Fluid Phase Equilibria 255 (2007) 17–23

Isobaric vapor–liquid equilibria for the quaternary reactive system:

Ethanol + water + ethyl lactate + lactic acid at 101.33 kPa
Patricia Delgado, Marı́a Teresa Sanz ∗ , Sagrario Beltrán
Department of Chemical Engineering, University of Burgos, 09001 Burgos, Spain
Received 5 January 2007; received in revised form 20 March 2007; accepted 22 March 2007
Available online 27 March 2007

Abstract
Isobaric vapor–liquid equilibrium (VLE) data of the reactive quaternary system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid (4) have
been determined experimentally. Additionally, the reaction equilibrium constant was calculated for each VLE experimental data. The experimental
VLE data were correlated using the UNIQUAC equation to describe the chemical and phase equilibria simultaneously. For some of the non-reactive
binary systems, UNIQUAC binary interaction parameters were obtained from the literature. The rest of the binary UNIQUAC parameters were
obtained by correlating the experimental quaternary VLE data obtained in this work. A maximum pressure azeotrope at high water concentration
for the binary reactive system ethyl lactate + water has been calculated.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Vapor–liquid equilibria; Chemical equilibrium; Esterification; Lactic acid; Ethyl lactate

1. Introduction
Lactic acid esters are used as powerful high-boiling sol-
vents. Ethyl lactate particularly is used as food and perfumery
additive, flavor chemical and solvent [1]. Methyl, ethyl, iso-
propyl and n-butyl lactates are usually produced by conventional
esterification of lactic acid with the corresponding alcohol.
Esterification reactions are equilibrium-limited reactions and
usually do not reach completion. Higher conversion can be
obtained by shifting chemical equilibrium towards products for-
mation by hybrid processes such as reactive distillation and
pervaporation aided-reactors. By removing directly the prod-
ucts from the reactive section of the reactive distillation column,
higher conversions can be obtained. Additionally, the integra-
tion of a pervaporation unit into conventional esterification
processes is also attractive because pervaporation is based on
the differences in solubility’s and transport rates in a dense
membrane.
The design of such hybrid processes requires the knowledge
of phase equilibrium as well as of reaction kinetics. During the
last years different studies on thermodynamic properties involv-
∗ Corresponding author. Tel.: +34 947 258810; fax: +34 947 258831.
E-mail address: tersanz@ubu.es (M.T. Sanz).
ing lactic acid and its derivatives have been carried out in our
work group. In a previous paper, VLE behavior for the quater-
nary reactive mixture methanol + water + methyl lactate + lactic
acid was studied [2]. In this work, VLE measurements for the
quaternary system involved in the esterification of lactic acid
with ethanol at 101.33 kPa are presented:
CH3 CHOHCOOH + CH3 CH2 OH
 CH3 CHOHCOOCH2 CH3 + H2 O
A previous kinetic study for the esterification of lactic acid
with ethanol has already been performed in detail [3].
Quaternary experimental VLE data with simultaneous chem-
ical equilibrium have been reported in the literature for different
esterification systems. Hirata and Komatsu [4,5] studied the VLE
of the systems involved in the esterification of acetic acid with
butanol [4] and with ethanol [5] in a modified Othmer still. They
reported the ratio of VLE composition establishing different cor-
relations with temperature and composition. Lee and Kuo [6]
presented VLE data for the esterification of acetic acid with iso-
propanol obtained in an Othmer type equilibrium cell. Similar
procedure was followed by Kang et al. [7], Lee and Lin [8] and
Lee and Liang [9] to determine the phase and reaction equilibria
of the esterification of acetic acid with ethanol [7], isoamyl alco-
hol [8] and 1-pentanol [9], respectively. Recently, Teodorescu et

