Fluid Phase Equilibria, 57 (1990) 307-316 307

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

LIQUID-LIQUID EQUILIBRIA FOR THE SYSTEMS WATER-

ALCOHOLS-ACETIC ACID

M.M. ESQUIVEL and M.G. BERNARDO-GIL *

Dep. Eng. Quimica, I.S. T., 1096 Lisboa codex (Portugal)
(Received April 10, 1989)

ABSTRACT

Esqulvel, M.M. and Bemardo-Gil, M.G., 1990. Liquid-liquid equilibria for the systems
water-alcohols-acetic acid, Fluid Phase Equilibria, 57: 307-316.

Liquid-liquid equilibria for the systems water-1-butanol-acetic acid and water-Z

butanol-acetic acid were obtained at 303.15 and 323.15 K. The binodal curves were
determined using the titration method and the tie-lines were obtained by analysing the
compositions of the organic phase. NRTL and UNIQUAC parameters were calculated using
a Nelder-Mead technique to minimize an objective function based on the concentration of
all components in all the phases.

INTRODUCTION

As part of a continuing study of liquid-liquid equilibria involving water,

alcohols and organic acids, this paper reports the determination of binodal
curves and tie-lines for ternary systems containing water, acetic acid and
l-butanol or 2-butanol, at 303.15 and 323.15 K. At these temperatures all
the systems are type I. Some results are published for water-acetic acid-l-
butanol at 298.15 K (Bevia et al., 1984, and Fuse and Iguchi in Sorensen and
Arlt, 1979) and at 299.85 K (Skrzec and Murphy, 1954).

EXPERIMENTAL

The experimental work was carried out using a thermostatted miniature

cell similar to that described by Soares et al. (1974). The temperature was
controlled to an accuracy of 0.05 K and was measured by a precision
thermometer.

* To whom correspondence should be addressed.

037%3812/90/$03.50 Q 1990 - Elsevier Science Publishers B.V.

308

Acetic acid (Merck, minimum purity, 99.0%), l-butanol (BDH, 99.5%)

and 2-butanol (Merck, 99%) were used as supplied. The water was redistilled
and run through an ion-exchange column until it showed an electrical
conductivity less than 7 X lo-’ mho cm-‘.

Determination of binodal curves

Mixtures of water and one of the alcohols of known compositions were

introduced into the equilibrium cell, the temperature remaining constant.
The mixtures were stirred with a magnetic stirrer enabling intimate contact
of the phases in order to attain equilibrium. Acetic acid was added dropwise

TABLE 1
Binodal curves of the system water (1)-l-butanol @)-acetic acid (3)

Weight fractions

XI x, x, x, x, x,
At 303.15 K At 323.15 K
0.2050 0.7950 0.0000 0.2100 0.7900 0.0000
0.2266 0.7155 0.0579 0.2757 0.6463 0.0780
0.2568 0.6487 0.0945 0.3039 0.5937 0.1024
0.3081 0.5658 0.1261 0.3310 0.5547 0.1147
0.3527 0.4950 0.1523 0.3579 0.5245 0.1176
0.3742 0.4727 0.1531 0.3821 0.4977 0.1202
0.4091 0.4305 0.1604 0.4205 0.4481 0.1314
0.4410 0.3979 0.1611 0.4551 0.4101 0.1345
0.4713 0.3720 0.1567 0.4844 0.3785 0.1371
0.4979 0.3493 0.1528 0.5094 0.3512 0.1394
0.5159 0.3258 0.1583 0.5341 0.3295 0.1364
0.5369 0.3083 0.1548 0.5529 0.3087 0.1384
0.5506 0.2898 0.1596 0.5724 0.2917 0.1359
0.5904 0.2486 0.1610 0.5871 0.2752 0.1377
0.6490 0.2050 0.1460 0.6172 0.2494 0.1334
0.6774 0.1786 0.1440 0.6421 0.2281 0.1298
0.7028 0.1586 0.1386 0.6623 0.2179 0.1198
0.7266 0.1434 0.1300 0.6855 0.1948 0.1197
0.7567 0.1195 0.1238 0.7083 0.1771 0.1146
0.7838 0.1272 0.0890 0.7235 0.1615 0.1150
0.8130 0.1034 0.0796 0.7424 0.1451 0.1125
0.8669 0.0864 0.0467 0.7626 0.1324 0.1050
0.9346 0.0654 0.0000 0.7898 0.1122 0.0980
0.8300 0.0986 0.0714
0.8681 0.0642 0.0462
0.9379 0.0621 0.0000
TABLE 2
Binodal curves of the system water (l)-Zbutanol (2)-acetic acid (3)

