c p r e s s u r e s ( p a z ) b y the
following empirical equation:
1
z = (5)
1 + m 1"23
M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98 89

Table 6
VLE data for acetone(1)/ethanol(2)
T (K) P (kPa) x1 Yl ln~/1 1n3'2 GE/(RTxlx2 )
344.19 75.7 0.0 0.0 - - -
94.6 0.095 0.256 0.465 0.0199 0.723
106.3 0.191 0.411 0.356 0.0192 0.488
118.8 0.293 0.524 0.273 0.0386 0.518
130.0 0.388 0.603 0.220 0.0870 0.585
138.1 0.489 0.673 0.154 0.132 0.571
144.1 0.592 0.737 0.0948 0.178 0.533
150.4 0.695 0.797 0.0521 0.252 0.534
157.0 0.795 0.854 0.0267 0.362 0.586
161.4 0.890 0.917 0.0115 0.443 0.602
164.3 1.0 1.0 - - -
353.18 108.7 0.0 0.0 - - -
131.2 0.0944 0.235 0.448 0.0115 0.617
147.5 0.190 0.384 0.350 0.0184 0.530
161.4 0.292 0.497 0.260 0.0379 0.497
175.0 0.387 0.577 0.205 0.0848 0.554
184.7 0.489 0.651 0.143 0.126 0.537
190.9 0.591 0.715 0.0774 0.178 0.490
200.6 0.695 0.782 0.0510 0.252 0.530
206.3 0.796 0.845 0.0199 0.335 0.518
211.8 0.890 0.913 0.0094 0.405 0.541
215.5 1.0 1.0 - - -
363.19 158.6 0.0 0.0 - - -
194.3 0.0942 0.246 0.604 0.00927 0.765
217.9 0.190 0.374 0.432 0.0417 0.753
232.9 0.292 0.466 0.279 0.0825 0.676
244.6 0.387 0.537 0.186 0.129 0.637
255.0 0.489 0.609 0.116 0.182 0.598
265.2 0.591 0.680 0.072 0.242 0.586
272.8 0.695 0.753 0.0377 0.303 0.560
278.5 0.795 0.828 0.0173 0.357 0.534
282.9 0.889 0.902 0.00515 0.426 0.525
285.8 1.0 1.0 - - -

with

m=
~ lPaz--e~]
IPaz P~I (6)

w h e r e Pa~ a n d P~, are the v a p o r p r e s s u r e s o f p u r e c o m p o n e n t s . T h e c o m p o n e n t s a a n d b are d e f i n e d to


m a k e the v a l u e o f m g r e a t e r t h a n u n i t y .
T h e e q u i l i b r i u m p h a s e c o m p o s i t i o n s are also to b e m e a s u r e d for the t e r n a r y s y s t e m o f
a c e t o n e / e t h a n o l / d i i s o p r o p y l ether at 3 5 3 . 2 7 K. T a b l e 9 p r e s e n t s the e x p e r i m e n t a l results. S i m i l a r l y
Eq. (1) w a s a p p l i e d to c a l c u l a t e the a c t i v i t y c o e f f i c i e n t for the c o n s t i t u e n t c o m p o n e n t s . Fig. 7 p r e s e n t s
the t i e - l i n e s d e t e r m i n e d in this study. It a p p e a r s n o t e r n a r y a z e o t r o p e b e i n g f o r m e d .
90 M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

4. Vapor-liquid equilibrium calculation


Vapor-liquid equilibrium data reduction is made with ~b- ~/ method for each binary isotherm.
The two-term virial equation and the solution models including the Wilson, NRTL, and UNIQUAC
are utilized to calculate the fugacity coefficient in vapor phase and the activity coefficient in liquid
phase, respectively. The optimal values of temperature-specific binary parameters of the solution