0378-3812/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.03.022
18 P. Delgado et al. / Fluid Phase Equilibria 255 (2007) 17–23
al. [10] and Bernatová et al. [11] investigated the VLE behavior
in a modified Dvorak and Boublı́k still for the esterification of
acetic with 2-propanol [10] and methanol [11], respectively. In
all cases, activity coefficient models were used to correlate the
VLE data of the quaternary reactive systems proving that the
experimental chemical equilibrium data could be also satisfac-
torily predicted using conventional activity coefficient models
with parameters calculated from vapor–liquid equilibrium data
[12].
In this work, the experimental data were correlated by using
the UNIQUAC equation to satisfy the phase as well as the chemi-
cal equilibrium of the mixture. The fitting procedure was similar
to the one proposed by Teodorescu et al. [10] and Bernatová et
al. [11]. For some of the non-reactive binary systems, interac-
tion parameters were obtained from the literature and fixed in
the fitting procedure. The rest of the UNIQUAC binary inter-
action parameters were obtained from the correlation of the
experimental VLE data of the quaternary system obtained in
this work.
2. Thermodynamics of VLE with chemical reaction
Carvoli and Delogu [13] considered two different ways to
study phase equilibrium of reacting systems: according to the
first one, chemical and phase equilibrium must be reached simul-
taneously; in the second one, experimental conditions allow
phase equilibrium to be reached in shorter time than chemi-
cal equilibrium. The second approach can be assumed for slow
reaction systems.
The general equation for VLE equilibrium at constant low
pressure, p, and temperature, T, of a given mixture is given by,
φi yi p = γi xi psat
i φi
sat
where γ i is the activity coefficient of component i, φi its fugacity
coefficient and xi and yi the composition of the liquid and vapor
phases respectively. φisat is the fugacity coefficient of pure satu-
rated vapor i at temperature T and the corresponding saturation
pressure psat
i .
When a reaction takes place in the liquid phase, an additional
constraint for the chemical potential, μi has to be included,
c description of the apparatus has been previously reported [16].

ν i μi = 0
i=1
where c is the number of components, μi the chemical poten-
tial of component i and νi is the stoichiometric coefficient of
component i in the reaction.
The thermodynamic equilibrium constant, Keq is expressed
in terms of the standard Gibbs energy change of reaction as:
 
−G0
Keq = exp
RT
This equilibrium constant is also expressed as a function of
the mole fraction (xi ) and the activity coefficients (γ i ) of products
and reactants by Eq. (4):
c c
 
Keq = Kx Kγ = (xi )νi (γi )νi (4)
i=1 i=1
3. Experimental
3.1. Materials
Ethyl lactate was supplied by Aldrich with a reported purity
of 99 wt%. It was purified by vacuum distillation, obtaining a
final purity of 99.9%, as determined by gas chromatography
(GC). Ethanol of 99.9 wt% purity was purchased from Lab-Scan.
Water was nanopure. An aqueous lactic acid solution (20 wt%)
was supplied by Acros. The amount of polymerized lactic acid
was considered negligible after being determined by back titra-
tion. As an additional purity check, some physical properties of
the pure components were measured and compared with values
reported in the literature. Results were presented in a previous
publication [14].
3.2. Sample analysis
The samples were analyzed using a Hewlett Packard (6890)
gas chromatograph (GC) equipped with series connected ther-
mal conductivity (TCD) and flame ionization (FID) detectors.
Helium, 99.999% pure, was used as carrier gas. The GC column
was a 30 m × 0.25 mm bonded phase fused silica capillary col-
umn. The injector and detectors were at 523.15 and 533.15 K,
respectively. The oven was operated at programmed tempera-
ture, from 363 to 473 K. 1,2-Propanediol was used as internal
standard for analysis of the quaternary samples [15]. Quantita-
(1) tive analysis of monomer lactic acid was carried out by titration
using phenolphthalein as indicator. Experimental concentration
uncertainties were ±0.0005.
3.3. Apparatus and procedure
VLE for the reactive quaternary system subject of this work
was determined in an all-glass still of the Gillespie type with
circulation of both the liquid and vapor phases. A detailed
(2) The still was operated under a nitrogen atmosphere. The total
pressure of the system was monitored with a digital manometer
and controlled to the desired value (±0.09 kPa) by means of a
pressure controller (Normastat 75). Temperature (±0.05 K) was
measured with a digital thermometer (Ertco-Hart, Model 850).
A kinetic study of the esterification reaction of lactic acid
with ethanol is necessary to establish how the phase and
chemical equilibria affect each other. As it was mentioned in
Section 1, such study has already been performed in detail [3].
In that work, some experiments were carried out without the
(3)
addition of external catalyst. Fig. 1 shows the experimental
mole fraction of ethyl lactate at different reaction times obtained
in the esterification of lactic acid with ethanol (T = 338.15 K,
initial molar reactant ratio REtOH/HL = 3) without adding any
 P. Delgado et al. / Fluid Phase Equilibria 255 (2007) 17–23 19

