Ind. Eng. Chem. Res.

2008, 47, 7927–7933 7927

Vapor-Liquid-Liquid Equilibria for Aqueous Systems with Methyl Acetate,

Methyl Propionate, and Methanol
Cheng-Ting Hsieh, Ming-Jer Lee,* and Ho-mu Lin
Department of Chemical Engineering, National Taiwan UniVersity of Science and Technology, 43 Keelung
Road, Section 4, Taipei 106-07, Taiwan

Vapor-liquid-liquid equilibrium (VLLE) properties were measured with a static apparatus for mixtures of
water + methyl acetate, water + methyl propionate, water + methyl acetate + methanol, and water + methyl
propionate + methanol at temperatures ranging from 313.24 to 348.15 K. Both ternary systems exhibit type
I liquid-liquid equilibrium (LLE) behavior. By checking with the Othmer-Tobias equation, the experimental
tie-line data of these two ternary systems appeared to be consistent. The binary VLLE data were correlated
satisfactorily with the UNIQUAC model for water + methyl acetate and water + methyl propionate. While
the UNIQUAC model with the parameters determined from the phase equilibrium data of the constituent
binaries overestimated the two-liquid-phase regions of the ternary systems, the representation of the binodal
loci was substantially improved as the six parameters of the UNIQUAC model were determined simultaneously
from the ternary VLLE data.

Introduction
Substantial amounts of waste acids, including carboxylic acids
and dibasic acids, are produced in caprolactam plants. Reactive
distillation is an economically attractive method to convert these
waste acids into methyl esters and diesters via esterification of
the acids with methanol.1 Because both chemical reaction and
phase equilibria govern the performance of reactive distillation
columns, the kinetics and phase equilibria data are fundamentally
important in process development. In this series of reactive
distillation systems, vapor-liquid-liquid multiphase coexistence
may occur due to the mixtures containing partially miscible
components, water and esters.
Since this study focused on recovery of acetic acid and
propionic acid simultaneously, the objective of this work is to
investigate the multiphase coexistence behavior of aqueous
mixtures containing methanol, methyl acetate, or methyl pro-
pionate. Among the constituent binaries, the vapor-liquid
equilibrium (VLE) data are available from the DECHEMA VLE
Data Collection for water + methanol,2 water + methyl acetate,3
and methyl acetate + methanol.4 The mutual solubility data of
water + methyl acetate5-7 and water + methyl propionate8,9
have been tabulated in the DECHEMA Liquid-Liquid Equi-
librium (LLE) Data Collection. Additionally, the mutual solubil-
ity data of water + methyl propionate were also reported by
Stephenson and Stuart.10 Polak and Lu11 measured the isother-
mal VLE data of methyl propanoate + methanol at 298.15 K.
Martin and Mato12 investigated the VLE behavior of water +
methyl acetate + methanol at atmospheric pressure. Bernatova
et al.13 determined the equilibrium pressures and compositions
of the coexistent vapor and liquid phases for the system
containing acetic acid, methanol, methyl acetate, and water at
chemical and phase equilibria simultaneously. In the present
study, VLLE data are measured for two binary systems of water
+ methyl acetate and water + methyl propionate and two ternary
systems of water + methyl acetate + methanol and water +
methyl propionate + methanol at temperatures ranging from
313.24 to 348.15 K. These new ternary VLLE data were used
* To whom correspondence should be addressed. Tel.: +886-2-2737-
6626. Fax: +886-2-2737-6644. E-mail: mjlee@mail.ntust.edu.tw.
10.1021/ie800840r CCC: $40.75  2008 American Chemical Society
Published on Web 09/24/2008
to test the validity of the UNIQUAC14 model for the multi-
component VLLE calculations.
Experimental Section
A static apparatus was employed in the present study to
measure the VLLE data. The schematic diagram and detailed
operation procedure have been given elsewhere.15,16 The central
part of the apparatus is an equilibrium cell with the internal
volume of 60 cm3, which was immersed in a thermostatic bath
(model TV 4000; stability ) (0.03 K, 40 L, Tamson, The
Netherlands). The phase behavior in the equilibrium cell can
be observed through the transparent windows. The bath tem-
perature was measured by a precision thermometer (model 1560,
Hart Scientific, USA) with a platinum RTD probe to an accuracy
of (0.02 K. A pressure transducer (model PDCR-912; 0-1000
kPa; Druck, U.K.) with a digital indicator (model DPI-261,
Druck, U.K.) measured the equilibrium pressure. The uncertainty
of the pressure measurement was estimated to be less than 0.1
kPa.
This apparatus was equipped with both liquid and vapor
circulation loops to promote attainment of equilibration. A four-
port liquid-sampling valve (model 7410, Rheodyne, USA) with
a 1 µL cavity disk was installed in the liquid circulation loop
to trap the liquid sample. A switch valve was utilized to select
one of the coexistent liquid phases to be circulated. The
circulated liquid was reheated by a preheater before returning
to the equilibrium cell. The gas circulation loop consists of
a six-port vapor-sampling valve (model 7010, Rheodyne,
USA) with a 100 µL sample loop, a magnetic gear pump,
and a preheater. The composition of the sample was analyzed
by gas chromatography (GC, model 8700, China Chroma-
tography Co., Taiwan) with a thermal conductivity detector.
High-purity helium (99.99%) was used as a carrier gas.
Information of GC columns for composition analysis is given
in Table 1.
A proper amount of solution was loaded into the degassing
unit at the beginning of an experiment. The degassing procedure
is similar to that of Lee and Hu.17 The degassed solution was
then transferred into the equilibrium cell in which the levels of
the vapor-liquid-liquid interfaces should be adjusted properly
7928 Ind. Eng. Chem. Res., Vol. 47, No. 20, 2008