Table 7
Results of the thermodynamic consistency tests
mixture T (K) consistency test index a G E / R T coefficient b ln(y 1/~/2 ) coefficient ¢
A I1 ~ Co C1 C2 DO D] D2 D3
ethanol/ 344.17 1.3(+) d 1.4(+) 6.2(+) 0.6(+) 1.357 -0.092 0.056 0.014 1.384 -0.132 0.075
diisopropyl
ether
353.22 1.8 ( + ) 1.6(+) 9.7(+) 3.3(+) 1.313 - 0 . 1 4 0 0.021 0.016 1.333 -0.182 0.101
363.20 1.7 ( + ) 1.3(+) 6.0(+) 2.8(+) 1.315 -0.033 0.077 0.013 1.339 -0.084 0.079
acetone/ 343.26 2.9 ( + ) 0 . 5 ( + ) 2 1 . 0 ( + ) 1 5 . 3 ( + ) 0.825 0.061 -0.125 0.006 0.831 0.050 0.024
diisopropyl
ether
353.27 2.4 ( + ) 0.6(+) 15.4(+) 5.0(+) 0.801 0.105 -0.009 0.006 0.813 0.027 0.019
363.29 2.4 ( + ) 0.3(+) 15.4(+) 2.5(+) 0.835 0.113 0.007 0.003 0.859 0.038 0.039
acetone/ 344.19 3.3(+) 0.4(+) 2 8 . 1 ( + ) 1 7 . 3 ( + ) 0.529 -0.013 0.156 0.004 0.554 0.018 0.005
ethanol
353.18 2.0(+) 0.5(+) 1 6 . 4 ( + ) 1 3 . 7 ( + ) 0.512 -0.026 0.083 0.005 0.526 -0.011 -0.009
363.19 0.4(+) 0.2(+) 1.7(+) 0.6(+) 0.605 -0.156 0.070 0.002 0.613 -0.163 0.067

a criteria for passing the thermodynamic consistency tests: 8 < 5, A < 3, I 1 < 30, 12 < 30; b G E / R T = Xl x2 [Cq + C 1
( x 1 - x 2 ) + C 2 (Xl- x2)2]; Cln(2/1/'y2)=Do+D1 ( x 2 - x 1 ) + O 2 ( 6 X l X 2 - 1 ) + D 3 ( x 2 - x 1) ( 1 - 8 X1 X2); o(+),
passes the consistency test.

200

,--,,1.Xl3_0
50 .i

EL 100-
ooooo P-x,(exp.)
~noDo P-yl(exp:) .
UNIQUAC(cal.)

50 ................................................
0.0 0.2 0.4 0.6 0.8 1.0
xl,yl
Fig. 3. Pressure-composition phase diagram for ethanol(l)/diisopropyl ether(2) at 353.22 K.
M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98 91

250

~200
0
n

13.. 1501
ooooo P-x,(exp.)
ooooo P-yl(exp.) .
UNIQUA(~(cal.)

100 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
0.0 0.2 0.4 0.6 0.8 1.0
Xl,Yl
Fig. 4. Pressure-composition phase diagram for acetone(1)/diisopropyl ether(2) at 353.27 K.

250

200

0
O_
-~150

O_

1 O0 ooooo P-x,(exp.)
ooooo P - y , ( e x p . ) .
UNIOUA(~(col.)

50 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
0.0 0.2 0.4 0.6 0.8 1.0
Xl,Yl
Fig. 5. Pressure-composition phase diagram for acetone(l)/ethanol(2) at 353.18 K.

Table 8
Azeotropic conditions for diisopropyl ether-containing mixtures
mixture (1)/(2) T (K) x~z pa~ (kPa)
ethanol/diisopropyl ether 344.17 0.646 133.9
353.22 0.629 180.5
363.20 0.582 249.3
acetone/diisopropyl ether 343.26 0.237 168.7
353.27 0.246 229.6
363.29 0.259 306.3
92 M.-J. Lee, C.-H. Hu /Fluid Phase Equilibria 109 (1995) 83-98

0.5

[]
0.4

N
o
X
o0.3

0.2
00000 dllsopropyl ether(o)/ocetone.(b)
ooooo ethanol(a)/diisopropyl ether(,b)
eqn.(5)
.1 ' '' ' ' r r ' ' l ' ' ' ' ' ' ' ' e ] ' ' ' ~ ' ' ' ' ~ l ' ' ' ' ' ' '' '

.0 1.5 2.0 2.5 3 .0


m
Fig. 6. Correlation of azeotropic composition with azeotropic pressure.

models are determined by the maximum likelihood principle, i.e., minimization of the following
objective function 7r"
~ {[p~al pexp]2 Tcal Texp]2 cal exp]2 [.t, cal.~,exp]2~
7r= + + --- + (7)
k=1 O'p orT O'xl

