Badajoz Et Al 2021 High Pressure Phase Equilibria in An Ethanol Water Binary System Experimental Data and Modeling

pubs.acs.
org/jced Article
High-Pressure Phase Equilibria in an Ethanol/Water Binary System:

Experimental Data and Modeling
Pedro Susial Badajoz,* Diego García-Vera, Patricia Herrera-Vega, and Anibal Marrero-Peŕ ez
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ABSTRACT: Experimental data of vapor−liquid equilibria (VLE) are reported for the binary
systems: ethanol (1) + water (2) at 100, 1500, and 2000 kPa. The data were verified for
thermodynamic consistency by using different low- and high-pressure tests. The following
minimum azeotropes were found for the binary systems: x1,az = y1,az = 0.899 and T = 351.39 K
Downloaded via 190.250.111.43 on April 3, 2024 at 23:53:57 (UTC).
at 100 kPa, x1,az = y1,az = 0.857 and T = 440.70 K at 1500 kPa, and x1,az = y1,az = 0.850 and T =
453.83 K at 2000 kPa. The quality of the azeotropic data obtained was established by
considering the trend of the bibliographic azeotropic data. The phase behavior was modeled
using the Peng−Robinson equation of state (EOS) with several mixing rules and the
perturbed-chain statistical associating fluid theory. The experimental data were satisfactorily
correlated and a qualitative agreement with these predictive models was observed.
■ RESEARCH HIGHLIGHTS
• VLE of water with ethanol was determined at 100, 1500,
the washed stream with approximately 5% (w/w) ethanol to
take advantage of approximately 0.3% (w/w) in fusel oil from
the first-stage distillate;2,3 (4) dehydration stage that can be
and 2000 kPa.
performed, among other different techniques, by extractive
• Data were verified with the area test, Van Ness direct
distillation4 and azeotropic distillation.5
test, and point-to-point test.
Consequently, to obtain anhydrous ethanol, it will be
• Data at high pressure were verified by using the Gibbs−
necessary to analyze different strategies to optimize energy
Duhem equation.
costs. Many studies have focused on analyzing the energy costs
• Azeotropic data of water/ethanol were correlated.
of separating ethanol and water using both extractive
• VLE data of water + ethanol mixtures are well modeled
distillation and azeotropic distillation as strategies.6,7 Notwith-
by using different EOSs.
standing the foregoing, some other techniques can also be used
to obtain anhydrous ethanol.
1. INTRODUCTION It has long been known that the compositions of azeotropes
Greenhouse gases are produced from fossil fuel combustion, can be modified by changing the pressure of the system.8
and those can be replaced by alternative fuels (biofuels) that However, it was Lewis9 who first suggested using the pressure
generate less pollution. In addition to the environmental swing distillation in mixtures that present an azeotrope. This
advantages, biofuels are an interesting alternative as they are a procedure has subsequently been suggested to separate other
renewable resource. azeotropic mixtures,10,11 although probably, the first significant
Ethanol is one of the main substances used in biofuel application was developed by Knapp and Doherty.12
technology. Ethanol is mainly obtained from sugar cane and Therefore, pressure swing distillation13,14 is a technique that,
sugar beet, but it can be obtained from other high cellulosic if applied in the appropriate conditions15,16 and by an
biological materials using yeasts.1 ingenious combination of the rectification columns,12 can
In estimating the costs necessary to obtain pure ethanol, the compete with previous rectification techniques.4,5 This requires
following steps should be considered: (1) a process of
separation and elimination of organic matter and solid particles
followed by distillation, which can be carried out by means of Received: July 27, 2020
steam dragging; (2) rectification of the product from the Accepted: January 11, 2021
previous stage with approximately 40% (w/w) in ethanol to Published: January 21, 2021
generate a distillate with a composition close to 95% (w/w) of
the alcohol; (3) recovery and recirculation of ethanol
discharged by a side stream, followed by a rectification of
© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.jced.0c00686

928 J. Chem. Eng. Data 2021, 66, 928−946
Journal of Chemical & Engineering Data pubs.acs.org/jced Article
Table 1. Experimental and Bibliographic Physical Properties of Pure Substances at 101 kPaa
chemical purity mass purification analysis ρ (298.15 K) nD
name CAS no. source (%) method method Tbp (K) (kg m−3) (298.15 K)
ethanol 64-17-5 ́
Panreac Quimica S.A 99.9 none GCb 351.45c 785.2a 1.35933a
distillation 351.45d 785.2d 1.3594d
Merck Farma 99.8 none GCb 352.07e 785.02e 1.35922e
Acros 99.5 GCb 351.46f 786.47f 1.35939g
351.443g 784.93g 1.35941g
water 7732-18-5 distillation 373.15c 997.1a 1.33249a
distillation 373.15e 997.0e 1.33250e
373.15g 997.05g 1.3325g
distillation 373.15h 997.00h 1.3332h
deionized 373.15i 997.04i 1.33249i
a
The combined expanded uncertainties U(k = 2) are as follows: U(p) = 1 kPa, U(T) = 0.02 K, U(ρ) = 0.2 kg m−3, and U(nD) = 0.0002. bGas
chromatograph informed by the suppliers. cThe combined expanded uncertainties U(k = 2) are as follows: U(Tbp) = 0.06 K and U(pi0) = 2 kPa.
d
Ref 32. eRef 33. fRef 34. gRef 35. hRef 36. iRef 37.
adequate information of the phase equilibrium in a wide range A Mettler Toledo DM-40 model, a digital densimeter with
of temperature and pressure. an accuracy of 0.0001 g/cm3, was used for the density (ρ)
Although, for the ethanol/water system, large amounts of measurements. In the densimeter calibration, air and bidistilled
VLE data17 can be found for both isothermal and isobaric water were employed. An Atago RX-7000α digital refrac-
conditions and, specifically, the latter at pressures close to tometer with an accuracy of 0.0001 was employed for the
atmospheric pressure, only a limited set of data is available for refractive index determinations. For refractometer calibration,
moderate and higher pressures.18,19 bidistilled water was employed.
This is the reasons why the VLE data for the ethanol (1) + Table 1 shows some significant differences in the properties,
water (2) mixture have been experimentally determined at which can be caused by the different purities of the substances,
pressures of 100, 1500, and 2000 kPa. The system presents a a consequence of the different commercial firms that supply
singular point, described in the bibliography,20 whose them, as well as by the different production processes.
composition is modified with the working pressure. As a previous step to VLE determinations, a calibration
The experimental data obtained have been analyzed curve of ethanol mole fraction (x1) versus density pairs (ρij)
thermodynamically considering the verification tests for low was obtained for the ethanol (1) + water (2) binary system.
pressure (area test and point-to-point test)21−24 as well as the The densities (ρij) of samples from the 0 to 1 mole fraction x1
Valderrama test25−27 for high pressure. range, prepared by mass in airtight-stoppered glass bottles
Subsequently, the validated data were used to study the using a Sartorius Lab Instruments GmbH & Co. Entris-224i-1S
predictive capabilities of a certain equation of state (EOS): the balance with an uncertainty of 10−4 g, were measured at 298.15
perturbed-chain statistical associating fluid theory28 (PC- K. In Table 2, the ethanol mole fraction, the density of binary
SAFT) and the Peng−Robinson−Stryjek−Vera model29,30 mixtures, and the excess volumes are shown.
with both quadratic (PRSV) and Wong−Sandler31 (PRSVWS)
mixing rules. Table 2. Densities (ρ) and Excess Volumes (vE) for the
Binary System Ethanol (1) + Water (2) at 298.15 K and 100
2. EXPERIMENTAL SECTION kPaa
2.1. Chemicals and Apparatus. Table 1 shows the ρ 109·vE ρ 109·vE
physical properties, density (ρii), and refractive index (nD) at x1 (kg m−3) (m3 mol−1) x1 (kg m−3) (m3 mol−1)
298.15 K as well as the normal boiling point (Tbp) determined 0.0000 997.1 0.0 0.2772 911.1 −1014.7
́
for ethanol (Panreac Quimica S.A., purity of 99.9% in mass) 0.0096 993.3 −49.5 0.3151 900.8 −1049.6
and water. The comparison with the values found in the 0.0310 985.9 −171.4 0.3552 890.5 −1069.7
bibliography32−37 is also included. 0.0333 985.2 −185.7 0.3971 880.6 −1083.0
Bidistilled water was used in all stages of the experimental 0.0568 977.6 −316.0 0.4546 868.1 −1082.8
work. Water was obtained in our chemical technology 0.0697 973.0 −373.0 0.5517 849.3 −1033.5
laboratory by using a semi-industrial distillation tower with 0.0875 967.1 −454.2 0.6108 838.8 −962.9
12 perforated plates, in which reflux flow was automatically 0.1059 961.6 −543.4 0.7026 824.6 −845.6
0.1267 955.6 −640.3 0.7307 820.1 −774.3
controlled by an electronic device. The flow divider works by
0.1438 949.6 −686.9 0.8250 807.4 −588.0
comparing a reference signal with the temperature measured
0.1495 947.8 −705.5 0.8318 806.5 −570.7
by a Pt-100 probe. In this work, 75% of reflux was established
0.1570 945.6 −733.0 0.8956 798.4 −399.3
and the boiling temperature was monitored with a Pt-100
0.1950 934.5 −853.6 0.9137 795.9 −326.5
probe. In addition to the water properties in Table 1, a
0.2194 927.7 −922.2 1.0000 785.2 0.0
conductivity of 22.0 μS/cm was measured at 298.15 K. 0.2486 919.0 −969.9
The normal boiling point at 101 kPa was obtained from both
substances. For such purpose, the equilibrium still38 was a
The combined expanded uncertainties U(k = 2) are as follows: U(p)
loaded with a pure substance, and a heating system that uses an = 1 kPa, U(T) = 0.02 K, U(ρ) = 0.2 kg m−3, U(x1) = 0.0002, and
electric resistance was run on. U(109·vE) = 14 m3 mol−1.
929 https://dx.doi.org/10.1021/acs.jced.0c00686
J. Chem. Eng. Data 2021, 66, 928−946
Table 3. Fittings Coefficients and Standard Deviations: ρ (eq 1) and vE (eq 2) at 298.15 K and VLE Data (eqs 4−6)
ethanol (1) + water (2)
FF p/kPa RV A0 A1 A2 A3
ρ versus x1 (eq 1) 100 0.31 −172.5 240.4 −518.7 363.7 SD(ρ/kg m−3) = 0.2
vE versus x1 (eq 2) 100 0.48 −5543.2 −3580.6 15193.3 −10,427.2 SD(vE/m3 mol−1) = 6.7 × 10−9
(y1−x1) versus x1 (eq 4) 100 0.20 9.1 −20.4 17.0 −5.8 SD(y1−x1) = 0.003
T versus x1 (eq 5) 100 0.20 −299.7 621.0 −485.7 141.5 SD(T/K) = 0.19
T versus y1 (eq 6) 100 0.68 −30.5 147.3 −357.7 222.7 SD(T/K) = 0.08
T versus x1 (eq 5) 1500 0.09 −300.9 −56.0 773.9 −454.6 SD(T/K) = 0.11
T versus y1 (eq 6) 1500 0.80 −30.1 5.2 −65.2 52.2 SD(T/K) = 0.21
T versus x1 (eq 5) 2000 0.08 −232.5 −276.0 982.9 −511.8 SD(T/K) = 0.11
T versus y1 (eq 6) 2000 0.90 −26.2 −27 −21.8 40.3 SD(T/K) = 0.21
∑1n(Fexp − Fcal)2
a
SD(F ) = with F being (vE/m3 mol−1), (ρ/kg m−3), (y1−x1), or (T/K); n is the number of data.
n−2
2.2. Equipment and Procedure. The ebulliometer homogenized and the boiling point of the pure substance is
described in previous papers38,39 was employed to obtain the verified at the established pressure.
vapor pressures as well as the VLE data for the ethanol (1) + After that time, approximately 15 cm3 of the other pure
water (2) mixtures at 100, 1500, and 2000 kPa. This substance (B) is charged, and therefore, a perturbation is
equipment is included in an experimental setup.39,40 The generated between the phases. This mixture is kept under
different elements as well as the measurement and control boiling conditions for about 90 min in the ebulliometer to
devices of the experimental installation have been previously ensure that an approximate stationary state, as in previous
described.39,40 works, was verified.39,40 When the recirculation time of both
The stainless steel ebulliometer38 has an operating capacity phases has elapsed, each phase is sampled in sealed containers
between 500 and 800 cm3, and it was operated with about 650 for annealing and then measuring the density at 298.15 K.
cm3. The minimum volume to flood the inverted double- Once the samples have been extracted, the equipment must
walled vessel is 500 cm3 and the maximum volume to flood the be reloaded to generate a new perturbation, with a new
still is 800 cm3. quantity (approximately 15 cm3) of the substance (B) to
The ebulliometer design makes the dynamic recirculation of modify the composition of the mixture inside the ebulliometer
both phases due to the steam pumping effect possible. without stopping its operation. In this way, a continuous
Therefore, the mass transfer process can be developed as a determination of the VLE data is achieved.
consequence of the intimate contact between the continuously
recirculated phases from the inverted vessel to the equilibrium 3. RESULTS AND DISCUSSION
chamber of the ebulliometer. 3.1. Excess Volumes and Refraction Index Deviations.
The VLE data are obtained after that mass transfer process, The composition of the liquid phase (x1) and vapor phase (y1)
which has been developed between the phases that are in of the ethanol mole fraction for the binary system ethanol (1)
contact. Every process of mass transfer is a function of the + water (2) at the different pressures of this work was obtained
coefficients of mass transfer and, therefore, of the speed of the through a calibration curve of composition versus density. This
contact between the phases, that is to say, the process is a calibration curve was obtained previously at 298.15 K by
function of the contact time or the length of contact between densimetric determinations of prepared mixtures by weight
the phases. For this reason, it is necessary to know the contact (see Table 2).
time in which the stationary condition is reached (T, p, x, and y The verification of data quality of these ethanol mole
constants). In practice, it is sufficient to know the residence fractions (x1) versus mixture density pairs (ρij) was made from
time for which the statistical constancy of the properties is excess volume (vE) calculations (Table 2). In addition, the
established. experimental pairs of data ρ versus x1 were correlated (Table
This process takes place when a perturbation is caused in the 3) by using the following fitting function (FF) equation
compositions of the phases that come into contact (strictly m
speaking, it should be considered that there is no equality of ρ = ρ1x1 + ρ2 (1 − x1) + x1(1 − x1) ∑ Ak
chemical potentials between the phases). That is why after the
ij yz
k=0
jj z
jj x + R (1 − x ) zzz
necessary residence time, the distribution of the substances k
x1
k 1 1 {
between the phases will generate the stationary condition or,
equivalently, the equality of chemical potentials. V (1)
The isobaric VLE data determination process begins by
charging the ebulliometer with one of pure substances (A). and the calculated excess volumes (vE) were correlated (see
Afterward, the heating devices are connected. Once the Table 3) through the polynomial equation (FF) as follows
ij yz
substance (A) reaches the boiling point, the ebulliometer is
ν E = x1(1 − x1) ∑ Ak jjj zz