Table 1. Composition Analysis and Gas Chromatography Calibration

systema mixture column phase average deviationb T injector (K) T oven (K) T detector (K)
M1 water (1) + methanol (2) Porapak QS organic 0.0004 403 307-403 c
403
aqueous 0.0004
water (1) + methyl acetate (2) Porapak QS organic 0.0024
aqueous 0.0002
M2 water (1) + methanol (2) CP-WAXd + Carbopack Ce organic 0.0011 513 311-443f 513
aqueous 0.0011
water (1) + methyl propionate (2) CP-WAX + Carbopack C organic 0.0004
aqueous 0.0004
a
M1: water + methyl acetate + methanol. M2: water + methyl propionate + methanol. b Average deviation )1/np ∑knp) 1 (|xcalb - xact|)k, where np is
the number of calibration points and x is the mole fraction of the component 1. c Initially keep the oven temperature at 307 K for 40 min, increase the
temperature up to 403 K within 5 min, and keep this temperature for 10 min. d CP-WAX (model CP7668, Varian, USA). e Carbopack C (0.1% SP-1000
on 80/100 Carbopack C). f Initially keep the oven temperature at 311 K for 20 min, increase the temperature up to 443 K within 5 min, and keep this
temperature for 25 min.

Table 2. Physical Properties and Parameters for the Constituent Compoundsa

compound Tc (K) Pc (kPa) Tb(K) ω µ (debye) rb qb C1c C2c C5 c C6c C7c C8c (K) C9c (K)
water 647.13 22064 373.13 0.345 1.8 0.92d 1.40d 66.74 -7258.2 -7.30 4.17E-06 2 273.16 647.13
methanol 512.50 8084 337.90 0.566 1.7 1.43d 1.43d 75.81 -6904.5 -8.86 7.47E-6 2 175.47 512.50
methyl acetate 506.55 4750 330.05 0.331 1.7 2.80d 2.58d 54.36 -5618.6 -5.65 2.11E-17 6 175.15 506.55
methyl propionate 530.60 4004 352.65 0.347 1.7 3.48e 3.12e 63.81 -6439.7 -6.98 2.01E-17 6 185.65 530.60
a
Taken from the Aspen property databank. b UNIQUAC constants. c Extended Antoine equation: ln (PS) ) C1 + (C2/(T + C3) + C4T + C5 ln T +
C6TC7 for C8 < T < C9, where PS is in kPa and T in K. The values of the coefficients were taken from the Aspen property databank, and the values of
C3 and C4 are zero for each compound. d Taken from ref 18. e Taken from ref 8.