Weight fractions

Xl x2 x3 x, x2 x,

At 303.15 K At 323.15 K
0.1670 0.8330 o.oooo 0.1950 0.8050 0.0000
0.1775 0.7865 0.0360 0.2273 0.7038 0.0689
0.2180 0.6817 0.1003 0.2576 0.6382 0.1042
0.2505 0.6265 0.1230 0.2883 0.5951 0.1166
0.2781 0.5797 0.1422 0.3151 0.5575 0.1274
0.3045 0.5442 0.1513 0.3387 0.5243 0.1370
0.3252 0.5085 0.1663 0.3813 0.4722 0.1465
0.3488 0.4847 0.1665 0.4191 0.4326 0.1483
0.3703 0.4631 0.1666 0.4511 0.3991 0.1498
0.4079 0.4252 0.1669 0.4784 0.3704 0.1512
0.4399 0.3930 0.1671 0.5050 0.3475 0.1475
0.4614 0.3553 0.1773 0.5438 0.3062 0.1500
0.4912 0.3414 0.1674 0.5770 0.2749 0.1481
0.5148 0.3220 0.1632 0.6398 0.2123 0.1479
0.5332 0.3032 0.1636 0.6872 0.1743 0.1385
0.5470 0.2851 0.1679 0.7169 0.1513 0.1318
0.5751 0.2569 0.1680 0.1674 0.1187 0.1139
0.6026 0.2356 0.1618 0.8110 0.0979 0.0911
0.6460 0.2020 0.1520 0.8250 0.1000 0.0750
0.6708 0.1748 0.1544 0.8510 0.1040 0.0450
0.7003 0.1564 0.1433 0.8760 0.0970 0.0270
0.7242 0.1415 0.1343 0.9209 0.0791 0.0000
0.7547 0.1179 0.1274
0.8150 0.1048 0.0802
0.8584 0.0754 0.0662
0.9174 0.0826 0.0000

from a burette until the mixture became homogeneous. The cell was then left
for 20 min to confirm the attainment of true equilibrium.
To obtain points on the water side of the binodal curve, mixtures of water
and acetic acid were introduced into the cell and the alcohol was added
dropwise from the burette until turbidity was obtained.
Tables 1 and 2 show the mutual solubility data for the systems studied.
The binodal curves are presented in Figs. 1 and 2. The plaitpoints were
estimated using the method of external construction (Coolidge, 1928) and
are also indicated in Figs. 1 and 2.
Tie-line determination

The tie-line data were obtained by preparing several mixtures of the three
components within the area of the binodal curve and by analysing the
Fig. 1. Binodal curves for the system water (1)-1-butanol (2)-acetic acid (3). 0, at 303.15 K,
q, plait point at 303.15 K; V, at 323.15 K, V, plait point at 323.15 K.

Fig. 2. Binodal curves for the system water (1)-2-butanol (2)-acetic acid (3). l , at 303.15 K,
q plait point at 303.15 K; v, at 323.15 K, v plait point at 323.15 K.
 311

organic phase by means of gas chromatography. Mixtures were placed into

the equilibrium cell and were stirred with a magnetic stirrer for at least 30
min and allowed to settle during a period of 3 h. After settling, the organic
phase was sampled using a syringe for direct injection into a gas chromato-
graph (Perkin-Elmer) with a flame ionization detector, connected to an
integrator (Hewlett-Packard).
Calibration curves were obtained using at least six mixtures of known
composition near the binodal curve on the organic side, of which four to six
chromatograms were obtained. Weight fraction measurements were repro-
ducible to within f0.002.
The analysis of the organic phase permits the calculation of the tie-line
point at this side of the binodal curve. With this point and the initial
composition it is possible to determine the concentration of the conjugate
aqueous phase.
To check the composition of acetic acid in the aqueous phase in equi-
librium with the organic phase, some samples of the water phase were
diluted with water and titrated with sodium hydroxide solution using
phenolphthalein as indicator. The average difference between the concentra-
tion of acetic acid obtained by the two methods was about 0.5%.