Table 9
VLE data for acetone(1)/ethanol(2)/diisopropyl ether(3) at 353.27 K
No. P kPa x1 x2 y~ Y2 In Yl In Y2 In "Y3
1 187.7 0.111 0.106 0.195 0.167 0.486 1.021 0.056
2 190.1 0.106 0.336 0.158 0.305 0.377 0.451 0.253
3 180.2 0.097 0.594 0.157 0.407 0.379 0.139 0.583
4 152.9 0.090 0.823 0.188 0.603 0.435 0.019 0.987
5 201.7 0.200 0.209 0.284 0.209 0.313 0.642 0.180
6 196.7 0.220 0.392 0.290 0.292 0.253 0.302 0.411
7 206.8 0.282 0.319 0.351 0.248 0.211 0.377 0.370
8 202.6 0.294 0.409 0.372 0.280 0.197 0.249 0.515
9 207.6 0.328 0.0987 0.426 0.110 0.255 0.821 0.159
10 185.9 0.334 0.578 0.462 0.382 0.203 0.099 0.893
11 207.3 0.327 0.341 0.394 0.250 0.177 0.322 0.448
12 212.8 0.395 0.200 0.457 0.168 0.158 0.521 0.322
13 212.2 0.395 0.201 0.456 0.168 0.157 0.521 0.322
14 211.2 0.402 0.302 0.466 0.214 0.135 0.344 0.475
15 203.2 0.395 0.413 0.472 0.276 0.141 0.212 0.657
16 222.8 0.567 0.104 0.608 0.088 0.095 0.608 0.367
17 205.5 0.562 0.345 0.635 0.230 0.075 0.242 0.800
18 215.9 0.600 0.206 0.625 0.151 0.057 0.398 0.577
19 217.8 0.800 0.105 0.798 0.0808 0.014 0.466 0.711
M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98 93

J ~5

t'q

tt~

c5

0 t'---

ca ¢¢
N

L)
<

¢a
Z
D
"0 c5
e.
cO

Z 0

I~ qr)
¢q I'~

"a I
tt% ¢e)

T
¢e~ t ' q
tr~ ~D
b~ ¢¢% ¢¢~

t".l
"0
II II

[.
94 M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

1.0
\

0.8 ~ oooooliquid phase


= . , . v a p o r phase

0.6

g~
XO.4

0.2

0.0 0.2 0.4 0.6 0.8 1.0


xl,yl
Fig. 7. Tie-lines for the ternary system of acetone(1)/ethanol(2)/diisopropyl ether(3) at 353.27 K.

where o-2 is the variance of the measured variables. The standard deviation or used here is 0.133 kPa
for pressure, 0.07 K for temperature, 0.001 for liquid composition, and 0.003 for vapor composition.
Basically, the optimization algorithm is similar to that of Prausnitz et al. (1980). Only minor revision

Table 11
VLE prediction with determined binary parameters for acetone ( 1 ) / e t h a n o l ( 2 ) / d i i s o p r o p y l ether(3) at 353.27 K
No Wilson NRTL UNIQUAC
A p a kPa Ay 1 a 102 Ay 2 a 102 A p kPa Ay I 102 Ay 2 102 A p kPa Ay I 102 Ay 2 102
1 2.4 -0.1 0.4 -1.0 -0.5 0.0 1.5 0.0 0.2
2 0.6 0.3 0.1 -2.9 -0.9 0.7 -0.2 -0.1 0.4
3 0.2 0.7 -0.6 -2.8 -0.5 -0.2 -0.4 0.4 -0.8
4 2.5 0.3 -0.5 -0.4 0.0 0.1 1.2 0.3 -0.6
5 3.1 0.5 -0.2 -1.1 0.0 -0.3 2.1 0.4 -0.1
6 -0.3 0.2 0.2 -5.1 -0.7 0.5 -1.6 -0.2 0.2
7 3.9 -0.1 0.4 -0.8 -0.4 0.4 2.7 -0.2 0.3
8 3.1 0.3 -0.3 -1.9 0.1 -0.1 1.7 0.2 -0.4
9 -0.8 -0.5 0.4 -3.8 0.0 -0.4 -1.6 -0.4 0.2
10 3.0 -0.7 0.0 -0.8 -0.1 0.7 1.7 -0.4 0.2
11 3.2 -0.2 0.4 -1.6 -0.3 0.4 1.9 -0.3 0.3
12 1.0 -0.4 0.5 -3.0 -0.1 -0.1 -0.1 -0.3 0.3
13 0.4 -0.6 0.5 -3.6 -0.1 -0.1 -0.7 -0.4 0.3
14 3.0 0.2 -0.2 -1.6 0.5 -0.4 1.7 0.2 -0.4
15 2.6 -0.6 0.1 -2.2 -0.1 0.4 1.2 -0.3 0.1
16 2.3 0.0 0.3 -0.2 0.6 -0.4 1.7 0.2 0.1
17 2.1 -0.1 -0.3 -1.4 0.8 -0.1 1.1 0.2 -0.3
18 0.2 -0.7 0.3 -3.2 0.1 -0.1 -0.7 -0.4 0.2
19 -0.8 -0.4 0.1 -2.8 0.4 -0.1 -1.3 -0.1 0.1
AAD 1.9 0.4 0.3 2.1 0.3 0.3 1.3 0.3 0.3