j x1 + R V(1 − x1) zz
m k
completely closed and the work pressure is established by x1
k {
introducing dry nitrogen into the ebulliometer. The equipment
operates for approximately 4 h until the temperature is k=0 (2)
J. Chem. Eng. Data 2021, 66, 928−946
The results of the correlations (see Figure 1) and the 3.2. Vapor Pressures. Vapor pressures of ethanol have
standard deviations (SDs) are presented in Table 3 (see FF been published43,44 in the 300 to 446 K range; however, in this
work, the pressure in the binary systems is higher than the
previously published data. In addition, the pressure control
equipment as well as the experimental installation was
implemented39,40 to operate at high pressure, and for this
reason, new vapor pressures were obtained (Table 4). Vapor
pressures of water in the 330 to 490 K range were also
obtained using the same equipment and experimental
installation.38−40 Table 4 shows the vapor pressures (pi0)
versus temperature (T) data pairs for each substance. These
data pairs were correlated with Antoine’s well-known equation
B
log10(pi 0 /kPa) = A −
T /K − C (3)
Figure 1. Experimental values at 298.15 K of vE versus x1 (red empty
circle) and ρ versus x1 (blue empty square) with fitting curves of The Antoine constants obtained for each substance of this
ethanol (1) + water (2). Comparison with bibliographic data: by work as well as the standard deviations (SDs) and the mean
Benson and Kiyohara41 (green solid up-pointing triangle); by Grolier proportional deviations (MPDs), calculated using the simplex
and Wilhelm (blue solid right-pointing triangle).42 nonlinear regression method modified by Nelder and Mead,45
are included in Table 5. The Antoine constants for the pure
representing eqs 1 and 2). Regarding the excess volumes substances from the bibliography46−52 calculated by us are
(Figure 1), when the data of this work are compared to the shown also in Table 5. These Antoine constants were utilized
bibliographic data,41,42 a very similar behavior is observed to validate the vapor pressure experimental data obtained by
when considering the effect of volumetric contraction in the us.
ethanol (1) + water (2) mixture. The negative excess volumes Consequently, the experimental data of vapor pressures
show that the volume of mixture is smaller than the sum of presented in Table 4 were checked with respect to the
pure substances volumes, and that may be a consequence of calculated data, obtained by using the Antoine constant
the intermolecular interactions including dipole−dipole or bibliography46−52 shown in Table 5. For this, the deviations in
hydrogen bonding interactions. pressure were determined for each temperature data (see
Table 4. Experimental Vapor Pressuresa

T/K pi0/kPa T/K pi0/kPa T/K pi0/kPa T/K pi0/kPa T/K pi0/kPa T/K pi0/kPa
b
Ethanol
322.35 28 360.75 144 384.05 320 416.95 826 434.55 1280 446.75 1700
330.05 40 362.15 152 385.05 330 419.95 895 436.15 1330 447.55 1729
333.25 46 364.45 166 387.65 360 422.05 944 437.35 1370 448.55 1768
338.85 60 365.55 172 390.45 390 423.45 975 439.15 1428 449.75 1816
340.45 64 367.65 186 392.95 420 424.35 999 440.45 1471 451.35 1878
344.05 74 369.25 196 394.05 434 425.55 1028 441.25 1500 451.85 1902
346.55 82 370.05 202 396.65 471 427.25 1072 441.35 1501 452.35 1923
348.75 90 371.55 212 401.35 536 428.25 1098 442.25 1530 453.55 1973
351.45 101 373.15 224 404.05 580 429.25 1126 443.45 1573 454.15 2000
353.25 108 374.35 234 406.05 615 431.25 1180 444.15 1600 454.25 2001
355.55 118 375.65 244 408.25 655 433.15 1250 445.05 1630 454.85 2026
356.75 124 378.25 265 413.35 751 433.95 1263 445.55 1650 456.05 2079
359.15 136 380.65 286 415.25 790
Water
333.45 20 383.15 144 424.35 490 449.95 928 464.15 1282 478.85 1746
339.25 26 386.65 161 427.95 540 451.35 958 465.55 1321 479.35 1765
348.55 40 390.25 181 428.05 541 452.15 976 466.35 1345 481.55 1846
353.05 48 391.85 191 431.45 590 452.75 991 467.05 1364 482.75 1889
357.75 58 393.95 204 434.05 631 453.95 1018 468.95 1423 483.25 1910
361.55 66 395.75 216 436.45 670 455.05 1045 469.65 1443 484.15 1945
365.45 76 397.15 225 439.25 720 456.25 1074 470.85 1480 485.55 2000
367.75 84 398.25 233 440.45 739 457.65 1110 471.45 1500 485.95 2016
370.75 93 403.25 270 442.65 780 459.35 1152 472.05 1520 487.45 2078
373.15 101 410.15 331 445.65 840 459.95 1168 474.15 1585 488.25 2111
375.85 112 414.05 370 446.25 851 461.75 1215 475.05 1616 489.45 2161
378.75 124 420.15 438 448.05 889 462.55 1237 476.65 1670
a
The combined expanded uncertainties U(k = 2) are as follows: U(T) = 0.4 K and U(pi0) = 3 kPa. bData from 322 to 375 K are in ref 43. Data
from 442 to 445 K are in ref 44.
J. Chem. Eng. Data 2021, 66, 928−946
Table 5. Calculated Antoine Constants for Ethanol and Wateri

