J. Chem.

Thermodynamics 1998, 30, 153]159

Isothermal ( vapour H liquid) equilibria of

( ethanol H propanone H acetonitrile H benzene)
at the temperature 318.15 K
Isamu Nagata a and Kazuhiro Tamura
Department of Chemistry and Chemical Engineering, Di¨ ision of Physical Sciences,
Kanazawa Uni¨ ersity, 40-20, Kodatsuno 2-chome, Kanazawa, Ishikawa 920, Japan

The Žvapour q liquid. equilibria are reported for Žethanol q propanone q acetonitrile q
benzene. at the temperature 318.15 K. The experimental results were measured with a
modified Boublik vapour-recirculating still and are analysed using the UNIQUAC formalism
having only binary parameters. Q 1998 Academic Press Limited

KEYWORDS: Žvapour q liquid. equilibria; activity coefficient; mixture

1. Introduction
Experimental quaternary Žvapour q liquid. equilibrium ŽVLE. results providing
some basic information about multicomponent distillation, azeotropic distillation
etc., are still limited in number Ž1. and isothermal VLE results are useful from a
theoretical point of view to check the validity of solution models. As part of our
studies on isothermal VLE equilibrium of quaternary mixtures involving
hydrogen-bonded molecules, isothermal VLE results for Žmethanol q propanone
q acetonitrile q benzene. were reportedŽ2. by this laboratory. This paper reports
the experimental VLE results at the temperature T s 318.15 K for Žethanol q
propanone q acetonitrile q benzene., which contains four binary azeotropic
mixtures Žethanol q propanone., Žethanol q acetonitrile ., Žethanol q benzene.,
and Žacetonitrile q benzene. that deviate greatly from ideality. The measured
quaternary results are compared with those predicted from the UNIQUAC
formalism with only binary parameters, determined from binary VLE results for six
mixtures: Žethanol q propanone. at T s 323.15 K,Ž3. Žethanol q acetonitrile . at
T s 313.5 K,Ž4. Žethanol q benzene. at T s 318.15 K,Ž5. Žpropanone q acetonitrile .
at T s 318.15 K,Ž6. Žpropanone q benzene. at T s 318.15 K,Ž7. and Žacetonitrile q
benzene. at T s 328.15 K.Ž8.

2. Experimental
Acetonitrile ŽAnalytical reagent: Wako Pure Chemical Industries Ltd.. was used
a
To whom correspondence should be addressed ŽE-mail: tamura@heikou1.ch.t.kanazawa-u.ac.jp..

0021]9614r98r020153 q 07 $25.00r0rct970283 Q 1998 Academic Press Limited

154 I. Nagata and K. Tamura

TABLE 1. Densities r ŽT s 298.15 K. of substances

used in this work

rrŽg . cmy3 .
Component This work Literature

C 2 H 5 OH 0.78503 0.78504 a
CH 3 COCH 3 0.78442 0.78440 a
CH 3 CN 0.77662 0.77660 a
C6 H6 0.87369 0.87370 a
a
Reference 9.

directly, ethanol and propanone ŽAnalytical reagent: Wako Pure Chemical

Industries Ltd.. were fractionated after storage over anhydrous copper sulfate and
chemically pure benzene was purified by repeated fractional crystallization. The
g.c. analysis confirmed that the purities of chemicals used were better than 0.999
mole fraction and the densities of the chemicals, measured with an Anton-Paar
densimeter at T s 298.15 K, agreed well with the literature values,Ž9. as shown in
table 1.
VLE results at T s 318.15 K were measured using a modified Boublik vapour-
recirculating still as described previously.Ž10. The liquid- and vapour-phase samples
of quaternary equilibrated mixtures were withdrawn with preheated Hamilton
syringes and their compositions were determined with a thermal conductivity-based
g.c. ŽShimadzu GC-8A. equipped with an electronic integrator ŽShimadzu
Chromatopac, C-R6A.. A good separation of the four components was obtained on
a 3 m Ži.d. 3 mm. column packed with PEG-1000 20-80M Ž15 per cent by volume
polyethylene glycol on Shimalite F.. The column temperature was 393.15 K and the
detector current was 100 mA at a helium flow rate of 1 cm3 . sy1 . The g.c. was
calibrated with gravimetrically prepared mixtures. Three analyses were made for
each sample to obtain a mean value. The experimental errors of the measured
variables were: mole fraction, 0.002; pressure, 13 Pa; temperature, 0.05 K.