TABLE 3
Tie-lines of the system water (1)-1-butanol (2)-acetic acid (3)

Weight fractions

x,1 x21 -731 x,2 x22 x32

At 303.15 K
0.2142 0.7609 0.0250 0.8960 0.0788 0.0253
0.2292 0.7144 0.0564 0.8740 0.0863 0.0396
0.2460 0.6694 0.0846 0.8399 0.0981 0.0620
0.2820 0.5976 0.1204 0.8289 0.1019 0.0692
0.3128 0.5576 0.1296 0.7557 0.1272 0.1172
0.5589 0.2797 0.1614 0.5589 0.2797 0.1614 =
At 323.15 K
0.2207 0.7639 0.0154 0.9179 0.0688 0.0132
0.2389 0.7216 0.0395 0.8946 0.0767 0.0287
0.2511 0.6950 0.0540 0.8699 0.0851 0.0450
0.2766 0.6436 0.0798 0.8292 0.0989 0.0719
0.3262 0.5607 0.1132 0.8234 0.1008 0.0758
0.3909 0.4843 0.1248 0.8041 0.1074 0.0886
0.5925 0.2713 0.1362 0.5925 0.2713 0.1362 a

a Plait point.
312

TABLE 4
Tie-lines of the system water (l)-Zbutanol(2)-acetic acid (3)

Weight fractions

41 x21 x31 x,2 x22 x32

At 303.15 K
0.1840 0.7701 0.0459 0.8459 0.0981 0.0560
0.2270 0.6616 0.1111 0.8109 0.1057 0.0834
0.2662 0.5997 0.1342 0.7783 0.1128 0.1090
0.3109 0.5351 0.1540 0.7350 0.1222 0.1428
0.5315 0.2921 0.1764 0.5315 0.2921 0.1764 =
At 323.15 K
0.2017 0.7815 0.0168 0.9057 0.0826 0.0117
0.2100 0.7547 0.0354 0.8747 0.0895 0.0358
0.2191 0.7274 0.0536 0.8647 0.0918 0.0436
0.2343 0.6868 0.0789 0.8525 0.0945 0.0530
0.2792 0.6051 0.1157 0.7934 0.1078 0.0988
0.3303 0.5360 0.1337 0.7659 0.1140 0.1201
0.5497 0.2947 0.1556 0.5497 0.2947 0.1556 =

a Plait point.

The tie-lines for the ternary system water-l-butanol-acetic acid are

presented in Table 3. The results for the system water-Zbutanol-acetic acid
are shown in Table 4.

ANALYSIS OF RESULTS

The reliability of the experimental results in terms of association was

verified using Campbell’s theory (1944).
Campbell observed that the majority of the experimental equilibrium data
were verified by the following expression

K= Lw
bcl (1)

TABLE 5
Values of s and K (Campbell’s method)

Solvent C Solvent B Temp. (K) s K

Water 1-butanol 303.15 0.906 0.985
323.15 0.924 0.889
Water 2-butanol 303.15 0.826 1.699
323.15 1.044 0.755
 313

TABLE 6
Structural parameters for UNIQUAC equation

r 4 4’
Water 0.92 1.40 1.00
Acetic acid 2.20 2.07 2.07
1-butanol 3.92 3.67 0.89
2-butanol 3.92 3.66 0.89

K being an equilibrium constant and [AB] and [AC] being the concentra-
tions of the solute in the organic phase (B) and in the aqueous phase (C),
respectively. If s (an empirical parameter) is equal to unity, this means that
the molecules have the same molecular structure in both phases. Values of s
and K are presented in Table 5.

NRTL and UNIQUAC equations

The NRTL equation (Renon and Prausnitz, 1968) and the UNIQUAC
equation (Abrams and Prausnitz, 1975) were used to correlate the experi-
mental phase equilibrium data.
Anderson and Prausnitz (1978a, b) slightly modified the UNIQUAC
equation to obtain better agreement with systems containing water and
alcohols. The molecular-geometric area parameter ( qi) for the component i
was substituted in the residual part of the UNIQUAC equation by an
empirical parameter q( that is smaller than the geometrical external surface
qi, indicating that, for alcohols, intermolecular attraction is determined
primarily by the OH group (Anderson and Prausnitz, I978a). The values of
the three parameters rj, qi and q,: used in this work for the components are
indicated in Table 6.
Binary parameters were calculated using the Nelder-Mead method
(Bernardo-Gil and Soares, 1986) for the minimization of the following
objective functions

F1 = f E [1n(Yil/Yi2) - ln(xi*/xil)l~ (2)

k=l i=l

F2 = 5 ; ; (xi”i”. - x;;f.)*
(3)
k=l j-1 j=l

with 3M > L, M being the available number of tie-lines, N the number of

components and L the number of parameters.
314

TABLE 7
UNIQUAC parameters and root mean square deviations

System Binary cij cji RMSD ( x 103)

(K) (K) b c

At 303.15 K
Water(l)- l-2 1142.1 390.0 a 8.9 8.0
1-butanol(2)- 1-3 38.30 - 19.14
acetic acid (3) 2-3 - 85.71 1219.5