substances A B C SD(pi0) (kPa) SD(T) (K) MPD(pi0) (%) MPD(T) (%)
ethanol 7.0155 1476.4 56.741 2.0 0.2 0.38 0.03
6.8574b 1364.727b 70.186b 9.3a 0.3a 0.84a 0.07a
6.9196c 1394.342c 67.761c 26.8a 0.8a 1.85a 0.16a
7.03339d 1486.82d 55.715d 3.6a 0.2a 0.47a 0.04a
6.8078e 1333.248e 73.79e 9.3a 0.4a 0.95a 0.08a
7.0145f 1475.739f 56.818f 2.9a 0.2a 0.74a 0.06a
water 7.1458 1716.762 39.021 0.8 0.1 0.13 0.01
7.0775b 1662.957b 45.267b 1.4a 0.1a 0.25a 0.02a
7.0906c 1673.622c 43.984c 1.6a 0.1a 0.26a 0.02a
7.0915f 1673.31f 44.163f 1.5a 0.1a 0.28a 0.02a
7.0733g 1659.155g 45.696g 1.8a 0.1a 0.31a 0.03a
7.2457h 1794.158h 30.675h 2.3a 0.2a 0.39a 0.04a
a
Fcalc values in SD(F) and MPD(F) represent the properties calculated by the equation of Antoine from references. bRef 46. cRef 47. dRef 48. eRef
100 n |Fexp − Fcal|
49. fRef 50. gRef 51. hRef 52. iMPD(F ) = n−2
∑1 Fexp
with F being (pi0/kPa) or (T/K); n is the number of data.
Figure 2. Plot of errors between experimental vapor pressures and bibliographic46−52 data. (A) For ethanol (from the 25 to 2100 kPa range); (B)
for water (from 20 kPa to 2200 kPa range). Bibliographic data used are in ref 46 (blue open left-pointing triangle), ref 47 (green open up-pointing
triangle), ref 48 (magenta open right-pointing triangle), ref 49 (black open square), ref 50 (red open star), ref 51 (magenta open circle), and ref 52
(black open down-pointing triangle).
Figure 2), as well as the mean proportional deviations determinations of vapor pressures, in the previous range cited,
(MPDs). The results for ethanol were as follows: MPD = enables their use in the processing of VLE data.
0.84 considering the bibliography46 as a reference, MPD = 1.85 Consequently, value pairs of pi0 versus T were employed to
considering the bibliography,47 MPD = 0.47 considering the calculate the acentric factor (ω) and kappa parameter (κ1) of
bibliography48 as a reference, MPD = 0.95 considering the Stryjek−Vera.30 By this, the critical properties from the
bibliography49 as a reference, and MPD = 0.74 considering the literature47 were used as well as eq 3 by considering the
bibliography.50 The results for water were as follows: MPD = reduced properties. The results of the acentric factor and the
kappa parameters were as follows: ω = 0.63607 [SD(pi0) = 1.9
0.25 considering the bibliography46 as a reference, MPD = 0.26
kPa] and κ1 = 0.02727 [SD(pi0) = 2.6 kPa] (0.64439 and
considering the bibliography,47 MPD = 0.28 considering the
−0.003374, respectively, from the bibliography30) for ethanol
bibliography50 as a reference, MPD = 0.31 considering the and ω = 0.3448 [SD(pi0) = 0.9 kPa] and κ1 = −0.06727
bibliography51 as a reference, and MPD = 0.39 considering the [SD(pi0) = 1.2 kPa] (0.3438 and −0.06635, respectively, from
bibliography52 as a reference. the bibliography30) for water.
Therefore, the aforementioned results make it possible to 3.3. VLE Data. Table 6 shows the VLE experimental data
indicate that the vapor pressure data presented in Table 4 (T−x1−y1) obtained for the ethanol (1) + water (2) binary
match the uncertainties shown in this table. On the other hand, mixtures at 100, 1500, and 2000 kPa. The data reduction was
it seems reasonable to accept that the quality of experimental verified by considering the statistical deviations as the previous
J. Chem. Eng. Data 2021, 66, 928−946
Table 6. Isobaric VLE Data of Ethanol (1) + Water (2)a

x1 y1 T/K x1 y1 T/K x1 y1 T/K
+ water (2) at 100 kPa
0.001 0.014 372.3 0.099 0.436 358.7 0.520 0.659 352.6
0.006 0.056 370.7 0.107 0.448 358.4 0.588 0.682 352.3
0.015 0.129 368.8 0.136 0.480 357.5 0.690 0.745 351.8
0.023 0.184 367.3 0.198 0.524 356.0 0.722 0.764 351.7
0.032 0.234 365.8 0.228 0.543 355.2 0.815 0.834 351.5
0.044 0.289 363.9 0.283 0.571 354.7 0.861 0.870 351.4
0.054 0.326 362.6 0.356 0.594 354.1 0.921 0.918 351.4
0.062 0.358 361.4 0.414 0.610 353.4 0.963 0.961 351.4
0.077 0.399 360.4 0.460 0.632 353.2
0.007 0.055 468.9 0.185 0.435 449.5 0.555 0.641 442.7
0.014 0.081 467.0 0.212 0.452 448.8 0.604 0.670 442.1
0.024 0.116 464.2 0.239 0.469 448.0 0.646 0.697 441.8
0.047 0.219 459.3 0.265 0.483 447.4 0.700 0.734 441.4
0.074 0.294 455.4 0.297 0.502 446.8 0.748 0.769 441.0
0.087 0.323 454.2 0.327 0.518 446.2 0.796 0.807 440.8
0.102 0.348 452.7 0.366 0.537 445.5 0.833 0.836 440.7
0.116 0.369 451.9 0.402 0.555 444.9 0.872 0.871 440.7
0.132 0.389 451.1 0.436 0.572 444.3 0.912 0.908 440.7
0.150 0.409 450.4 0.475 0.593 443.7 0.966 0.964 440.9
0.165 0.419 450.0 0.515 0.616 443.2
0.005 0.036 484.0 0.204 0.431 462.7 0.590 0.651 455.5
0.010 0.062 482.6 0.227 0.447 462.1 0.627 0.676 455.1
0.019 0.091 480.3 0.252 0.462 461.4 0.662 0.701 454.7
0.036 0.155 476.2 0.276 0.475 460.7 0.704 0.729 454.4
0.058 0.230 472.3 0.317 0.497 459.9 0.744 0.760 454.2
0.072 0.267 470.2 0.342 0.510 459.4 0.788 0.796 454.0
0.082 0.284 469.1 0.363 0.523 458.9 0.828 0.831 453.9
0.085 0.293 468.7 0.382 0.533 458.6 0.863 0.862 453.8
0.097 0.321 467.6 0.410 0.547 458.0 0.895 0.893 453.9
0.109 0.338 466.5 0.443 0.566 457.5 0.926 0.921 453.9
0.128 0.364 465.2 0.476 0.583 457.0 0.951 0.945 454.0
0.146 0.386 464.5 0.508 0.602 456.5 0.970 0.965 454.1
0.160 0.401 464.1 0.540 0.621 456.0 0.985 0.983 454.1
0.183 0.417 463.2 0.565 0.637 455.7
a
The combined expanded uncertainties U(k = 2) are as follows: U(T) = 0.4 K, U(p) = 3 kPa, and U(x1) = U(y1) = 0.004.
stage to perform the thermodynamic treatment. The following pressure (see FF representing eqs 4−6). The VLE
polynomial equations were used to correlate the experimental experimental data of each binary mixture (see Table 6) were
data plotted together with the correlation curves of the literature
ji zyz
= ∑ Ak jjj
data18,19,53−55 for comparison purposes (see Figures 3 and 4).
z
j x1 + R V(1 − x1) zz
m k
x1 All data of this work were fitted by using eqs 4−6 to
k {
−1
(y1 − x1)[x1(1 − x1)]
correlate them. The composition−composition and temper-
k=0
(4)
ature−composition pairs of data in all systems were plotted
together with x1 and y1, being respectively the ethanol
[T − x1Tbp1 − (1 − x1)Tbp2] [x1·(1 − x1)]−1 composition from the liquid and vapor phases expressed as
ji zyz
mole fractions, to observe the compression effect in the
= ∑ Ak jjj z
j x1 + R V(1 − x1) zz
m k
x1 mixtures (see Figures 3 and 4). In addition, Figures 3 and 4
k {
show that the mixtures of ethanol/water present an azeotropic
k=0 (5) point at 100, 1500, and 2000 kPa that moves with increasing
pressure toward regions with a lower molar fraction of alcohol.
[T − y1Tbp1 − (1 − y1)Tbp2][y1(1 − y1)]−1 The quantity of isothermal and isobaric systems of the
ij yz
= ∑ Ak jjjj zz
ethanol/water mixture in the bibliography17 is very high, but a
z
j y + R V(1 − y ) zz
m k
y1 small number of systems have been selected from among all
k 1 1 {
k=0 (6)
those that have shown a good relationship in the graphic and
analytical position with respect to the data of this work. The
Table 3 shows the results for each fitting function (FF) result is shown in Figures 3 and 4. On the other hand, in
equation from the ethanol (1) + water (2) systems at each Figure 4, the data of this work have been presented with
J. Chem. Eng. Data 2021, 66, 928−946
corresponding to 101 kPa have been presented in the form of

an analytical correlation for better verification of the similarity
regarding the data at 100 kPa of this work.
3.4. Azeotropic Data. The azeotropic point for the
ethanol/water mixtures at 100, 1500, and 2000 kPa has been
verified in this paper. For the singular-point calculation, we
have used the data in Table 6. The natural cubic Spline
method56 was carried out to interpolate and to obtain more
accurate results instead of standard polynomial correlations.
We have used the Thomas algorithm,56 adapted and
optimized for our purpose. Combining this method with the
natural cubic Spline method made it possible to get accurate
results even in the neighborhood of the compositions 0 and 1
of molar fractions. This work results are presented in Table 7,
Figure 3. Experimental isobaric data of (y1−x1) versus x1 at 100 kPa and also, we have plotted them in Figure 5, adding the
(black open right-pointing triangle), 1500 kPa (black open up- azeotropic points of the bibliography.20
pointing triangle), and 2000 kPa (black open circle) for ethanol/water
systems. The bibliographic17 data are plotted by fitting curves: at 33.3
kPa by Kirschbaum and Gerstner53 [orange line (A)]; at 101.3 kPa by
Kojima et al.54 [red line (B)], Stabnikov et al.55 [dark brown line
(C)], and Otsuki and Williams19 [green line (D])]; at 344.74 kPa by
Otsuki and Williams19 [pink line (E)]; at 515.0 kPa by Othmer et
al.18 [blue line (F)]; at 689.48 kPa by Otsuki and Williams12 [sky blue
line (G)]; at 1378.95 kPa Otsuki and Williams19 [magenta line (H)];
and at 2068.43 kPa by Otsuki and Williams19 [black line (I)].
Figure 5. Three-dimensional plot of the bibliographic20 (blue solid