Table 3. VLLE Data for Water (1) + Methyl Acetate (2) Table 4. VLLE Data for Water (1) + Methyl Propionate (2)
T (K) P (kPa) organic phase x2I aqueous phase x2II vapor phase y2 T (K) P (kPa) organic phase x2I aqueous phase x2II vapor phase y2
313.24 53.1 0.6970 0.0684 0.8808 318.24 35.0 0.8893 0.0110 0.8774
323.24 78.2 0.6594 0.0700 0.8613 323.24 43.7 0.8838 0.0109 0.7532
333.15 112.3 0.6152 0.0705 0.8359 328.24 53.3 0.8759 0.0108 0.7299
343.15 157.0 0.5571 0.0770 0.8249 333.15 65.2 0.8494 0.0107 0.7195
for sampling. Liquid and vapor mixtures were circulated 338.15 79.2 0.8325 0.0106 0.7049
343.15 95.3 0.8230 0.0101 0.7267
alternatively by circulation pumps to promote equilibration. 348.15 113.8 0.8067 0.0109 0.7407
While the system reached equilibrium, pressure reading of the
cell should approach a constant. Four to five samples were Figures 1 and 2 illustrate the phase compositions varying with
replicated for each phase at fixed experimental conditions. temperature for water + methyl acetate and water + methyl
Generally, the area fractions of the components can be propionate, respectively. The literature values are also marked
reproduced to within (0.2%. The averaged area fraction from on the graphs for comparison. Within the experimental tem-
GC analysis was converted into mole fraction via calibration
equations. Calibrations were made with gravimetrically prepared
samples within two composition ranges in accordance with those
in the organic-rich (including the vapor phase) and the water-
rich phases for the investigated systems. The uncertainties of
the composition analysis are tabulated in Table 1.
Methanol (99.8%) was purchased from Sigma-Aldrich,
Germany. Methyl acetate (99%) and methyl propionate (99+%)
were supplied by Acros, USA. The purity of each substance
was checked with chromatographic analysis. The area fractions
are 0.9984, 0.9974, and 0.9966 for methanol, methyl acetate,
and methyl propionate, respectively, from GC analysis. These
chemicals were used without further purification. Deionized
distilled water was prepared in our laboratory. The measured
normal boiling point and other physical properties of each pure
compound are listed in Table 2.

Experimental Results
Binary VLLE Systems. Tables 3 and 4 list the VLLE data
of water + methyl acetate and water + methyl propionate,
respectively. Trace amounts of methanol were detected from
the liquid phase of the water + methyl propionate system,
indicating that hydrolysis of methyl propionate took place
slowly even without the presence of any acidic or basic
catalyst. Nevertheless, the mole fraction of methanol was still
negligible at the end of the run, even at the highest operating Figure 1. Temperature-composition VLLE phase diagram for water (1)
temperature. + methyl acetate (2).