Table 1
Experimental VLE data corresponding to chemical equilibrium for the qua-
ternary system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid (4) at
101.33 kPa: liquid phase mole fraction xi , vapor phase mole fraction yi , tem-
perature T and equilibrium reaction constant Keq

T (K) x1 x2 x3 y1 y2 y3 Keq

356.27 0.2622 0.7004 0.0161 0.5160 0.4815 0.0024 1.8627

357.07 0.2643 0.6914 0.0210 0.5285 0.4681 0.0033 1.6150
357.49 0.1956 0.7646 0.0180 0.4921 0.5041 0.0037 2.2598
357.92 0.1971 0.7687 0.0155 0.7038 0.2921 0.0041 1.4724
358.04 0.1942 0.7648 0.0189 0.5449 0.4505 0.0045 2.4107
358.18 0.2017 0.7656 0.0160 0.5699 0.4253 0.0047 1.6720
358.44 0.1541 0.8142 0.0136 0.5603 0.4357 0.0039 2.1438
358.55 0.1533 0.8057 0.0168 0.6962 0.2969 0.0068 1.3454
359.12 0.1581 0.8031 0.0152 0.5329 0.4624 0.0046 3.1960
359.19 0.1560 0.7985 0.0181 0.4423 0.5525 0.0051 3.0813
Fig. 1. Ethyl lactate mole fraction versus time for the auto-catalyzed esterifica- 359.51 0.1248 0.8389 0.0136 0.4129 0.5829 0.0041 4.7481
tion reaction of lactic acid with ethanol at 338.15 K, initial molar reactant ratio 359.92 0.1597 0.7958 0.0167 0.4703 0.5250 0.0046 4.8014
REtOH/HL = 3 (䊉 experimental data, — autocatalytic kinetic model [3]). 360.01 0.1155 0.8360 0.0164 0.5351 0.4587 0.0061 2.5895
360.32 0.1193 0.8323 0.0147 0.4078 0.5873 0.0048 2.9171
external catalyst. It can be observed that the reaction rate is not 360.72 0.1072 0.8367 0.0163 0.4739 0.5196 0.0064 2.2505
360.76 0.1037 0.8535 0.0131 0.5528 0.4408 0.0063 2.4631
negligible, even without the addition of external catalyst.
360.85 0.1361 0.7984 0.0200 0.4372 0.5556 0.0070 2.1911
The VLE data for the reactive quaternary mixture have been 361.06 0.1066 0.8428 0.0143 0.4890 0.5048 0.0060 2.0376
obtained by using the Gillespie type still previously described 361.20 0.1309 0.8004 0.0186 0.7482 0.2434 0.0083 1.8297
where chemical and phase equilibria are expected to be reached. 361.23 0.1069 0.8520 0.0134 0.4458 0.5482 0.0058 2.1266
In order to avoid long operation times till chemical and phase 361.33 0.1197 0.8255 0.0155 0.5384 0.4531 0.0084 3.0229
361.35 0.1205 0.8273 0.0174 0.3672 0.6253 0.0072 2.3110
equilibrium were reached, the still was filled with quaternary
361.54 0.1237 0.8184 0.0190 0.4554 0.5377 0.0067 2.4139
mixtures with a composition close to the chemical equilibrium. 361.62 0.1182 0.8263 0.0159 0.4427 0.5492 0.0079 2.0240
In addition, mixtures were kept in the still more than 4 h once 361.70 0.1067 0.8370 0.0171 0.4551 0.5376 0.0072 2.7250
temperature remains constant to ensure chemical and phase equi- 361.79 0.0795 0.8787 0.0121 0.3141 0.6805 0.0051 2.1879
librium. Subsequently, samples of liquid and condensed vapor 361.98 0.0881 0.8551 0.0155 0.3770 0.6156 0.0072 2.5711
362.13 0.0911 0.8504 0.0151 0.3700 0.6226 0.0072 2.7446
were withdrawn for analysis. Some authors [6–11] add a hetero-
362.18 0.0863 0.8673 0.0120 0.4853 0.5070 0.0075 2.1878
geneous catalyst to the system in order to shorten the operating 362.19 0.0928 0.8471 0.0160 0.3722 0.6207 0.0069 3.3287
time. 362.20 0.0756 0.8780 0.0116 0.4004 0.5932 0.0062 2.1114