circle) and azeotropic points of this work at 100 kPa (red solid up-
pointing triangle), 1500 kPa (red solid left-pointing triangle), and
2000 kPa (red solid right-pointing triangle) for the ethanol (1) +
water (2) system with fitting curves [eqs 7 and 8, red lines (A)] and
bibliographic19 fitting curves [eqs 9 and 10, green lines (B)]. The
symbols as blue color (blue open circle) and red color (red open up-
pointing, left-pointing, and right-pointing triangles) are from the two-
dimensional representation.
Figure 4. Representation for ethanol/water systems of experimental
data of T versus x1 and y1 (blue or red symbols, respectively, at 100
kPa (blue and red solid right-pointing triangles), 1500 kPa (blue and
red solid up-pointing triangles), and 2000 kPa (blue and red solid In addition, the azeotropic data of this work obtained as
down-pointing triangles)) as well as the bibliographic17 data at 33.3 previously indicated and all the azeotropic points of the
kPa by Kirschbaum and Gerstner53 (blue and red open stars), at 101.3 bibliography20 were correlated using a multiple linear
kPa by Stabnikov et al.55 (blue and red lines), at 344.74 kPa by Otsuki regression FORTRAN program, considering the reduced
and Williams19 (blue and red hexagrams), at 515.0 kPa by Othmer et
properties of the singular points by using the critical properties
al.18 (blue and red open squares), at 689.48 kPa by Otsuki and
Williams19 (blue and red open left-pointing triangle) at 1378.95 kPa of the bibliography.47
Otsuki and Williams19 (blue and red open diamonds), and at 2068.43 However, the initial correlation of all the data generated a
kPa by Otsuki and Williams19 (blue and red open circles). poor reproducibility due to the enormous dispersion of the
data, which could be verified by making the representations
with both x1,az versus TR,az and x1,az versus log10(pR,az). This is
respect to the data of the bibliography18,19,53,55 for graphical the reason why a reduction of the azeotropic data taken from
three-dimensional verification of the evolution of the mixture the bibliography20 was carried out in such a way that from the
at increasing pressure. In Figure 3, the Stabnikov et al.55 data 121 initial data, only 84 azeotropic data were correlated.
Table 7. Verification of Azeotropic Data of This Worka
x1,az paz/kPa PAD(x1,az) PAD(paz/ x1,az paz/kPa PAD(x1,az) PAD(paz/

Taz/K x1,az p/kPa (eq 7) (eq 8) (eq 7) kPa) (eq 8) (eq 9) (eq 10) (eq 9) kPa) (eq 10)
351.39 0.899 100 0.893 102.6 0.7 2.6 0.895 100.9 0.5 0.9
440.70 0.857 1500 0.858 1485.8 0.1 0.9 0.859 1471.6 0.2 1.9
453.82 0.850 2000 0.856 1963.2 0.7 1.8 0.854 1977.6 0.5 1.1
a |Fexp − Fcal|
PAD(F ) = 100 Fexp
with F being (x1,az) or (p/kPa).
J. Chem. Eng. Data 2021, 66, 928−946
Table 8. Results for Fugacity Coefficients (ϕi,V) Activity Coefficients (γi) and Excess Gibbs Free Energy (GE/RT) Using Virial
EOS
ethanol (1) + water (2) at 100 kPa
x1 ϕ1,V ϕ2,V ϕ10 ϕ20 POY1 POY2 γ1 γ2 GE/RT
0.001 0.981 0.984 0.975 0.984 0.998 1.000 6.504 0.999 0.001
0.006 0.980 0.984 0.974 0.984 0.998 1.000 4.578 1.018 0.027
0.015 0.979 0.983 0.973 0.983 0.998 1.000 4.501 1.015 0.038
0.023 0.978 0.983 0.973 0.983 0.998 1.000 4.410 1.013 0.047
0.032 0.976 0.983 0.972 0.982 0.998 1.000 4.248 1.015 0.060
0.044 0.975 0.982 0.971 0.982 0.999 1.000 4.082 1.024 0.084
0.054 0.974 0.982 0.971 0.981 0.999 1.000 3.930 1.030 0.102
0.062 0.973 0.982 0.970 0.981 0.999 1.000 3.926 1.036 0.118
0.077 0.973 0.982 0.970 0.981 0.999 1.000 3.653 1.024 0.121
0.099 0.971 0.982 0.969 0.980 0.999 1.000 3.305 1.051 0.163
0.107 0.971 0.981 0.969 0.980 0.999 1.000 3.177 1.050 0.167
0.136 0.970 0.981 0.968 0.979 0.999 1.000 2.769 1.059 0.188
0.198 0.969 0.981 0.967 0.979 1.000 1.000 2.197 1.108 0.238
0.228 0.969 0.981 0.967 0.979 1.000 1.000 2.037 1.141 0.264
0.283 0.968 0.981 0.967 0.978 1.000 1.000 1.759 1.177 0.276
0.356 0.968 0.981 0.966 0.978 1.000 1.000 1.488 1.270 0.295
0.414 0.967 0.981 0.966 0.978 1.000 1.000 1.350 1.379 0.312
0.460 0.967 0.981 0.966 0.978 1.000 1.000 1.268 1.424 0.300
0.520 0.966 0.982 0.965 0.977 1.000 1.000 1.197 1.521 0.295
0.588 0.966 0.982 0.965 0.977 1.000 1.000 1.108 1.673 0.272
0.690 0.965 0.982 0.965 0.977 1.000 1.000 1.052 1.821 0.221
0.722 0.965 0.983 0.965 0.977 1.000 1.000 1.035 1.887 0.201
0.815 0.965 0.984 0.965 0.977 1.000 1.000 1.008 2.013 0.136
0.861 0.965 0.984 0.965 0.977 1.000 1.000 0.999 2.108 0.103
0.921 0.965 0.985 0.965 0.977 1.000 1.000 0.986 2.342 0.054
0.963 0.965 0.986 0.965 0.977 1.000 1.000 0.987 2.380 0.019
The dispersions could not be verified with the representa- work, a three-dimensional representation (Figure 5) was made
tion log10(pR,az) versus TR,az. Therefore, for the reduction for the ethanol/water binary mixtures using the experimental
process, an error percentage equal to 1% was considered on the data of this work and the bibliographic20 data. On the other
curve x1,az versus TR,az and also on the curve x1,az versus hand, the correlation curves of this work (eqs 7 and 8) and the
log10(pR,az) in such a way that the data that were observed bibliographic19 correlations (eqs 9 and 10) were plotted in
scattered and, hence, outside the margin established by the Figure 5. The azeotropic data of this work were calculated also
error curves were not considered reliable for the correlation. by using eqs 7−10, and the results and the percent absolute
The correlations of the 84 azeotropic data of the ethanol/water deviation (PAD) in data prediction are included in Table 7.
system were as follows. The comparison regarding the bibliography allows one to
0.818 − 1.531TR,az observe the considerable displacement of the binary system
x1,az = due to the pressure increase (see Figure 4). In addition, good
1 − 1.841TR,az (7) correspondence can be observed (see Figure 3) between the
data of this work at 100 kPa and the bibliographic data by
11.451 − 11.648TR,az Otsuki and Williams,19 Kojima et al.,54 and Stabnikov et al.55
log10 pR,az =
1 − 4.734TR,az (8) and an adequate ratio between the data at 1500 and 2000 kPa
by Otsuki and Williams19 at 1378.95 and 2068.43 kPa
The statistical values of MPD(x1,az), SD(x1,az), MPD(paz), bibliography data. The inset included in Figure 3 shows
and SD(paz/kPa) from eqs 7 and 8 were 0.8, 0.010, 1.2, and more details of azeotropic data identification and verification
5.5, respectively, considering all the 121 data. These fitting about the bibliographic data.19,54,55
curves to azeotropic data of ethanol/water systems (eqs 7 and Regarding the correlation curves (eqs 7−10) plotted in
8) are significantly different from those indicated in the Figure 5, it can be seen that the bibliographic19 fitting curves
bibliography19 presented with S.I. units as follows (eqs 9 and 10) are useful from 50 kPa to high pressure
log10 x1,az = 0.0208 − 1.97· 10−4Taz /K because, at very low pressure (from the 12 to 50 kPa range),
(9)
the percent absolute deviations (PADs) in mole fraction and
1597 pressure are higher than 3.4 and 2.7% (mean values),
log10 paz /kPa = 7.1849 − respectively, therefore much higher than MPD(x1,az) = 1.4
Taz /K − 43.15 (10)
and MPD(paz) = 1.6 by considering the total set of azeotropic
Similarly, with all 121 data, we calculated the statistical data (from the 12 to 2100 kPa range).
values of MPD(x1,az), SD(x1,az), MPD(paz), and SD(paz/kPa) However, at high pressure, the bibliographic19 curves (eqs 9
from eqs 9 and 10; results were 1.4, 0.020, 1.6, and 8.0, and 10) show a very good prediction of the azeotropic data.
respectively. In addition, to verify the azeotropic data of this On the other hand, the fitting curves in this work (eqs 7 and 8)
J. Chem. Eng. Data 2021, 66, 928−946
can be utilized over the range because the PADs in mole Table 9. Results of Thermodynamic Consistency Test in the
fraction and pressure are less than 0.9 and 1.8% (mean values), Ethanol/Water System at 100 kPaa
respectively, from the 12 to 50 kPa range, values not much
parameters area test parameters point test
greater than MPD(x1,az) = 0.8 and MPD(paz) = 1.2 from the 12
to 2100 kPa range. When the prediction of the azeotropic data L 0.3051 103 MAD(y1) 7.28
of this work using eqs 7−10 is considered, it is seen in Table 7 W 0.3227 MPD(y1) 3.58
that the PAD for each of them is satisfactory with respect to D 2.80 103 BIAS(y1) −5.66
the corresponding MPD of the correlations, which seems to J 9.26 MAD(p/kPa) 0.61
report favorably on the quality of the calculated data. ABS(D−J) 6.46 MPD(p) 0.02
3.5. Treatment and Thermodynamic Verification of Redlich−Kister21 test passes BIAS(p/kPa) −0.05
VLE Data. 3.5.1. Low-Pressure Data Verification. The Herington22 test passes Van Ness et al.23,24 test passes
nonideality of both the liquid and vapor phases of the direct test
ethanol/water binary systems at 100 kPa was established for ∑[d(G E / RT ) / dx1 − ln(γ1 / γ2)]2 0.105
RMS =
the activity coefficient of liquid phase (γi) calculations using n−2
ÄÅ
the following equation Van Ness59 index if 0.100 < RMS < 0.125 5
ÅÅ p − p0
ÅÅ
∑1n(Fexp − Fcal) ∑1n |Fexp − Fcal|
ÅÅ
a
ÅÅ RT
yp p(2Bij − Bii − Bjj ) BIAS(F ) = ; MAD(F ) = with F being (y1)
ÅÅÇ
n−2 n−2
i i L
γi = exp ( B − v ) + or (p/kPa); n is the number of data.
ÉÑ
0 ii i
RT
ÑÑ
xipi
Ñ
(1 − yi )2 ÑÑÑÑ
When checking the statistics of the aforementioned data, it is
ÑÑ
observed that the numerical values for δy1 showed a significant
ÑÖ (11) bias (see Table 9) and failed from the 0.015 to 0.055 mole
fraction range in the distribution about the zero line, but the
with p, pi 0 , and R being the total pressure, the vapor pressure of tendency is not marked enough as to be correlated. The
the pure substance, and the universal gas constant, respectively. numerical values for δp indicate totally random distribution
The equation of Yen−Woods57 was used for the liquid molar without any remarkable tendency. Therefore, the analysis for
volumes of pure substance (vLi ) calculations in the pointing δp and for δy1 of the ethanol/water system at 100 kPa suggests
factor corrections (POYi). The virial equation of state that the positive consistency in the system is not fully
truncated at the second coefficient was utilized to calculate established. It is the reason why, to establish the quality of the
the fugacity coefficients of substance i in the vapor mixture data, other different tests were applied.21,22,59
(ϕVi ) and the fugacity coefficient of pure vapor i at equilibrium The area consistency test21,22 was applied by employing the
system temperature (ϕ0i ). For this reason, the Hayden and following equations
O’Connell58 method was employed to obtain the second virial L−W |Tbp1 − Tbp2|
coefficients for pure substances (Bii and Bjj) and the second D = 100 ; J = 150
L+W Tmin (12)
cross-virial coefficients (Bij). The critical properties taken from
the bibliography47 and the constants of the Antoine equation When applying the Redlich−Kister test, D in eq 12 must 21
presented in Table 5 were utilized in this work for the be calculated. For this purpose, the areas below the curve (W)
calculation of the activity coefficients of the liquid phase (see and above the curve (L) must be calculated, which are
Table 8) and for applying the point-to-point test.23,24 obtained by solving the integral formed in the plot ln(γ1/γ2)
The point-to-point test proposed by Van Ness et al.23 was versus x1. The condition D < 10% must be met to satisfy the
used in the explicit form of Fredenslund et al.24 with the consistency criterion. Table 9 shows the results of the positive
purpose of verifying the ethanol + water binary system consistency of the ethanol/water system at 100 kPa of this
obtained at 100 kPa. This method applies the differential work.
equation of Gibbs−Duhem to each of the data. Legendre On the other hand, the area test of Herington22 proposed
polynomials are used to model activity coefficients. Once the the resolution of eq 12 and establishes the criterion |D−J| < 10
data are correlated, the equilibrium equation is used in an to indicate that if this condition is met, the system is probably
iterative process of recalculating the activity coefficients, which consistent. The results of applying the Herington22 area test to
ends by optimizing the pressure at each point. The data are the ethanol/water system at 100 kPa of this work are shown in
considered to be consistent24 if the absolute mean deviation in Table 9.
vapor-phase mole fraction is lower than 0.01. However, as Van Ness59 suggested, the area test is a global
In this work, the results obtained from the ethanol/water test of the data, and hence, the Redlich−Kister21 area test and
system at 100 kPa are shown in Table 9. It can be seen that the the Herington22 area test could be a necessary condition, but
system globally meets the criteria established by Fredenslund not sufficient, of the consistency of the data. For this reason, to
et al.24 However, it was observed that 23% of the data do not confirm the thermodynamic consistency of the data of this
meet the criterion of Fredenslund et al.24 This is why we work, they were checked with the direct area test from Van
proceeded to check, as a further consistency test, the residuals Ness.59 It was proceeded by using the extended equation of
obtained at each point. Consequently, the residual values (δy1 Redlich−Kister to correlate the activity coefficients of the
= y1,exp − y1,calc) of the molar fraction of the vapor phase, as liquid phase and the excess Gibbs free energy (GE/RT), for
well as the residual values (δp = pexp − pcalc) of the pressure, which the data of Table 8 and the following equations were
were determined. The average residuals (BIAS), the mean employed
absolute deviations (MADs), and the mean proportional
GE
deviations (MPDs) of the F properties (F being y1 or p) (see = x1x 2[B + C(x1 − x 2) + D(x1 − x 2)2 + ...]
Table 9) were also calculated. RT (13)
J. Chem. Eng. Data 2021, 66, 928−946
ji γ zy
lnjjjj 2 zzzz = a + b(x 2 − x1) + c(6x1x 2 − 1) + ...
as κ1, an adjustable parameter characteristic of each pure
k γ1 {
substance. This modification makes it possible that the
(14) PRSV29,30 EOS can be used for polar substances.62 Equation
59 16 can be presented as a function of the compressibility
The results of the direct area test from Van Ness obtained
ÄÅ 2Ñ
É
when eqs 13 and 14 were applied to obtain the root mean coefficient (Z), in a form useful for both phases, by
ij bp yz 2 ÅÅÅÅ a(T )p ij bp yz ÑÑÑÑ