Figure 2. Temperature-composition VLLE phase diagram for water (1)
+ methyl propionate (2).
Figure 3. Saturated pressures at VLLE for water + methyl acetate and
water + methyl propionate.
perature range of this work, from 313 to 348 K, the agreement
is satisfactory except for the liquid compositions of the methyl
propionate-rich phase compiled in Sorensen and Arlt,9 whose
data are obviously lower than the results of Stephenson and
Stuart10 and ours as shown in Figure 2. In those previous works
Sorensen and Arlt9 and Stephenson and Stuart10 conducted LLE
measurements by analyzing the compositions of coexistence
liquid phases with GC. Only the phase compositions of the
aqueous phase were determined experimentally by Sorensen and
Arlt.5-8 While the mole fraction of methyl acetate in the vapor
phase (y2) decreases with increasing temperature, that of methyl
propionate (y2) has a minimum value at about 338 K. Figure 3
is the P-T diagram at VLLE, indicating that the saturated
pressure varying with temperature appears to obey the Antoine
relationship.
Ind. Eng. Chem. Res., Vol. 47, No. 20, 2008 7929
Ternary VLLE Systems. The ternary VLLE measurements
were conducted at temperatures ranging from 313.24 to 348.15
K. Tables 5 and 6 report the experimental results for water +
methyl acetate + methanol and water + methyl propionate +
methanol, respectively. Since the concentrations of methanol
in the vapor phase are generally too dilute to be accurately
determined in water + methyl acetate + methanol, only one
point of vapor composition was reported for this system. Figures
4 and 5 illustrate the enlarged phase diagrams of water + methyl
acetate + methanol at 323.24 K and water + methyl propionate
+ methanol at 333.15 K, respectively. Because water/ester is
the only partial miscibility pair, these two investigated ternary
systems behave as type I of LLE. As seen from the experimental
results, the solubility of the organic compounds is rather small
in the aqueous phase, while water dissolves appreciably in the
organic-rich phase. Owing to the fact that the mutual solubility
between water and ester increases with increasing temperature,
the area of the liquid-liquid splitting region becomes smaller
at higher temperatures. Figures 1 and 4 show that the composi-
tions of vapor phase are not located in the liquid-liquid splitting
region of water + methyl acetate + methanol, and Figure 5
indicates that those are also beyond the two-liquid-phase region
of water + methyl propionate + methanol as the total mole
fractions of methanol are greater than about 0.1. The vapor
mixtures should form a homogeneous liquid phase in a total
condenser when the vapor compositions are beyond the two-
liquid-phase zone.
The phase compositions of the two ends of the tie lines were
correlated with the empirical equation of Othmer-Tobias19
ln
( ) 1 - wII1
wII1
) n + m ln
( )
1 - wI2
wI2
(1)
where w1II is the weight fraction of water in the aqueous phase
and w2I is the weight fraction of the ester in the organic phase.
The values of n and m and the coefficient of correlation (R2)
are listed in Table 7. Figures 6 and 7 illustrate that the LLE
data follow a linear relationship as given by eq 1. It was found
that the isothermal tie-line data are fitted by the Othmer-Tobias
equation consistently. The values of R2 are no less than 0.90
for all isotherms.
VLLE Calculation
At VLLE, the compositions of three coexistent phases (yi,
xiI, and xiII) and the fraction of each phase (R and β) can be
calculated via VLLE flash calculations20 at a given temperature
and feed composition (zi). According to the material balance
equations and equilibrium criteria for a VLLE system, two flash
equations were obtained as follows
nc
(KIi - 1)zi
∑ RK + (1 - R)[β + (1 - β)K ⁄ K ] ) 0
I I II
(2)
i)1 i i i
nc
(KIIi - 1)zi
∑ RK )0 (3)
i + (1 - R)[β(Ki ⁄ Ki ) + (1 - β)]
II I II
i)1
with
KIi ) yi ⁄ xIi ) γIi φSi PSi exp[(P - PSi )VLi ⁄ RT] ⁄ (φ̂iP) (4)
KIIi ) yi ⁄ xIIi ) γIIi φSi PSi exp[(P - PSi )VLi ⁄ RT] ⁄ (φ̂iP) (5)
Since the equilibrium pressures (P) are sufficiently low in the
investigated systems, the values of φiS, φ̂i, and the Poynting
7930 Ind. Eng. Chem. Res., Vol. 47, No. 20, 2008