3. Results and analyses

Table 2 shows the experimental results for Ž1 y z 2 y z 3 y z 4 .C 2 H 5 OH q
z 2 CH 3 COCH 3 q z 3 CH 3 CN q z 4 C 6 H 6 4 . Here z s x for liquid-phase mole fraction,
z s y for vapour-phase mole fraction, and p is the total pressure. The activity
coefficients f i and fugacity coefficients f i were calculated using the following
equations:

f i s pyi f ir x i pTi fTi exp  ViT Ž p y pTi . rRT 4 , Ž 1.

ln f i s 2 . Ý y j Bi j y
ž Ý Ý yi yj Bi j / prRT , Ž 2.
j i j

where pTi and ViT are the observed pure-component vapour pressures and liquid
TABLE 2. Experimental results for Ž1 y x 2 y x 3 y x 4 .C 2 H 5 OH q x 2 CH 3 COCH 3 q x 3 CH 3 CN q x 4 C 6 H 6 4 at the temperature T s 318.15 K;
f i and fi are the activity coefficients and fugacity coefficients, respectively

x2 x3 x4 y2 y3 y4 prkPa f1 f2 f3 f4 f1 f2 f3 f4

0.107 0.337 0.269 0.150 0.277 0.311 43.263 1.709 0.915 1.278 1.705 0.980 0.976 0.943 0.993
0.050 0.544 0.212 0.071 0.428 0.283 40.423 1.953 0.861 1.132 1.823 0.983 0.978 0.943 0.998
0.198 0.413 0.175 0.273 0.308 0.211 44.530 1.856 0.918 1.177 1.818 0.981 0.976 0.939 0.995
0.151 0.561 0.227 0.219 0.420 0.275 41.717 2.531 0.906 1.109 1.714 0.984 0.977 0.941 0.997
0.045 0.588 0.119 0.066 0.480 0.193 38.650 1.750 0.852 1.123 2.138 0.984 0.981 0.942 1.003
0.050 0.268 0.529 0.072 0.247 0.474 42.796 2.488 0.922 1.414 1.289 0.982 0.976 0.949 0.988
0.163 0.424 0.331 0.222 0.330 0.337 43.743 2.545 0.891 1.211 1.504 0.983 0.975 0.942 0.992
0.125 0.174 0.614 0.189 0.173 0.497 43.970 3.066 0.994 1.571 1.193 0.984 0.976 0.952 0.985
0.172 0.163 0.428 0.237 0.145 0.388 46.516 1.936 0.957 1.479 1.415 0.981 0.974 0.947 0.986
0.054 0.243 0.470 0.074 0.222 0.450 43.023 2.014 0.882 1.409 1.385 0.982 0.976 0.949 0.988
0.194 0.191 0.348 0.267 0.157 0.338 46.543 1.778 0.956 1.365 1.519 0.980 0.974 0.945 0.988
0.051 0.164 0.466 0.071 0.164 0.464 42.943 1.740 0.894 1.544 1.436 0.982 0.976 0.952 0.987
0.104 0.167 0.338 0.153 0.161 0.379 44.503 1.498 0.979 1.536 1.678 0.980 0.975 0.948 0.988
0.051 0.088 0.457 0.081 0.098 0.486 43.223 1.539 1.028 1.910 1.515 0.982 0.977 0.955 0.986
0.106 0.070 0.411 0.165 0.072 0.440 44.156 1.483 1.028 1.636 1.585 0.981 0.976 0.954 0.986
0.152 0.331 0.230 0.210 0.269 0.278 44.383 1.611 0.917 1.282 1.812 0.980 0.975 0.942 0.993
0.157 0.406 0.227 0.216 0.310 0.261 44.023 1.916 0.906 1.194 1.712 0.981 0.976 0.941 0.994
0.105 0.401 0.248 0.144 0.317 0.313 42.716 1.918 0.876 1.202 1.626 0.981 0.976 0.943 0.994
VLE of Žethanol q propanone q acetonitrile q benzene.

0.207 0.487 0.239 0.293 0.352 0.264 43.210 2.523 0.915 1.109 1.615 0.983 0.976 0.941 0.995
0.073 0.117 0.676 0.124 0.122 0.544 43.343 2.923 1.102 1.631 1.168 0.984 0.977 0.956 0.984
155
 156

TABLE 3. Vapour pressure pTi , liquid molar volume ViT , structural parameters ri and qi for the pure components, and second virial
coefficients Bi i for the pure components, and cross second virial coefficients Bi j at T s 318.15 K