square (RMS) are presented in Table 9. The consistency index
Z + jjj − 1zzzZ + ÅÅ − 3jjj zzz ÑÑZ
ÅÅ (RT )2 k RT { ÑÑÖÑ
from Van Ness59 is shown as well in Table 9.
k RT {
bp
ÇÅ
3
−2
ÅÄÅ É
Therefore, after verifying the correlation of the data for the
3Ñ
ij bp yz ÑÑÑÑ
RT
ÅÅ a(T )bp2 ij bp yz
ethanol/water system at 100 kPa with respect to the
− ÅÅ Å − jjj zzz − jjj zzz ÑÑ

bibliographic19,54,55 data (see Figure 3), observing the system’s
ÅÅ (RT )3 k RT { ÑÑÑÖ
2
ÅÇ k RT {
azeotrope disposition with respect to the azeotropic data from
the bibliography19,20,54,55 (see insets of Figures 3 and 5), and
considering the obtained results when the different consistency =0 (17)
tests21−24,59 were applied, it can be indicated that the quality of
data from this work obtained at 100 kPa is acceptable. In both eqs 16 and 17, the attractive (a) and repulsive
3.5.2. High-Pressure Thermodynamic Test and PR parameters (b) correspond to the PRSV29,30 EOS. Therefore,
Modeling. The experimental data at 1500 and 2000 kPa for the fugacity coefficient in the binary mixture can be calculated
ethanol/water have been verified following the procedure and
using the expression applicable to both phases, with the
by using the thermodynamic relationships suggested in the
appropriate expression of the compressibility coefficient,60 as
bibliography.25,26 As the authors explained in previous papers,
follows
1 ijj ∂nbm yzz

the consistency method proposed by the authors can be
i b py
j z(Z − 1) − lnjjjjZ − m zzzz −
considered as a modeling procedure25 because, to check the
bm jjk ∂ni zz{ k RT {

experimental data consistency, a thermodynamic model that am
ln φi =
ÄÅ ÉÑ
can accurately fit the experimental data must be used.25,60
ÅÅÅ ∂n2am ÑÑÑl ÅÄÅ ÑÉ|
2 2 RTbm
ÅÅ ∂n ÑÑo ÅÅ Z + (1 + 2 ) bmp ÑÑÑo o