Table 5. VLLE Data for Water (1) + Methyl Acetate (2) + Methanol (3)
organic phase, xiI aqueous phase, xiII vapor phase, yi
T (K) P (kPa) methyl acetate methanol water methanol methyl acetate methanol
313.24 52.8 0.6190 0.0131 0.9061 0.0119
52.7 0.5631 0.0260 0.8914 0.0201
52.6 0.4220 0.0447 0.8496 0.0386
323.24 78.1 0.5991 0.0143 0.9011 0.0155
77.9 0.5150 0.0243 0.8943 0.0182
77.8 0.4727 0.0333 0.8849 0.0256
77.5 0.4124 0.0388 0.8661 0.0324
333.15 112.1 0.5469 0.0148 0.9086 0.0108
112.0 0.4269 0.0316 0.8891 0.0236
111.8 0.4035 0.0322 0.8802 0.0265
343.15 156.6 0.4976 0.0087 0.9178 0.0051
156.2 0.4272 0.0173 0.8991 0.0161 0.7805 0.0237

Table 6. VLLE Data for Water (1) + Methyl Propionate (2) + Methanol (3)
organic phase, xiI aqueous phase, xiII vapor phase, yi
T (K) P (kPa) methyl propionate methanol water methanol methyl propionate methanol
318.24 36.7 0.8442 0.0324 0.9453 0.0397 0.8256 0.0387
37.6 0.8193 0.0513 0.9206 0.0630 0.7975 0.0525
38.8 0.7506 0.0842 0.8815 0.0993 0.6906 0.1334
39.2 0.6714 0.1134 0.8601 0.1165 0.6669 0.1463
40.0 0.4606 0.1946 0.7872 0.1693 0.6364 0.1721
40.3 0.3372 0.2159 0.6965 0.2019 0.6264 0.1792
41.1 0.3130 0.2174 0.6441 0.2065 0.5563 0.2169
333.15 68.3 0.8096 0.0357 0.9481 0.0375 0.6881 0.0646
69.9 0.7676 0.0586 0.9180 0.0622 0.6877 0.0668
71.9 0.6743 0.0939 0.8838 0.0948 0.6754 0.0872
72.6 0.6140 0.1221 0.8577 0.1184 0.6576 0.1103
73.2 0.5172 0.1592 0.8353 0.1361 0.6356 0.1349
73.9 0.3556 0.1994 0.7892 0.1717 0.6242 0.1478
74.9 0.2859 0.2050 0.7656 0.1834 0.5797 0.2086
348.15 119.4 0.7414 0.0411 0.9492 0.0368 0.6709 0.0689
122.2 0.6802 0.0689 0.9232 0.0589 0.6237 0.1082
125.2 0.6309 0.1086 0.8889 0.0915 0.5905 0.1358
126.3 0.5431 0.1353 0.8570 0.1089 0.5286 0.1801
127.0 0.5202 0.1487 0.8022 0.1210 0.5103 0.1957
pressure correction factor could be reasonably assumed as unity The constituent activity coefficient γi was calculated, in the
and eqs 4 and 5 become present work, from the UNIQUAC model14 with the interaction
variable (τij) defined as
KIi ) yi ⁄ xIi ) γIi PSi ⁄ P (6)
KIIi ) yi ⁄ xIIi ) γIIi PSi ⁄ P (7) (
τij ) exp aij +
bij
T
+ cijT) (9)
Thus, the equilibrium pressure at VLLE was calculated from
where aij, bij, and cij are the UNIQUAC binary parameters.
nc nc nc

∑ y P)∑ γ x P ) ∑ γ x P
Binary VLLE Systems. For the binary systems of water (1)
P) i
I I S
i i i
II II S
i i i (8) + methyl acetate (2) and water (1) + methyl propionate (2)
i)1 i)1 i)1