362.48 0.0903 0.8498 0.0156 0.3429 0.6503 0.0066 2.5006
362.66 0.1006 0.8298 0.0232 0.3796 0.6111 0.0090 2.5693
4. Results and discussion
362.83 0.0954 0.8574 0.0140 0.7079 0.2837 0.0083 1.5579
362.87 0.2923 0.4596 0.1453 0.7761 0.1967 0.0270 1.4601
In this work, 115 experiments were carried out to determine 362.96 0.0917 0.8481 0.0147 0.3454 0.6472 0.0072 2.6470
the VLE behavior corresponding to chemical equilibrium at 363.02 0.1411 0.7380 0.0452 0.3439 0.6444 0.0115 5.8912
101.33 kPa for this reactive quaternary mixture. The pressure, 363.22 0.1120 0.7965 0.0285 0.3597 0.6297 0.0103 3.2127
363.31 0.2851 0.4676 0.1429 0.5612 0.4160 0.0224 2.0407
temperature and vapor and liquid composition were determined
363.43 0.0739 0.8637 0.0138 0.3003 0.6928 0.0068 4.2311
experimentally and are listed in Table 1. The concentration range 363.50 0.0739 0.8651 0.0141 0.3581 0.6345 0.0071 2.5375
of high monomer lactic acid concentration was not studied in 363.67 0.1364 0.7243 0.0547 0.4292 0.5544 0.0161 3.0356
order to avoid its polymerization. 363.70 0.2339 0.5219 0.1380 0.3871 0.5928 0.0198 4.4559
The vapor phase fugacity coefficients have been calculated 363.74 0.1159 0.7728 0.0349 0.2751 0.7143 0.0104 5.8547
363.91 0.0797 0.8488 0.0181 0.3045 0.6868 0.0084 3.7689
using the virial equation of state truncated after the second term
363.95 0.0705 0.8674 0.0132 0.2820 0.7112 0.0066 3.9534
and the second virial coefficients were obtained from the Hay- 364.00 0.2424 0.4868 0.1472 0.4788 0.4976 0.0231 2.5093
den and O’Connell [17] correlation. Because of the low vapor 364.09 0.1497 0.6823 0.0678 0.3353 0.6493 0.0149 3.4909
pressure of lactic acid, it was not necessary to use the “chemi- 364.10 0.0848 0.8334 0.0215 0.3610 0.6287 0.0101 4.1820
cal” theory as was proved for the system water + lactic acid [2]. 364.14 0.2491 0.4917 0.1381 0.6496 0.3222 0.0278 1.9399
364.33 0.2369 0.5173 0.1313 0.4037 0.5760 0.0200 4.4622
Activity coefficients were calculated from Eq. (1) by using the
364.45 0.0749 0.8440 0.0215 0.3781 0.6103 0.0114 4.7655
experimental VLE data from the quaternary system taking into 364.53 0.0615 0.8746 0.0119 0.2838 0.7090 0.0070 3.7100
account the non-ideality of the vapor phase. The vapor pressure 364.57 0.1358 0.6852 0.0723 0.3406 0.6418 0.0172 4.0611
of the pure components used in the vapor–liquid equilibrium 364.58 0.2317 0.4992 0.1380 0.4795 0.4949 0.0250 2.2745
calculations were obtained through the Antoine equation. Ai , Bi 364.72 0.0882 0.8060 0.0283 0.2459 0.7443 0.0095 4.2227
364.91 0.0550 0.8801 0.0112 0.2231 0.7707 0.0060 4.8151
and Ci Antoine coefficients are given in Table 2 together with
364.92 0.0895 0.8003 0.0326 0.2889 0.6985 0.0122 4.6689
the van der Waals properties, ri and qi . 364.95 0.0553 0.8853 0.0114 0.2725 0.7201 0.0073 5.3519
According to Eq. (4), the equilibrium constant has been cal- 365.05 0.1986 0.5449 0.1287 0.4154 0.5619 0.0223 3.8292
culated for each experimental data. Similar to other esterification 365.08 0.1489 0.6466 0.0850 0.3562 0.6238 0.0196 4.6032
20 P. Delgado et al. / Fluid Phase Equilibria 255 (2007) 17–23