ÑÑo o ÑÑo
Generally, the methods to check the thermodynamic
ÅÅ o ÅÅ RT Ñ o
ÅÅ ÑÑo mlnÅÅ }
( ) ( ) ∂nbm
bmp Ño Ñ
consistency are based on the Gibbs−Duhem equation, which
ÅÅ nam ÑÑo Å
ÅÅ ÑÑo o ÅÅÅÇ Z + (1 − 2 ) RT ÑÑÑÖo o
o
i ∂ni
can be applied for both the phases of the homogeneous
ÅÅÇ ÑÑÖn ~
−
mixture27,61 in terms of residual molar properties. In this work, bm
the Peng−Robinson−Stryjek−Vera29,30 (PRSV) model has
been utilized because this EOS can fit accurately the (18)
experimental data and can be applied to check the consistency
by using the Gibbs−Duhem equation. The attractive and repulsive parameters in eq 18 are both
Therefore, the Gibbs−Duhem equation for an isobaric functions of the compositions of the substances in the mixture.
mixture of two substances, expressed as a function of the The following relations were utilized
fugacity coefficients (ϕi) in the corresponding phase at the N N
temperature and pressure of the system, can be written as a
function of both substances and expressed in the integral form
am = ∑ ∑ ξiξj[ai(T )aj(T )]0.5 (1 − k1ij ); bm
i bi + bj yz
∑ ∑ ξiξjjjjjj
i j
zz(1 − k 2 )
to be applied to each phase as follows
ij RT yz dϕ2 zz
N N
jj R zz k {
Ti + 1 ϕ2, i + 1
=
k H { ϕ2
∫ Ti
dT
ξ2T
=− ∫
ϕ2, i
i j 2
ij
(19)
i y
jij RT zyzjjj 1 − ξ2 zzz dϕ1
therefore, in this work, the quadratic Van der Waals mixing
j R zjj z
ϕ1, i + 1
k H {k ξ2 z{ ϕ1
− ∫ ϕ1, i (15)
rules with two parameters (k1ij = k1ji) and (k2ij = k2ji), which
can be obtained by fitting the experimental data, were applied.
By selecting the model and using the fugacity coefficient
with ξi being the concentration of substance i in the liquid or equation, the residual enthalpy can be calculated by using the
vapor phase and HR being the residual molar enthalpy of the relationship between the residual enthalpy and the compres-
substance i in the mixture. sibility coefficient, which for the binary mixture results
The proposed method25−27,60 to check completely the high
pressure data by using eq 15 must be applied regardless of the HR 1
= (Z − 1) −
l
liquid and vapor phases.25 Therefore, for this purpose, the
o
RT 2 2 RTbm
o
o
PRSV29,30 EOS, which is one of the most common methods to
m
o
o
o i j
correlate the properties of the mixtures, is used in eq 15. The
n
PRSV29,30 EOS is expressed as follows ∑ ∑ xi x j(1 − kij) ai(T )aj (T )
ÄÅ ÉÑ| l ÅÄÅÅ
o
É|
bmp Ñ
ÑÑo
ÅÅ ÑÑoo
o o
o ÅÅÅ Z + (1 + ÑÑo
ÑÑo
ÅÅ1 − (Mi + Mj)ÑÑ}o o
RT a(T )
ÅÅÇ Ñ o olnÅÅÅÅ
m bmp Ñ
}
o
p= −
ÑÖo
oo 2 ) RT ÑÑo Ñ
Ñ
2 ) RT
o ÅÅ Z + (1 − o
1
~o Öo
v−b v(v + b) + b(v − b) (16)
n Ç ~
with a(T) = a·α(T), where the dimensionless factor (α) is a 2
function of a specific parameter for each substance (κ). This (20)
parameter has been expressed for 90 pure substances by
Stryjek−Vera30 as a function of the acentric factor (ω) as well with Mi, and its equivalent Mj, being represented by
J. Chem. Eng. Data 2021, 66, 928−946
Table 10. Results of Mean Absolute Deviations, Mean Proportional Deviations, and Standard Deviations from Data Prediction
Using the PC-SAFT Model as well as the PRSV and PRSVWS EOSs
azeotropic data
MAD(T/ MPD(T/ MPD(y1/ SD(T/
K) MAD(y1) %) %) K) SD(y1) k12 k21 α τ12 τ21 x1,az Taz/K
Ethanol (1) + water (2) at 100 kPa
TWa 0.899 351.39
PC-SAFT28,65 1.03 0.024 0.29 10.28 1.20 0.029 −0.0269 −0.0269
PC-SAFT28 1.11 0.033 0.31 15.47 1.55 0.043 0.1443 0.1443 0.916 351.17
(TW)
PRSV29,30 0.22 0.009 0.06 4.13 0.24 0.011 0.0642 0.1514 0.903 351.13
PRSVWS29−31 0.55 0.012 0.15 4.44 0.66 0.013 0.0534 0.0534 0.47 0.5902 2.0537 0.939 351.17
TWa 0.857 440.70
PC-SAFT28,65 0.90 0.016 0.20 4.42 1.10 0.018 −0.0269 −0.0269
PC-SAFT28 1.12 0.011 0.25 3.92 1.16 0.013 0.1443 0.1443
(TW)
PRSV29,30 0.75 0.005 0.17 1.91 1.05 0.006 0.0642 0.1514 0.883 441.09
PRSVWS29−31 0.29 0.005 0.06 2.78 0.45 0.010 0.0534 0.0534 0.47 0.5902 2.0537 0.864 440.83
TWa 0.850 453.82
PC-SAFT28,65 1.04 0.014 0.23 3.24 1.46 0.016 −0.0269 −0.0269
PC-SAFT28 0.99 0.010 0.21 3.37 1.05 0.012 0.1443 0.1443
(TW)
PRSV29,30 0.53 0.007 0.11 2.40 0.82 0.007 0.0642 0.1514 0.879 454.06
PRSVWS29−31 0.27 0.008 0.06 3.64 0.31 0.012 0.0534 0.0534 0.47 0.5902 2.0537 0.852 453.72
a
TW, this work.
TR0.5i of each pair of data (i,i + 1) and the mean error (%EA) (see
Mi = [κ1i(1 − TR0.5i )(0.7 − 2TR0.5i − 3TRi) Table 11) in a similar way and by applying the
1 + κ0(1 − TR0.5)
bibliography25−27 equations.
− κ 0i ] (21) The obtained results (Table 11) inform that the verification
To verify the data consistency, it has been accepted, procedure suggested25−27 in the current form could not be
according to Valderrama−Faúndez,25,26 that the selected always used in all systems that present an azeotropic point or
model (PRSV in this work) is satisfactory if it complies with in those systems of which the composition−temperature
the condition of MPD, which must be less than 10%, for both function has an asymptotic tendency. These are the reasons
the temperature and the vapor-phase composition. why the PADs of some pairs of data (i,i + 1) have an imprecise
This is the reason why the data shown in Table 6 were and numerically unstable behavior, especially with the current
correlated for the PRSV29,30 EOS, obtaining the following
uncertainties of our devices (see Table 6). Such a trend is
results: MPD(y1) = 2.27% and MPD(T) = 0.12% for the
binary system at 1500 kPa, whereas MPD(y1) = 2.19% and independent of the equation of state and/or model used. This
MPD(T) = 0.07% for the binary system at 2000 kPa. In Table is the reason why the data of the integrals of eq 22 (see Table
10, all results from treatment and correlation for the 1500 and 11) were used to calculate the PAD of %ΔA for n data by using
2000 kPa ethanol/water systems can be found by fitting to the eq 23
PRSV29,30 EOS. Therefore, it is shown that the systems of this
work meet these previous conditions.25,26 j=n−1
∑j = 1 |Aϕ , j | − ∑j = 1
j=n−1
|A T , j |
After verifying the adequacy between the model and the %ΔA = 100· j=n−1
procedure, the fugacity coefficients of the phases were ∑j = 1 |A T , j | (23)
calculated using eqs 16−19, as well as the corresponding
residual enthalpies by using eqs 20 and 21. The results are The obtained results were 0.8 and 0.6% for the ethanol/
shown in Table 11. water system at 1500 kPa and 0.6 and 0.4% for the ethanol/
Subsequently, the integrals of the left side (AT) and the right water system at 2000 kPa, respectively, for liquid and vapor
side (Aϕ1 and Aϕ2) of eq 15, presented as follows
phases. These results are less than 20%, such as suggested in
i y
jij RT zyzjjj 1 − ξ2 zzz dϕ1 ;
Tn
the literature 25−27 as the lower limit to declare the
j R zjj z
ϕ1, n
∫ ∫ k H {k 2 z{ ϕ1
dT
AT = ; Aϕ = −
1
thermodynamically consistent data.
ξ2T ξ
ϕ1, i Therefore, to be able to compare globally the errors of the
ij RT yz dϕ2
Ti
jj R zz
ϕ2, n
data, those data that generated numerical instability were not
∫ k H { ϕ2
Aϕ = − used and the percentage of error (%EA) in each of the phases
2
ϕ2, i (22) of both systems was calculated. First, the error of each pair (j,j
were applied to calculate the proportional absolute deviation + 1) affected by the uncertainty (see Table 6) of the
[PAD(Aj)] of the different data pairs, as well as the error (EA,j) experimental data was calculated as in eq 24
J. Chem. Eng. Data 2021, 66, 928−946
Table 11. High-Pressure Consistency Test Results
HR HR
x1 ϕ1,L ϕ2,L ( )
RT
L
PAD(Aj) |EA,j| y1 ϕ1,V ϕ2,V ( )
RT
V
PAD(Aj) |EA,j|
ater (2) at 1500 kPa
0.007 6.617 0.886 −9.401 0.055 0.889 0.932 −0.216
0.014 6.159 0.853 −9.435 0.57 0.051 0.081 0.887 0.931 −0.224 0.01 0.000
0.024 5.559 0.806 −9.490 0.64 0.002 0.116 0.883 0.930 −0.236 0.61 0.001
0.047 4.503 0.732 −9.570 1.44 0.046 0.219 0.877 0.929 −0.268 1.83 0.005
0.074 3.649 0.680 −9.610 0.91 0.073 0.294 0.872 0.928 −0.295 0.64 0.012
0.087 3.346 0.666 −9.609 0.16 0.001 0.323 0.870 0.927 −0.306 0.28 0.001
0.102 3.034 0.650 −9.614 0.15 0.015 0.348 0.868 0.927 −0.316 0.02 0.003
0.116 2.805 0.644 −9.598 0.05 0.001 0.369 0.867 0.927 −0.324 0.03 0.000
0.132 2.581 0.639 −9.579 0.19 0.003 0.389 0.865 0.927 −0.332 0.05 0.001
0.150 2.369 0.637 −9.551 0.19 0.007 0.409 0.864 0.927 −0.340 0.12 0.002
0.165 2.222 0.638 −9.523 0.07 0.001 0.419 0.864 0.927 −0.344 0.65 0.000
0.185 2.052 0.641 −9.486 0.22 0.001 0.435 0.863 0.927 −0.350 0.96 0.001
0.212 1.859 0.645 −9.440 0.29 0.000 0.452 0.862 0.927 −0.357 0.44 0.000
0.239 1.697 0.648 −9.403 0.18 0.002 0.469 0.861 0.927 −0.365 0.03 0.001
0.265 1.571 0.654 −9.363 0.21 0.000 0.483 0.860 0.927 −0.371 0.10 0.000
0.297 1.446 0.664 −9.313 0.25 0.000 0.502 0.859 0.927 −0.379 0.61 0.000
0.327 1.348 0.673 −9.272 0.21 0.000 0.518 0.858 0.927 −0.386 1.18 0.000
0.366 1.245 0.686 −9.220 0.35 0.001 0.537 0.857 0.927 −0.395 0.67 0.000
0.402 1.169 0.700 −9.175 0.29 0.000 0.555 0.856 0.927 −0.403 0.70 0.000
0.436 1.108 0.712 −9.137 0.23 0.000 0.572 0.855 0.927 −0.411 0.00 0.000
0.475 1.051 0.727 −9.095 0.19 0.001 0.593 0.854 0.927 −0.421 0.40 0.000
0.515 1.005 0.744 −9.052 0.30 0.000 0.616 0.853 0.928 −0.431 0.46 0.000
0.555 0.967 0.761 −9.013 0.28 0.000 0.641 0.852 0.928 −0.442 0.42 0.000
0.604 0.929 0.782 −8.969 0.34 0.002 0.670 0.851 0.929 −0.456 0.30 0.002
0.646 0.906 0.802 −8.926 0.41 0.000 0.697 0.851 0.929 −0.468 0.88 0.000
0.700 0.881 0.828 −8.877 0.54 0.000 0.734 0.850 0.930 −0.485 1.84 0.000
0.748 0.863 0.849 −8.840 0.24 0.001 0.769 0.849 0.931 −0.501 0.21 0.001
0.796 0.852 0.872 −8.797 0.46 0.001 0.807 0.848 0.933 −0.519 0.21 0.001
0.833 0.846 0.891 −8.764 0.52 0.000 0.836 0.848 0.934 −0.532 1.00 0.000
0.872 0.842 0.912 −8.726 0.000 0.871 0.848 0.935 −0.548 0.000
0.912 0.840 0.933 −8.688 0.001 0.908 0.848 0.936 −0.566 0.001
0.966 0.842 0.965 −8.630 0.57 0.051 0.964 0.848 0.939 −0.592 2.28 0.000
%ΔA = 0.8 %EA = 14.9 %ΔA = 0.6 %EA = 11.8