Figure 4. VLLE phase diagram for water (1) + methyl acetate (2) + Figure 5. VLLE phase diagram for water (1) + methyl propionate (2) +
methanol (3) at 323.24 K: (open circles) liquid phase; (open triangles) vapor methanol (3) at 333.15 K: (open circles) liquid phase; (open triangles) vapor
phase; (solid curves) experimental tie lines; (dash-dot-dot curves) phase; (solid curves) experimental tie lines; (dash-dot-dot curves)
UNIQUAC prediction; (dashed curves) UNIQUAC correlation. UNIQUAC prediction; (dashed curves) UNIQUAC correlation.
 Ind. Eng. Chem. Res., Vol. 47, No. 20, 2008 7931
Table 7. Coefficients of Othmer-Tobias Correlation for the Two
Ternary Data
T (K) n m R2a
water + methyl acetate + methanol
313.24 0.0924 0.5474 0.9993
323.24 - 0.2773 0.3582 0.9019
333.15 - 0.3723 0.3705 0.9622
343.15 - 0.2462 0.5672 1.0000
water + methyl propionate + methanol
318.24 0.8197 0.8496 0.9752
333.15 0.0736 0.6276 0.9659
348.15 1.4913 1.3903 0.9407
a
R2: coefficient of correlation.

Figure 7. Othmer-Tobias correlation for water (1) + methyl propionate

(2) + methanol (3).

from the phase equilibrium data of the six constituent binaries.

Figure 6. Othmer-Tobias correlation for water (1) + methyl acetate (2)
+ methanol (3).
the parameters of the UNIQUAC model were determined from
the binary VLLE data by minimizing the objective function π1
Table 9 reports the predicted results. The UNIQUAC parameters
used in the VLLE predictions are listed in Table 10, where the
values of the water/ester pair were determined from the binary
LLE data of this study and those of the rest constituent binaries
were taken from the literature.11,18 Using these predetermined
model parameters, the UNIQUAC model appears to overesti-
mate the two-liquid-phase regions as illustrated in Figures 4
and 5.
The ternary VLLE data were also correlated with the
UNIQUAC model by adjusting six binary parameters (b12, b21,
b13, b31, b23, and b32 with aij ) aji ) cij ) cji ) 0) simultaneously.
The objective function for the VLLE data correlation was
defined as π2

{[ ] [ ] {[ ] [ ]
nP
(Pcalcd - Pexpt
k )
2
(Tcalcd - Texpt
k )
2

∑
nP
(Pcalcd - Pexpt
k )
2
(Tcalcd - Texpt
k )
2

∑
k k
π1 )
k
+
k
+ π2 ) + +
σP σT σP σT

∑ ([ ] [ ]
k)1

[ ] [ ] [ ]}
k)1
nc
(x2,k - xI,expt - xII,expt (xI,calcd - xI,expt
j,k )
2
(xII,calcd - xII,expt) 2
2,k - y2,k )
I,calcd 2
2,k ) (xII,calcd
2,k 2,k )
2
(ycalcd expt 2
j,k
+
j,k j,k
+
+ + σxjI σxjII
σx2I σx2II σy2