C 2 H 5 OH CH 3 COCH 3 CH 3 CN C6 H6

pTi rkPa 23.100 68.350 27.771 29.800

ViT rŽcm3 . moly1 . 59.43 76.35 53.75 91.60
ri 1.69 2.06 1.50 2.56
qi 1.12 1.85 1.40 2.05
yBi irŽcm3 . moly1 . 1887 1496 4768 1349
ŽC 2 H 5 OH q CH 3 COCH 3 . ŽC 2 H 5 OH q CH 3 CN. ŽC 2 H 5 OH q C 6 H 6 .
I. Nagata and K. Tamura

yBi j Žcm3 . moly1 . 1277 2303 665

ŽCH 3 COCH 3 q CH 3 CN. ŽCH 3 COCH 3 q C 6 H 6 . ŽCH 3 CN q C 6 H 6 .
3. y1 .
yBi jrŽcm mol 2458 1092 1193
 TABLE 4. The results of fitting the association model with the VLE results for binary mixtures and root mean square deviations:
d p, d T, d x, and d y; x B s 1 y xA

Binary mixture TrK K AB ŽT . a yhAB rŽkJ . moly1 . aAB rK aBA rK d prkPa d TrK Ž10 3 . d x . Ž10 3 . d y .

Ž xAC 2 H 5 OH q
x B CH 3 COCH 3 . 323.15 35.0 21.0 314.20 y9.78 0.0347 0.00 0.1
Ž xAC 2 H 5 OH q
x B CH 3 CN. 315.15 50.0 17.0 517.81 66.11 0.1187 0.02 0.6 3.7
Ž xAC 2 H 5 OH q
xBC6 H6 . 318.15 3.0 8.3 y5.22 104.74 0.1107 0.02 0.6 3.7
Ž xACH 3 COCH 3 q
x B CH 3 CN. 318.15 y17.86 37.09 0.1067 0.03 0.3 1.5
Ž xACH 3 COCH 3 q
xBC6 H6 . 318.15 y48.30 130.97 0.1307 0.04 0.4 2.7
Ž xACH 3 CN q
xBC6 H6 . 328.15 y37.07 313.15 0.2160 0.00 0.6 7.9
a
T s 323.15 K.
VLE of Žethanol q propanone q acetonitrile q benzene.
157
158 I. Nagata and K. Tamura

molar volumes calculated from a modified Rackett equation,Ž11. R is the gas

constant, and Bii and Bi j are the pure and cross second virial coefficients: values
of Bi i were mainly taken from the literature,Ž12 ] 14. and values of Bi j were
estimated by the method of Hayden-O’Connell.Ž15. The values of pTi , ViT , B and
pure-component molecular-size and molecular-area parameters ri and qi , estimated
from the method of Vera et al.,Ž16. are summarized in table 3.
The experimental quaternary VLE results were analysed using the UNIQUAC
formalismŽ17. with only binary parameters obtained from the binary VLE results.
We assume that alkanol ŽA. self-associates to yield linear polymers of any length
A i and solvates with one active non-associating molecule ŽB. to form A i B, where i
ranges from 1 to `. The equilibrium constants are assumed to be independent of
the chain size: the association constant for ethanol is K A s 110.4 at T s
323.15 K;Ž18. the enthalpy of a hydrogen bond is hA s y23.2 kJ . moly1 ;Ž19. the
solvation parameters were taken from Nagata.Ž17. The temperature-dependence of
the equilibrium constants is fixed by the van’t Hoff equation. An optimum set of
the binary molar energy parameters of the model was obtained using a computer
programme based on the maximum likelihood principle.Ž20. The standard deviations
for the experimental values in obtaining the binary parameters were set as 0.13 kPa
for pressure, 0.05 K for temperature, 0.001 for liquid mole fraction, and 0.003 for
vapour mole fraction. Table 4 gives the solvation constant K AB , the enthalpy hAB
of complex formation, the binary parameters aAB and aBA , and the root-mean
square deviations between experimental and the most probable calculated values of
the measured variables Ž d p for pressure, d T for temperature, d x for liquid mole
fraction, and d y for vapour mole fraction.. Table 5 shows the absolute arithmetic-
mean and root-mean deviations of the vapour mole fractions and pressures
between the quaternary experimental results and those calculated from the
UNIQUAC formalism using the binary parameters from table 5, indicating
agreement is good in the summarized results for 15 quaternary mixtures.Ž2,21. We
conclude that quaternary VLE data for Žethanol q propanone q acetonitrile q
benzene. at T s 318.15 K compare well with those predicted by using the
UNIQUAC formalism with only binary parameters and are considered to be
thermodynamically consistent.

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x 3 CH 3 CN q x 4 C 6 H 6 4

Deviations 10 3 . d Ž1 y y 2 y y 3 y y4 . 10 3 . d y 2 10 3 . d y 3 10 3 . d y4 d prkPa 10 2 . d prp

Mean 4.9 5.1 4.8 4.7 0.2753 0.63

Root-mean square 5.6 5.9 5.7 5.5 0.3013 0.69
 VLE of Žethanol q propanone q acetonitrile q benzene. 159

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(Recei¨ ed 2 June 1997; in final form 18 July 1997)

WE-101