0.005 5.775 0.892 −8.924 0.036 0.870 0.917 −0.265
0.010 5.512 0.869 −8.947 0.38 0.044 0.062 0.868 0.917 −0.274 0.15 0.000
0.019 5.084 0.833 −8.984 0.63 0.007 0.091 0.865 0.916 −0.286 0.57 0.002
0.036 4.387 0.773 −9.050 1.04 0.045 0.155 0.859 0.914 −0.311 0.33 0.005
0.058 3.705 0.720 −9.096 0.84 0.054 0.230 0.852 0.913 −0.342 1.13 0.008
0.072 3.355 0.695 −9.116 0.20 0.030 0.267 0.849 0.912 −0.359 0.07 0.006
0.082 3.147 0.682 −9.118 0.13 0.047 0.284 0.847 0.911 −0.367 0.16 0.008
0.085 3.086 0.678 −9.121 0.00 0.011 0.293 0.847 0.911 −0.371 1.91 0.002
0.097 2.874 0.667 −9.117 0.07 0.002 0.321 0.845 0.911 −0.383 0.16 0.000
0.109 2.684 0.656 −9.115 0.11 0.000 0.338 0.843 0.911 −0.392 0.46 0.000
0.128 2.433 0.646 −9.099 0.16 0.010 0.364 0.841 0.911 −0.406 0.12 0.003
0.146 2.244 0.644 −9.067 0.22 0.007 0.386 0.839 0.911 −0.416 0.13 0.002
0.160 2.119 0.645 −9.039 0.05 0.004 0.401 0.838 0.911 −0.423 0.74 0.002
0.183 1.934 0.643 −9.003 0.19 0.006 0.417 0.837 0.910 −0.432 0.19 0.002
0.204 1.798 0.647 −8.961 0.32 0.000 0.431 0.836 0.910 −0.439 1.04 0.000
0.227 1.668 0.650 −8.919 0.13 0.000 0.447 0.835 0.910 −0.447 0.18 0.000
0.252 1.547 0.654 −8.879 0.15 0.000 0.462 0.834 0.910 −0.456 0.22 0.000
0.276 1.447 0.658 −8.844 0.16 0.000 0.475 0.833 0.910 −0.464 0.12 0.000
0.317 1.314 0.671 −8.774 0.50 0.002 0.497 0.831 0.910 −0.476 0.28 0.002
0.342 1.247 0.678 −8.736 0.16 0.000 0.510 0.830 0.911 −0.483 0.40 0.000
0.363 1.196 0.684 −8.708 0.01 0.002 0.523 0.829 0.911 −0.491 0.02 0.001
0.382 1.157 0.691 −8.678 0.11 0.001 0.533 0.829 0.911 −0.496 0.74 0.001
0.410 1.104 0.700 −8.643 0.15 0.001 0.547 0.828 0.911 −0.505 0.28 0.000
0.443 1.053 0.713 −8.596 0.19 0.000 0.566 0.826 0.911 −0.516 0.70 0.000
J. Chem. Eng. Data 2021, 66, 928−946
Table 11. continued

0.476 1.010 0.726 −8.553 0.18 0.000 0.583 0.825 0.911 −0.526 0.42 0.000
0.508 0.974 0.738 −8.514 0.19 0.000 0.602 0.824 0.912 −0.537 1.01 0.000
0.540 0.942 0.750 −8.478 0.14 0.001 0.621 0.823 0.912 −0.548 1.22 0.001
0.565 0.922 0.761 −8.448 0.09 0.001 0.637 0.823 0.912 −0.558 1.26 0.001
0.590 0.906 0.773 −8.415 0.29 0.001 0.651 0.822 0.913 −0.566 1.37 0.001
0.627 0.883 0.789 −8.373 0.21 0.000 0.676 0.821 0.914 −0.580 1.15 0.000
0.662 0.864 0.804 −8.337 0.12 0.001 0.701 0.820 0.914 −0.596 0.01 0.001
0.704 0.848 0.824 −8.289 0.30 0.001 0.729 0.820 0.915 −0.612 1.14 0.001
0.744 0.836 0.843 −8.242 0.42 0.000 0.760 0.819 0.917 −0.631 0.10 0.000
0.788 0.826 0.865 −8.193 0.48 0.001 0.796 0.818 0.918 −0.652 0.35 0.001
0.828 0.819 0.885 −8.147 0.46 0.000 0.831 0.818 0.920 −0.674 2.04 0.000
0.863 0.815 0.902 −8.109 0.05 0.002 0.862 0.817 0.921 −0.693 1.90 0.002
0.895 0.814 0.920 −8.066 0.63 0.000 0.893 0.817 0.923 −0.712 2.39 0.000
0.926 0.813 0.936 −8.030 0.001 0.921 0.817 0.925 −0.729 0.001
0.951 0.813 0.950 −7.997 0.16 0.000 0.945 0.817 0.926 −0.744 1.21 0.000
0.970 0.815 0.961 −7.971 0.01 0.000 0.965 0.817 0.927 −0.757 0.69 0.000
0.985 0.814 0.968 −7.955 0.044 0.983 0.817 0.928 −0.769 0.000
%ΔA = 0.6 %EA = 17.9 %ΔA = 0.4 %EA = 15.8
Aϕ , j + 1 − Aϕ , j Aϕ , j + 1 − Aϕ , j sufficient quality when considered both individually and

EA , j = · U (T ) + ·U (y1) globally.
Tj + 1 − Tj yj + 1 − yj On the other hand, although the use of quadratic mixing
(24) rules is frequently discouraged for highly polar mixtures,
sometimes, these types of mixtures correlate well. The classical
and after this, the global error percentage was calculated as in mixing rules with one binary interaction parameter are not
eq 25 sufficient to describe mixtures with strong asymmetry in the
j=n−1
∑j = 1 |EA , j| sizes and shapes. This is the reason why a second interaction
%EA = 100· parameter in the PRSV EOS is added in the systems that
j=n−1
∑j = 1 |Aϕ , j | (25) exhibit higher polarity.63 In any case, considering the
aforementioned result, when taking the bibliography as a
The following results were obtained: 14.9 and 11.8% for the reference,62,63 the PRSV29,30 EOS using quadratic mixing rules
ethanol/water system at 1500 kPa and 17.9 and 15.8% for the is of great utility and industrial interest due to its simple
ethanol/water system at 2000 kPa, respectively, for liquid and application and only needs the available properties. These are
vapor phases (see Table 11). Again, the obtained results have the reasons why this EOS has been used in this work.
been less than 20% as a percentage of error cited in the In Table 10, the results of the modeling of the ethanol/water
bibliography.26 system at 100 kPa of this work are included, together with the
Considering the above results, the absolute deviations results obtained from the system studied for 1500 and 2000
between (AT) and (Aϕ) were calculated since it has been kPa, by applying the PRSV29,30 EOS and using the two
reported26 that a set of data is considered to be consistent parameters classical mixing rules (see eq 19) with the binary
when (AT) is equal to (Aϕ) within an acceptable deviation. parameters k1ij and k2ij, which are determined by the VLE data
Therefore, the following equation was applied fitting.
δAj = |Aϕ|j − |AT |j An isobaric bubble point algorithm (p−x1 scheme) was
(26) applied to check the data predictions for ethanol/water
and the results of the individual deviations were less than 0.005 systems at 100, 1500, and 2000 kPa. The simplex method of
for each data. After this, and considering the uncertainties of Nelder−Mead45 was applied. The uncertainties informed in
temperature U(T) = 0.4 K and vapor composition U(y1) = Table 6 were applied to carry out the minimization procedure
0.004 (see Table 6), we proceeded to determine the average for all the binary systems of this work. The objective function
deviation of the data by using eq 27 as follows (OF) was applied, given by the equation as follows
j=n−1 n n
1 1 1
MAD(EA) = ∑ [ |AT , j |·U (T ) + |Aϕ , j |·U (y1) ] OF = ∑ |T exp − T calc| + ∑ |y1exp − y1calc |
n−2 j=1
U (T ) 1
U (y1) 1
(27) (28)
31
The results obtained for MAD(EA) were 0.0193 and 0.0040 Nevertheless, Wong−Sandler (WS) mixing rules can be
for the ethanol/water system at 1500 kPa and 0.0164 and used with nonideal mixtures, that is, highly polar and
0.0035 for the ethanol/water system at 2000 kPa, respectively, asymmetric mixtures, as their application generates very good
for liquid and vapor phases. Therefore, when verifying the correlations of the VLE. The WS31 mixing rules are
previous results together with the data deviations shown in represented by two parameters am and bm that combine to
Table 11, it can be shown that the experimental data of this express the liquid and gas states using the following two
work, after the thermodynamic analysis is performed, have equations
J. Chem. Eng. Data 2021, 66, 928−946
Figure 6. Representation of the experimental data of T−x1−y1 (blue open circle and red open square) from the ethanol/water (ET-WAT) system
at 100, 1500, and 2000 kPa. The fitting curves represent the application of the PC-SAFT28 (TW) model and the PRSV29,30 and PRSVWS29−31
EOSs.
l
n xixj o a(T ) o
|
o
m o
}(1
2 o o RT j o
o
The binary systems of this work were correlated using the
n ~
n
(b − ) + (b −
a(T )
)
ÅÄÅ ÑÉ
∑i ∑ j − kij)
PRSVWS29−31 EOS and by using the simplex method of
ÅÅ1 − A∞E − ∑N xiai(T ) Ñ
ÑÑ
RT i
ÅÅ RTbi Ñ
Ñ
bm = ;
Nelder−Mead45 with the objective function (OF) for
ÅÅÇ Ñ
ÑÖ
ÄÅ n É
ÅÅ EÑ ÑÑ
ÅÅ ÑÑ
CRT i minimization purposes (see eq 28). In Table 10, the results
am= bmÅÅÅ∑ xi ÑÑ
ÅÅ i C ÑÑÑÑ
ai(T ) A∞ obtained after modeling the experimental data of the ethanol/
ÅÇ Ö
+
bi (29) water system at 100, 1500, and 2000 kPa are presented.
To check the modeling of the binary systems using
The binary interaction parameter for each system is kij = kji PRSV29,30 and PRSVWS29−31 EOSs, the critical properties
(see eq 29) and C = −0.62323 is the numerical constant, while were taken from the literature.47 The acentric factor (ω) and
a and b represent respectively the attractive and repulsive the specific parameter (κ1) of Stryjek−Vera30 were calculated
parameters of the EOS that has been used. On the other hand, (see Section 3.2). The vapor pressures (see Table 4) and the
in the WS31 mixing rules, the excess free energy of Helmholtz Antoine equations (see Table 5) of this paper were also
(AE∞) can be assumed equal to the excess Gibbs energy in a employed.
low-pressure model. In this paper, the NTRL model of Consequently, p−T−x1−y1 data from this paper were
Renon−Prausnitz64 is used checked with the predictive PRSV29,30 and PRSVWS29−31
n n EOSs. The mean absolute deviation (MAD), mean propor-
E
A∞ ∑ j xjGjiτji Gij tional deviation (MPD), and standard deviation (SD) of both
= ∑ xi n with = exp(−αijτij)
the alcohol vapor phase mole fraction and the temperature are
RT i
∑r xrGri RT (30)
presented in Table 10.
with αij = αji as well as τij and τji being fitting parameters to In addition, the azeotropic point results obtained by using
obtain optimal agreement between theory and experiment for these EOSs are included in Table 10 for comparison with the
the VLE system. The parameter αij = αji was fixed to 0.47 as calculated azeotropic data from this work. Also, the calculated
informed by Renon−Prausnitz64 to be used with alcohol/water parameters of each model are presented in Table 10. In Figures
mixtures. 6 and 7, the fitting curves of the predictions from PRSV29,30
J. Chem. Eng. Data 2021, 66, 928−946
Figure 7. Representation of the experimental data of x1 versus y1−x1 (circle symbols) from the ethanol/water (ET-WAT) system at 100, 1500, and
2000 kPa. The fitting curves represent the application of the PC-SAFT28 (TW) model and the PRSV29,30 and PRSVWS29−31 EOSs.
and PRSVWS29−31 EOSs are plotted with the experimental and 2000 kPa, the composition of the azeotropes is reproduced
data from Table 6. with errors greater than 3% when using the PRSV29,30 EOS
As in previous papers,39,40 the PRSVWS29−31 EOS shows and errors less than 1% when using the PRSVWS29−31 EOS. In
globally the best results for all the experimental data of this all cases, the errors are less than 0.1% when reproducing the
work (see Table 10). However, the PRSV29,30 EOS reproduces temperatures of the different azeotropes.
well the system at 100 kPa, and there are no significant 3.5.3. The PC-SAFT Model Predictions. Several areas of
differences between the PRSV29,30 and PRSVWS29−31 EOSs. engineering, including the design, control, and modeling of
The systems at 1500 and 2000 kPa are properly reproduced processes and equipment, need reliable and robust tools. The
using the PRSV29,30 EOS, and such differences are not perturbed chain form of the statistical associating fluid
appreciable in the graphical representation (see Figure 6). theory28,65 (PC-SAFT) has probably been developed funda-
In general, when simultaneously checking the predictions mentally for a practical purpose and consequently to be used in
generated by both models for the molar fraction of the vapor different engineering applications.
phase, the predictions made by PRSV29,30 and PRSVWS29−31 The PC-SAFT28,65 model reliability makes the use of
EOSs are not very different (see Figure 7). The differences are different types of properties in the prediction possible, as
more significant when considering the reproduction of the well as in the checking and modeling of the phase equilibria.
temperatures of the systems (see Table 10). However, to achieve these objectives, it is necessary to verify
However, when verifying the prediction that both EOSs the quality and, hence, the errors and deviations when
make on the azeotropic points at different pressures, reproducing the experimental data for the different types of
appreciable differences are observed from both EOSs with mixtures. For that reason, as a previous step, it is essential to
respect to the data calculated in this work (see Table 10). This obtain the appropriate model parameters for the properties of
happens in such a way that the composition of the azeotrope in pure substances.
the system at 100 kPa is predicted with an error greater than The procedure and formulation of PC-SAFT EOS applied to
0.6% when using the PRSVWS29−31 EOS and less than 5% the phase equilibria used in this work are the same as
when using the PRSV29,30 EOS, while in the systems at 1500 previously described.28,65 Consequently, the perturbation
J. Chem. Eng. Data 2021, 66, 928−946
Table 12. PC-SAFT Pure Substance Parameters