[ ] )}
j)1

(10)
where σ is the standard deviation of the measured variables. In
the VLLE calculations, the values of σ were set to 0.05 kPa for
pressure, 0.02 K for temperature, 0.0005 for organic phase
composition, 0.0001 for aqueous phase composition, and 0.0009
for vapor composition.
Table 8 summarizes the results of binary VLLE calculations
in which the UNIQUAC model parameters were treated as a
temperature-dependent function with cij ) cji ) 0. The calculated
phase compositions were compared with the experimental values
in Figures 1 and 2. The agreement is generally satisfactory, but
all the calculated vapor compositions, under the ideal vapor-
phase assumption, exhibit negative deviations from the experi-
mental values for both two systems. Additionally, Figure 3
illustrates that the calculated equilibrium pressures agree
quantitatively with the experimental values.
Ternary VLLE Systems. For a ternary system, the VLLE
properties may be estimated using the parameters determined
j,k - yj,k )
(ycalcd expt 2
(11)
σyj
Table 11 lists the calculated results. Figures 4 and 5 compare
the correlated phase compositions with the experimental and
predicted values. As expected, the correlated results yielded a
substantially better representation than the predictions from the
model with the parameters obtained from the phase equilibrium
data of the constituent binaries.
Conclusion
Isothermal VLLE properties were measured for two binary
and two ternary systems containing water, methanol, methyl
acetate, and methyl propionate at temperatures ranging from
313 to 348 K. The UNIQUAC model with temperature-
dependent parameters can represent well the mutual solubility
properties of water + methyl acetate and water + methyl
propionate over the entire experimental temperature range.
7932 Ind. Eng. Chem. Res., Vol. 47, No. 20, 2008

Table 8. Correlated Results of VLLE for Water (1) + Methyl Acetate (2) and Water (1) + Methyl Propionate (2)
mixture 1 + 2 ∆T AADa (K) ∆P/P AADb (%) organic phase ∆x2I AADa aqueous phase ∆x2II AADa vapor phase ∆y2 AADa
water + methyl acetatec 1.21 2.09 0.0180 0.0008 0.0247
water + methyl propionated 0.19 0.85 0.0047 0.0002 0.0542
a
∆M AAD ) (1/np) ∑knp) 1 (|Mcalcd-Mexpt|)k, where np is the number of data points and M represents T, x2I, x2II, or y2. b ∆P/P AAD (%) ) 100%/np
∑k n)p 1 (|Pcalcd-Pexpt|/Pexpt)k. c UNIQUAC model: τ12 ) exp[-1.3743 + 359.04/T(K)] and τ21 ) exp [2.5424 - 1100.94/T(K)]. d UNIQUAC model: τ12 )
exp[-1.9283 + 503.01/T(K)] and τ21 ) exp [4.2454 - 1808.58/T(K)].

Table 9. Predicted Results from the UNIQUAC Model for the Ternary Systems
T (K) n ga ∆T AADb (K) ∆P/P AADc (%) ∆xI AADd ∆xII AADd ∆y AADd
water (1) + methyl acetate (2) + methanol (3)
313.24 3 1.29 0.68 0.0596 0.0268
323.24 3 1.71 1.06 0.0510 0.0429
333.15 2 2.33 1.34 0.0654 0.0352
343.15 1 2.80 1.53 0.0360 0.0363
water (1) + methyl propionate (2) + methanol (3)
318.24 5 1.23 6.01 0.0394 0.0221 0.0900
333.15 5 0.91 2.01 0.0369 0.0040 0.0660
348.15 5 0.97 1.19 0.0390 0.0147 0.0463
a
ng is the number of calculated data points. The deviations consider only the data points which are in the predicted immiscible region, that is, ng may
not be equal to the number of experimental data points. b ∆T AAD (K) )1/ng ∑kng) 1 (|Tcalcd - Texpt|)k. c ∆P/P AAD (%) ) 100%/ng ∑kng) 1 (|Pcalcd -
P |/Pexpt)k. d ∆M AAD ) 1/ng × nc ∑kng) 1 ∑jn)c 1 (|Mjcalcd - Mjexp t|)k, where nc is the number of components and M represents xI, xII, or y.
expt

Table 10. UNIQUAC Parametersa Determined from Constituent Binaries

i-j aij aji bij (K) bji (K) cij (K-1) cji (K-1) source
water (1) + methyl acetate (2) + methanol (3)
1-2 -1.3743 2.5424 359.04 -1100.94 this work
1-3 2.0585 -3.1453 -219.04 575.68 -0.0070149 0.0060713 Popken et al.18
2-3 -0.72476 0.71011 -326.2 -62.972 0.0023547 -0.001167 Popken et al.18
water (1) + methyl propoinate (2) + methanol (3)
1-2 -1.9283 4.2454 503.01 -1808.58 this work
1-3 2.0585 -3.1453 -219.04 575.68 -0.0070149 0.0060713 Popken et al.18
2-3 -394.99 58.92 Polak and Lu11
a
UNIQUAC model: τij ) exp(aij + bij/T + cijT).