Table 1 (Continued )
T (K) x1 x2 x3 y1 y2 y3 Keq

365.08 0.0553 0.8791 0.0110 0.2999 0.6921 0.0077 3.2282

365.13 0.1160 0.7631 0.0417 0.3094 0.6783 0.0120 4.8424
365.18 0.0853 0.7995 0.0344 0.2735 0.7146 0.0116 5.5521
365.19 0.0521 0.8816 0.0103 0.2821 0.7102 0.0075 3.8682
365.43 0.0532 0.8809 0.0105 0.3037 0.6884 0.0077 3.4710
365.62 0.0837 0.7909 0.0387 0.2786 0.7073 0.0137 4.5285
365.62 0.1484 0.6320 0.0953 0.2980 0.6820 0.0193 3.6764
365.67 0.1935 0.5423 0.1344 0.4414 0.5316 0.0262 2.2175
365.91 0.0987 0.7467 0.0521 0.2935 0.6899 0.0161 3.8474
365.92 0.1013 0.7397 0.0521 0.2906 0.6934 0.0156 5.2200
366.17 0.0455 0.8915 0.0092 0.2432 0.7497 0.0068 3.8997
366.23 0.1659 0.5824 0.1213 0.3865 0.5878 0.0252 4.4764
366.24 0.1038 0.7360 0.0584 0.2864 0.6970 0.0163 5.9182
366.39 0.0952 0.7373 0.0571 0.2466 0.7372 0.0157 4.7338
366.42 0.1387 0.6297 0.1041 0.3021 0.6754 0.0219 4.0730
366.77 0.1157 0.6972 0.0705 0.2479 0.7341 0.0175 5.6465
366.78 0.0388 0.9019 0.0081 0.2406 0.7529 0.0062 2.9516
366.94 0.1645 0.5622 0.1277 0.3375 0.6376 0.0242 3.4282
366.98 0.1052 0.6989 0.0699 0.2665 0.7149 0.0180 4.0890
367.02 0.1456 0.5815 0.1224 0.3124 0.6623 0.0247 4.7324 Fig. 2. VLE for the binary reactive system water (2) + ethyl lactate (3) at 40
367.20 0.1134 0.6822 0.0770 0.2457 0.7348 0.0190 6.1031 (, ) and 60 ◦ C (, ). The continuous lines represent the VLE calculated by
367.36 0.0974 0.7032 0.0746 0.2300 0.7511 0.0184 5.9360 using parameters from Table 3. The points correspond to experimental data of
367.52 0.1501 0.5933 0.1178 0.3272 0.6475 0.0245 3.2474 Vu et al. [20].
367.71 0.1082 0.6862 0.0826 0.3556 0.6177 0.0260 3.4521
367.77 0.1376 0.5668 0.1332 0.3111 0.6607 0.0275 4.7025
368.02 0.1356 0.6036 0.1151 0.2993 0.6755 0.0245 4.0901 the values obtained from the literature, i.e.: ethanol + water [19],
368.20 0.1172 0.6386 0.0985 0.3495 0.6240 0.0258 3.7611 ethanol + ethyl lactate [14] and water + lactic acid [2,3]. The
368.34 0.1908 0.4584 0.1807 0.3318 0.6375 0.0299 3.5898 rest of the binary interaction parameters were obtained directly
368.47 0.1247 0.6211 0.1102 0.3227 0.6501 0.0267 6.0058 from the quaternary VLE data correlation. These UNIQUAC
368.50 0.1321 0.6060 0.1159 0.3219 0.6514 0.0260 4.0961
binary interaction parameters were obtained by minimizing the
368.62 0.1203 0.6171 0.1095 0.2989 0.6739 0.0265 4.8147
368.64 0.1417 0.5967 0.1362 0.2970 0.6740 0.0284 5.8757 following objective function through the Simplex-Nelder-Mead
368.86 0.1568 0.5272 0.1584 0.3502 0.6164 0.0328 5.2353 method:
369.08 0.1633 0.4847 0.1820 0.3359 0.6295 0.0339 4.8087 n 
c
369.36 0.1197 0.5953 0.1245 0.3013 0.6679 0.0300 4.6300