ap = p~ - p~xp, Ay~ = 100 ( y ~ l - y~"P), A y 2 = 100 (y~a _ y~xp).


M.-J. Lee, C.-H. Hu /Fluid Phase Equilibria 109 (1995) 83-98 95

has been made for estimating the second virial coefficients (Tsonopoulos, 1974). Table 10 lists the
results of data reduction which appears that all the activity coefficient models give satisfactory
representations, while the Wilson model leads to the best correlation. As an illustration, the smooth
curves in Figs. 3-5 show the calculated results from the UNIQUAC model. Moreover, those three
theoretical models with the determined binary parameters are used in the present study for predicting
the bubble points of acetone/ethanol/diisopropyl ether system at 353.27 K. As a comparison made in
Table 11, it is found that the UNIQUAC model yields the best prediction.

5. Conclusion

Isothermal VLE data were determined experimentally with a static apparatus for the binary and
ternary mixtures composed of ethanol, acetone, and diisopropyl ether in a temperature range of
343-363 K. All the binary data passed the point, area, and infinite dilution thermodynamic
consistency tests. Among the investigated binary systems, maximum pressure azeotropes formed in
the mixtures containing diisopropyl ether. An empirical function was developed for correlating the
azeotropic pressures with azeotropic compositions reasonably well. The study also found that the
Wilson, NRTL, and UNIQUAC models were capable of correlating the binary VLE data to adequate
accuracy and the UNIQUAC model yielded the best prediction for the ternary system.

6. List of symbols

A index of area consistency test


AAD average absolute deviation
B second virial coefficient (cm 3 mol- 1)
Ck coefficients
c number of component
Ok coefficients
G Gibbs free energy (J mol- 1)
g0 - gii parameters of the NRTL model (kPa cm 3 mol- 1)
/1, I2 indices of infinite dilution consistency test
m dimensionless variable
n number of data points
P pressure (kPa)
R gas constant (kPa cm 3 mol- 1 K- 1)
T temperature (K)
uij - - uii parameters of the UNIQUAC model (kPa c m 3 mol- 1)
V molar volume ( c m 3 mol- 1)
VPi coefficients of the Wagner vapor pressure equation
x mole fraction of liquid phase
Y mole fraction of vapor phase
Zm~ parameter in the modified Rackett equation
96 M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

Greek letters
Ol parameter of the NRTL model
activity coefficient
6 index of point consistency test
pressure effect term in the Gibbs-Duhem equation
0 dimensionless variable, 0 = 1 - (T/T c)
parameters of the Wilson model (kPa cm 3 mol- 1)
tx dipole moment (Debye)
objective function
(7" standard deviation
4, fugacity coefficient
o.I acentric factor

Subscripts

a component a
b component b
c critical
i component i
ij i-j pair interaction
j component j
ji j - i pair interaction
m mixture

Superscripts

az azeotrope
cal calculated
E excess property
exp experimental
L liquid phase
lit literature
s saturation