Table 11. Correlated Results from the UNIQUAC Modela for the factorily with the UNIQUAC model by adjusting six binary
Ternary Systems parameters simultaneously.
∆T ∆P/P ∆xI ∆xII ∆y
T (K) AADb (K) AAD (%)c AADd AADd AADd
Acknowledgment
water (1) + methyl acetate (2) + methanol (3)
Financial support from the Ministry of Economic Affairs,
313.24 0.64 2.27 0.0123 0.0049
323.24 0.71 1.80 0.0197 0.0029 Taiwan, through Grant No. 95-EC-17-A-09-S1-019 is gratefully
333.15 0.96 1.28 0.0195 0.0021 acknowledged.
343.15 0.96 0.73 0.0318 0.0072
water (1) + methyl propoinate (2) + methanol (3) Nomenclature
318.24 0.26 2.41 0.0265 0.0054 0.0590
333.15 0.30 0.87 0.0176 0.0082 0.0387 aij ) parameters of the UNIQUAC model
348.15 0.29 0.39 0.0209 0.0054 0.0333 bij ) parameters of the UNIQUAC model
cij ) parameters of the UNIQUAC model
a
UNIQUAC model: τij ) exp(bij/T), where bij and T are both in K. Ki ) distribution ratio for component i
Optimized value of UNIQUAC parameters for water (1) + methyl m, n ) Othmer-Tobias constants
acetate (2) + methanol (3): b12 ) -101.32, b21 ) -254.26, b13 ) nc ) number of components
-1452.27, b31 ) 425.20, b23 ) -1407.71, b32 ) 344.14. Optimized ng ) number of calculated data points
value of UNIQUAC parameters for water (1) + methyl propionate (2) +
methanol (3): b12 ) -157.48, b21 ) -369.90, b13 ) -1010.10, b31 )
np ) number of data points
376.93, b23 ) -894.24, b32 ) 257.84. b ∆T AAD (K) )1/np ∑k n)p 1 P ) pressure (kPa)
(|Tcalcd - Texpt|)k, where np is the number of data points. c ∆P/P AAD q ) surface area parameter of the UNIQUAC model
(%) ) 100%/np ∑knp) 1 (|Pcalcd - Pexpt|/Pexpt)k, where np is the number of r ) volume parameter of the UNIQUAC model
data points. d ∆M AAD ) 1/np × nc ∑k n)p 1 ∑j n)c 1 (|Mjcalcd-Mjexpt|)k, R ) gas constant (J mol-1 K-1)
where nc is the number of components and M represents xI, xII, or y.
R2 ) coefficient of correlation
T ) temperature (K)
Using the parameters determined from the phase equilibrium V ) molar volume (cm3 mol-1)
data of the constituent binaries, the UNIQUAC model w ) weight fraction in the liquid phase
overestimated the two-liquid-phase regions of water + methyl x ) mole fraction in the liquid phase
acetate + methanol and water + methyl propionate + y ) mole fraction in the vapor phase
methanol. The ternary VLLE data can be correlated satis- zi ) mole fraction of component i in the feed
 Ind. Eng. Chem. Res., Vol. 47, No. 20, 2008 7933
R ) fraction of the total material in the vapor phase (6) Sorensen, J. M.; Arlt, W. Liquid-Liquid Equilibrium Data Collection-
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1979; Vol. V, Part 1, p 177 (original data from Venkataratnam et al., 1957).
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φi ) fugacity coefficient of compound i Binary Systems. Chemistry Data Series; DECHEMA: Frankfurt, Germany,
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