369.66 0.1036 0.6534 0.0977 0.2852 0.6875 0.0266 5.1095
O.F. = (γexp,ij − γcalc,ij )2 (5)
369.67 0.1419 0.5495 0.1618 0.3720 0.5918 0.0356 4.8949 j=1 i=1
369.69 0.1639 0.4895 0.1865 0.2983 0.6673 0.0336 5.4114
369.72 0.1467 0.5162 0.1823 0.4157 0.5434 0.0400 3.1378 where n is the number of experimental VLE data, c the num-
369.83 0.1700 0.4623 0.1922 0.3216 0.6430 0.0341 3.0433 ber of components, and γ exp , and γ calc the experimental and
369.85 0.1681 0.4271 0.2067 0.3413 0.6193 0.0383 3.4887 calculated activity coefficients, respectively. All the binary UNI-
369.94 0.1175 0.5812 0.1365 0.3107 0.6561 0.0323 4.4716 QUAC parameters are listed in Table 3.
370.16 0.1864 0.4028 0.2290 0.3362 0.6235 0.0391 3.6044
370.27 0.1079 0.6139 0.1135 0.2501 0.7221 0.0266 3.7076
By using the binary UNIQUAC interaction parameters listed
370.86 0.1172 0.5641 0.1474 0.2867 0.6775 0.0347 4.4206 in Table 3, it is possible to calculate the binary reactive systems
370.94 0.1390 0.5092 0.1753 0.3066 0.6557 0.0369 5.6410 that could not be experimentally determined in the circulation
371.21 0.1393 0.4850 0.1953 0.3488 0.6061 0.0438 3.4285 still used in this work. Fig. 2 shows the VLE calculated for
371.49 0.1172 0.5595 0.1533 0.2789 0.6840 0.0357 3.8025 the binary reactive system water (2) + ethyl lactate (3) with the
371.92 0.1459 0.4627 0.2133 0.3359 0.6187 0.0442 3.8223
372.31 0.1336 0.5475 0.1588 0.2590 0.6999 0.0397 4.6487
UNIQUAC parameters presented in Table 3 at 40 and 60 ◦ C.
372.73 0.1794 0.2583 0.4107 0.1948 0.7360 0.0664 5.4682 In this graph, experimental results obtained by Vu et al. [20]
373.39 0.1100 0.5342 0.1756 0.2989 0.6525 0.0463 2.7115 for this binary reactive system are also shown. As can be
374.23 0.1132 0.4940 0.1984 0.2828 0.6665 0.0486 3.3047 observed not big differences exist between the VLE behav-
374.69 0.1200 0.4828 0.2050 0.3066 0.6385 0.0529 3.3265 ior predicted by UNIQUAC equation with binary interaction
parameters obtained from correlation of the quaternary VLE
data and VLE experimental data obtained directly in the study
reactions, the equilibrium constant shows a slight dependence of the VLE behavior for this binary reactive system. A maxi-
on temperature in the range considered in this work. mum pressure azeotrope is formed at high water concentration.
Experimental VLE data for this reactive quaternary system Vu et al. [20] reported a predicted azeotropic composition at
were correlated by using the UNIQUAC equation to satisfy 6.5–6.7 mol% ethyl lactate based on their UNIQUAC fit. In
the chemical equilibrium condition as well as the vapor–liquid this work, azeotropic compositions at 6.4–6.6 and 6.8–7.0 mol%
equilibrium condition. In the fitting procedure some of the non- ethyl lactate have been predicted by using the binary interaction
reactive binary UNIQUAC interaction parameters were fixed in parameters listed in Table 3 at 40 and 60 ◦ C, respectively.
 P. Delgado et al. / Fluid Phase Equilibria 255 (2007) 17–23 21