Water(l)- 1-2 1041.3 640.8 = 10.8 10.8

2-butanol(2)- 1-3 13.51 - 10.53
acetic acid (3) 2-3 - 253.6 104.1

At 323.15 K
Water(l)- l-2 1240.0 389.8 a 6.1 6.1
1-butanol(2)- 1-3 19.87 - 17.57
acetic acid (3) 2-3 - 207.6 142.1

Water(l)- l-2 1137.3 481.1 a 7.2 7.2

2-butanol(2)- 1-3 13.05 - 9.60
acetic acid (3) 2-3 - 316.5 133.5
a Parameters determined from mutual binary solubilities; b Four parameters determined by
correlation of ternary data; ’ Six parameters determined by correlation of ternary data.

TABLE 8
NRTL parameters and root mean square deviations

System Binary bij b,i “ij RMSD (x 103)

(K) b c

At 303.15 K
Water (l)- 1-2 1312.2 - 97.58 0.2860 a 7.3 6.6
1-butanol(2)- 1-3 619.1 - 253.4 0.3287
acetic acid (3) 2-3 109.0 - 84.64 0.4140

Water(l)- l-2 1168.6 14.98 0.3009 a 6.5 5.9

2-butanol(2)- 1-3 619.1 - 253.4 0.3287
acetic acid (3) 2-3 172.4 - 184.5 0.2520
At 323.15 K
Water(l)- 1-2 1420.9 - 115.6 0.2860 a 8.2 5.0
1-butanol(2)- 1-3 564.5 - 180.1 0.3287
acetic acid (3) 2-3 736.5 300.9 0.4140
Water(l)- l-2 1295.6 - 40.52 0.3009 a 8.5 5.1
2-butanol(2)- 1-3 564.5 - 180.1 0.3287
acetic acid (3) 2-3 171.1 -231.1 0.2520
a Parameters determined from mutual binary solubilities; b Six parameters determined by
correlation of ternary data; ’ Nine parameters determined by correlation of ternary data.
 315

The objective function F2 is time consuming. We therefore begin the

calculation by using the objective function Fl and, when the parameters are
near optimized, the calculation continues with the objective function F2.
The UNIQUAC equation has two adjustable parameters per binary. For
ternary mixtures we must fit six parameters. The NRTL equation contain
three parameters, including the non-randomness parameter aij. The value of
aij may be preset or it may be left as a parameter to be calculated. Thus the
NRTL equation has six or nine adjustable parameters for describing a
ternary data set.
Ssrensen et al. (1979) showed that for a type I system, one may choose to
prefix two UNIQUAC parameters from the mutual solubility data of the
partly miscible binary.
In Tables 7 and 8, respectively, the UNIQUAC and the NRTL parame-
ters are presented; these are obtained by correlation of ternary data, fixing
the two parameters describing the interactions water-l-butanol and water-
2-butanol.
Agreement between calculated and experimental data is expressed in
terms of composition root mean square deviations (RMSD)

Tables 7 and 8 also show the values of RMSD between experimental and
calculated compositions. In the same tables, the values of RMSD when the
correlation is obtained calculating all the parameters (six for the UNIQUAC
and nine for the NRTL) are indicated.
The NRTL and UNIQUAC equations represent the binodal curves and
the tie-lines correctly. As we can see, the results are the same when one uses
four or six adjustable parameters in the correlation with the UNIQUAC
equation. With the NRTL equation the results are slightly better when we
calculate nine parameters.

ACKNOWLEDGMENT

We express our gratitude to the Instituto National de Investiga@o

Cientifica, which through the CPQ (Technical University of Lisbon) sup-
ported this work.

LIST OF SYMBOLS

bij NRTL parameter, K

‘ij UNIQUAC parameter, K
316

Fl, F2 objective functions

gij? uij measure of the interaction energy between molecules i and
j
4i
pure component area parameter of component i
41 empirical pure component area parameter for alcohols and
water
pure component volume parameter of component i
l& gas-law constant
RMSD root mean square deviation
xij weight fraction of component i in phase j
xij molar fraction of component i in phase j
“ij
non-randomness NRTL parameter
Yi activity coefficient of component i
T~;(NRTL) NRTL adjustable parameters defined as (Renon and
Prausnitz, 1968) 7ij = (gij - gjj)/( RT) = bij/T
T~~(UNIQUAC) UNIQUAC adjustable parameters defined as (Abrams and
Prausnitz, 1975) rij = exp - (uij - ujj)/(RT) = exp -
(Auij)/(RT) = exp - cij/T
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