Acknowledgements

Financial support from the National Science Council, ROC, through Grant No. NSC84-2214-E011
012 is gratefully acknowledged.
M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98 97

Appendix A

Equations for thermodynamic consistency tests (Kojima et al., 1990)

Point test

100 n
~= Y'. I~k*[ (gl)
n k=l
with
d
6k = --(GE/RT)k- ln('Y1/T2)k- •k (A2)
dx 1
where
V E dP
(A3)
RT dx 1

For isothermal VLE data, e is always less than 3 X 10 -5. The effect of • on the test result is
negligible. The excess Gibbs free energy and activity coefficient ratio in Eq. (A2) were expressed as
the Redlich-Kister equation, respectively.
G E

RT
= XlX2[Cot Jr" C I ( x I - x2) + C2( x 1 - X2)21' (A4)

l n ( y l / y 2 ) = D o + D l ( x 2 - Xl) + D 2 ( 6 x l x 2 - 1) + D3(x 2 - Xl)(1 - 8XlX2) (AS)


The criterion for passing the point test is 6 < 5.

A r e a test

A= IOOIA*I (A6)
with

A*= fo IIn ( "~1/'~2) dXl (A7)

The criterion for passing the area test is A < 3.

Infinite dilution test

11 = 100[ I ( [ (A8)
and
12= 100{ I21 (A9)
98 M.-J. Lee, C.-H. Hu / Fluid Phase Equilibria 109 (1995) 83-98

with

[o']
RTxlx2 x,=O
,nt'at \ ")/2 Ix,=O
1:-- ,n(,l/
T2 ! x,=O
and

oE]
(RTxIX2) x~=0
-- In t l)
m

T2 x2=0
I2 = (All)

ln( )x o
The criteria for passing the infinite dilution test are both 11 and 12 < 30.

References

Abrams, D.S. and Prausnitz, J.M., 1975. Statistical thermodynamics of liquid mixtures: a new expression for the excess
Gibbs energy of partly or completely miscible systems. AIChE J., 21: 116-128.
Campbell, S.W., Wilska, R.A. and Thodos, G., 1987. Vapor-liquid equilibrium measurements for the ethanol-acetone
system at 372.7, 397.7, and 422.6 K. J. Chem. Eng. Data, 32:357-362.
Gmehling, J., Onken, U. and Arlt, W., 1980. Vapor-liquid equilibrium data collection-aliphatic hydrocarbons, C 4 - C 6.
Chemistry Data Series, Vol. 1, Part 6a, DECHEMA, Frankfurt, Germany, p. 233.
Gmehling, J., Onken, U. and Arlt, W., 1982. Vapor-liquid equilibrium data collection-organic hydroxy compounds:
alcohols (Supplement 1). Chemistry Data Series, Vol. 1, Part 2c, DECHEMA, Frankfurt, Germany, pp. 301-312.
Horsley, L.H., 1973. Azeotropic data-III. Advances in Chemistry Series 116, American Chemical Society, Washington,
D.C., USA, p.136 and p. 171.
Kojima, K., Moon, H.M. and Ochi, K., 1990. Thermodynamic consistency test of vapor-liquid equilibrium data methanol-
water, benzene-cyclohexane and ethyl methyl ketone-water. Fluid Phase Equilibria, 56: 269-284.
Prausnitz, J.M., Anderson, T.F., Grens, E.A., Eckert, C.A., Shieh, R. and O'Connell, J.P., 1980. Computer Calculations for
Multicomponent Vapor-liquid and Liquid-liquid Equilibria. Prentice-Hall, New York, NY, USA.
Reid, R.C., Prausnitz, J.M. and Poling, B.E., 1987. The Properties of Gases and Liquids. 4th edn., McGraw-Hill, New York,
NY, USA.
Renon, H. and Prausnitz, J.M., 1968. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J.,
14: 135-144.
Spencer, C.F. and Danner, R.P., 1972. Improved equation for prediction of saturated liquid density. J. Chem. Eng. Data, 17:
236-241.
Tsonopoulos, C., 1974. An empirical correlation of second virial coefficients. AIChE J., 20: 263-272.
Wilson, G.M., 1964. Vapor-liquid equilibrium. XI: a new expression for the excess free energy of mixing. J. Am. Chem.
Soc., 86: 127-130.