Table 2
Pure components parameters: van der Waals properites, ri and qi , and Antoine equationa coefficients Ai , Bi and Ci
Compound ri qi Antoine constants Literature for the
Antoine constants
A B C

Water 0.9200 1.4000 7.0436 1636.91 224.92 [18]

Ethanol 2.1055 1.9720 7.1688 1552.60 222.42 [18]
Ethyl lactate 4.4555 3.9280 7.8269 2489.7 273.15 [18]
Lactic acid 3.1648 2.8800 7.2471 1968.21 158.94 [19]
a Antoine equation: log(p(kPa)) = A − B/[(T(◦ C)) + C].

No azeotrope was found for the other two calculated VLE phase was about 30 wt%. Although the presence of lactoyllactic
systems: ethanol (1) + lactic acid (4) and ethyl lactate (3) + lactic acid is not very important at this concentration (about 1 wt%),
acid (4). oligomers formation and esterification could take place in some
To evaluate the quality of the correlation, the experimental extent. Barbosa and Doherty [22] pointed out the need for hav-
variables have been recalculated by taking into account phase ing accurate thermochemical data to correctly describe the phase
and chemical equilibrium. To solve the phase and chemical reac- and chemical equilibrium of reactive mixtures. The deviations
tion equilibrium simultaneously, an algorithm similar to the one obtained in the value of the reaction equilibrium constant could
proposed by Barbosa and Doherty [12] has been used in this be also responsible for the differences between experimental and
work. In this study, the following empirical expression for the calculated variables.
reaction equilibrium constant was used:
2431.2 4.1. Reactive phase diagrams
ln Keq = 7.8927 − (6)
T (K)
This expression for the reaction equilibrium constant was For a graphical representation of a quaternary system Barbosa
obtained by using the experimental data obtained in this work and Doherty [23] introduced a set of transformed composition
as well as the data obtained in the previous kinetic study [3], variables. In this work, the calculation of these transformed com-
where Kγ was evaluated by using the new UNIQUAC inter- position variables was done by taking ethanol (reactive) as the
action parameters obtained in this work. The average absolute reference component:
percent deviations between experimental and calculated vari-
ables were the following: x2 /% = 2.67, x4 /% = 15.54, T/% = 0.18, X2 = −(x2 + x1 ); X3 = −(x3 + x1 ); X4 = (x4 − x1 ) (7)
y1 /% = 13.60, y2 /% = 11.79; y3 /% = 9.64, and y4 /% = 27.89.
Deviations between experimental data and the calculated vari- Y2 = −(y2 + y1 ); Y3 = −(y3 + y1 ); Y4 = (y4 − y1 ) (8)
ables are slightly high. The highest errors were obtained for
lactic acid, specially its vapor composition due to the low vapor There are two constraints for these new composition vari-
pressure of lactic acid. Lactic acid can suffer self-esterification ables:
reactions at concentration higher than 20 wt% in water [21]. In
this work, the presence of lactic acid oligomers was avoided X2 + X3 − X4 = −1 (9)
by using commercial dilute aqueous solutions of lactic acid.
The highest superficial lactic acid concentration in the liquid Y2 + Y3 − Y4 = −1 (10)

Table 3
UNIQUAC binary interaction parameters for the quaternary system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid (4) at 103.33 kPa, τ ij = exp[−(aij + bij T)/T]

Component 1 Component 2 i j aij /K bij Reference

Ethanol Lactic acid 1 2 191.28 – This work

2 1 −43.32 – This work
Ethanol Ethyl lactate 1 2 −148.67 – [14]
2 1 341.77 – [14]
Ethanol Water 1 2 728.97 −2.0046 [19]
2 1 −756.95 2.4936 [19]
Water Lactic acid 1 2 −39.61 – [3]
2 1 155.18 – [3]
Water Ethyl lactate 1 2 64.53 – This work
2 1 99.80 – This work
Ethyl lactate Lactic acid 1 2 52.64 – This work
2 1 125.29 – This work
22 P. Delgado et al. / Fluid Phase Equilibria 255 (2007) 17–23

List of symbols
G0 standard Gibbs energy (J/mol)
Keq reaction equilibrium constant
Kx reaction equilibrium constant based on concentration
n number of experimental VLE data
O.F. objective function
p pressure (kPa)
R gas constant (J mol−1 K−1 )
T absolute temperature (K)
x liquid mole fraction
y vapor mole fraction

Greek symbols
γ activity coefficient
Fig. 3. The bubble and dew point temperature surfaces at 101.325 kPa for the
quaternary reactive system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid φ fugacity coefficient
(4) at chemical equilibrium: X3 /Y3 , X2 /Y2 , versus temperature, T. μ chemical potential in the liquid phase
ν stoichiometric coefficient

By using the transformed composition variables the condition Subscripts

for a reactive azeotrope can be expressed as [23]: calc calculated value
eq equilibrium
Xi = Yi (11) exp experimental value
i component
Fig. 3 represents the reactive vapor and liquid surfaces cal- 1 ethanol
culated by using the transformed molar fractions. The binary 2 water
mixtures formed by one reactant and one product do not react. 3 ethyl lactate
Any other mixture will react obtaining a quaternary mixture in 4 lactic acid
chemical and phase equilibrium represented by a point inside
the temperature-composition diagram. As can be observed, the Superscripts
two surfaces do not have a common tangent plane, which means c number of components
that reactive azeotropy does not occur for this particular system. sat saturation
Different equilibrium conditions would be achieved by using
higher concentration of lactic acid aqueous solutions instead of Acknowledgments
dilute aqueous solution (20 wt%). A 50 superficial wt% lactic
acid solution contains already 46 and 3 true wt% of lactic acid Financial support of “Junta de Castilla y León” through
monomer and dimmer respectively [24]. For aqueous lactic acid Grant BU019A/05 and “Consejerı́a de Educación y Fondo Social
solutions higher than 20 wt% the role of oligomers should be Europeo” through predoctoral Grant EDU/1490/2003 (P. Del-
taken into account. gado) is gratefully acknowledged.

5. Conclusions References

The VLE for the quaternary reactive system ethanol + water +
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a global understanding of the real system.
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