ethanol water
parameters TW ref 65 TW ref 65
mi 5.301170 2.3827 2.104350 1.0656
σi [Ȧ ] 2.391487 3.1771 2.269558 3.0007
εi/k [K] 178.009 198.24 261.486 366.51
κAiBi 0.689987 0.032384 0.315925 0.034868
εAiBi/k [K] 955.912 2653.4 1993.670 2500.7
MAD(pi0/kPa) 1.10 0.75
MPD(pi0/%) 0.23 0.99 0.25 1.88
SD(pi0/kPa) 1.39 0.98
MAD(ρ/kmol m−3) 0.006 0.04
MPD(ρ/%) 0.04 0.79 0.07 6.83
SD(ρ/kmol m−3) 0.007 0.05
theory of second order is applied to the reference system of this paper (see Table 4), the molar volumes of the
hard chains for the dispersion term, and the contributions to bibliography,50,57 the critical properties from Daubert−
describe the hard-chain formation as well as the association are Danner,47 and a multiobjective function67 to minimize the
identical to those of the original SAFT model.28 molar densities as well as the vapor pressures were employed.
The PC-SAFT28,65 EOS can be described with different The parameters obtained for ethanol and water are presented
kinds of additive contributions in terms of the reduced together with the bibliography65 parameters in Table 12.
Helmholtz free energy (Ares/NkT). It can be expressed by the By using the pure fluid parameters of the PC-SAFT28 model
equation obtained by us in this work (TW), an isobaric bubble point
algorithm (p−x1 scheme) was applied to perform the
Ares Ahs Achain Adisp Aassoc predictions of the VLE data. The binary systems of ethanol
= + + +
NkT NkT NkT NkT NkT (31) (1) + water (2) at 100, 1500, and 2000 kPa were modeled.
hs
where A /NkT is the hard-sphere reference contribution, The adjustable binary interaction parameter kij of the PC-
Achain/NkT is the hard-sphere chain contribution, Adisp/NkT is SAFT28 model was computed [see the PC-SAFT28 (TW) in
the contribution of the radial distribution function of the hard- Table 10] for all the binary systems of this work by using the
chain fluid, and Aassoc/NkT is the contribution of the simplex method45 and an objective function (see eq 28).
associating interactions to the compressibility factor. Furthermore, the PC-SAFT28 (TW) results obtained by
For the practical application of the PC-SAFT28 model, three modeling the VLE data of this work are presented in Table 10.
pure substance parameters of the pure substance i need to be In addition, the parameters of the bibliography65 corre-
used: the number of segments per chain (mi), the segment sponding to the PC-SAFT28 model (see Table 12) were also
diameter (σi), and the segment energy parameter (εi). applied to the data of the VLE of this work. The statistical
However, the dispersive contribution term, as indicated by results corresponding to the predictions obtained are shown in
Gross−Sadowski,28 require to describe the segment−segment Table 10 (see PC-SAFT28,65). By considering the VLE systems
interactions of some combination rules. The conventional at 1500 and 2000 kPa, appreciable differences in data
Berthelot−Lorentz rules are combining rules that can be predictions are observed with respect to the data calculated
applied to obtain the segment energy parameter (εij) and the by using the parameters obtained in this work, mainly caused
segment diameter (σij) of the mixture, including the binary by deviations in vapor-phase mole fraction reproduction.
interaction parameter (kij) as follows However, the prediction in the VLE system at 100 kPa is much
better. Furthermore, when using the predictions obtained, it is
1 observed that at none of the pressures of the VLE, the
σij = (σii + σjj); εij = εiiεjj (1 − kij)
2 (32) identification of the azeotropic point is achieved.
Two pure substance parameters are necessary to describe Among the reasons why these differences appear, it can be
the associating interactions64 between the association sites Ai indicated that these discrepancies are a consequence of the
and Bi of a pure substance i: the association energy parameter different data used to determine the constants of the model.
εAiBi and the effective association volume parameter κAiBi. For the constants obtained in this work, a smaller range of
However, approximate values for cross-association parameters temperatures has been used and close to that of the VLE data.
are also needed, and these can be determined from pure However, it does not seem that the cause can be attributed
substance association parameters by simple combining rules solely to the different data of the vapor pressures. This
for cross-association as suggested by Wolbach and Sandler66 circumstance is evident when considering the differences
between the data. For the data of the vapor pressures used by
us (see Table 4) and those used in the bibliography50,65 (see
ÄÅ ÑÉ3
ÅÅ σiiσjj ÑÑÑ
1 AiBi
ε AiBj = + ε AjBj); κ AiBj = κ AiBiκ AjBj Table 5), the following statistical results are observed:
ÅÅ
(ε
ÅÅ ÑÑ
ÅÅ 1 (σ + σ ) ÑÑÑ
2 MPD(T/K) = 0.06, MPD(pi0) = 0.74, SD(T/K) = 0.2, and
ÅÅ 2 ii jj Ñ ÑÖ
SD(pi0/kPa) = 2.9 for ethanol (see Figure 2A) and MPD(T/
Ç
K) = 0.02, MPD(pi0) = 0.28, SD(T/K) = 0.1, and SD(pi0/kPa)
(33)
= 1.5 for water (see Figure 2B).
To obtain the five pure substance parameters, we have It should probably be considered that the different objective
proceeded as indicated previously.39 The vapor pressures of functions used in each of the computation procedures to
J. Chem. Eng. Data 2021, 66, 928−946
obtain the parameters of the model are objectively the reason criterion. The systems at 1500 and 2000 kPa were verified by
for the mentioned discrepancies in the predictions. In the applying the high-pressure consistency test of Valderrama−
determination of the constants obtained for this work, a Faúndez. It is checked that both binary systems satisfy the
multiobjective function67 was used, which contains a factor of consistency criteria at high pressure.
weight for minimizing each one of the pi0 and ρii properties. The azeotropic point for the ethanol/water mixtures at 100,
The aim is to reduce the dispersion when reproducing the data 1500, and 2000 kPa has been correlated and verified in this
of the properties used to obtain the model constants since any paper by comparison regarding the bibliographic data and by
systematic error observed in these calculations will be probably using the bibliographic correlation curve for high pressure of
propagated into mixture calculations.28 Otsuki and Williams.
The PC-SAFT28,65 results presented in Table 10 show We have focused on a Peng−Robinson equation of state by
globally a good data reproduction for all the ethanol/water employing both the two-parameter quadratic mixing rules and
mixtures, particularly considering a complex mixture, for which the Wong−Sandler mixing rules. The binary interaction
different strategies can be established for the sites where the parameters for the mixtures of this work were obtained, and
association is formulated. Therefore, after applying a 2B it is observed that VLE data of the systems of this work can be
association scheme for both alcohol and water, good accurately predicted by using both mixing rules.
predictions and a qualitative agreement are shown in the The PC-SAFT model was probed by considering a 2B
temperature of the systems (see Figure 6). association scheme for each substance. After the binary
However, despite the fact that the reproduction of the interaction parameter was obtained from the mixtures of this
evolution of the systems is generally adequate and similar to work, it is observed that the weak reproduction of the data may
that performed with PRSV29,30 and PRSVWS29−31 EOSs, as have its origin in not having used the polar contribution in the
can be seen in Figure 6, when it comes to predicting specific model since water and ethanol are polar substances. Therefore,
points of the mixtures, fundamentally at high water this particular contribution probably should be used to
compositions, the results are not precise enough (see Figure adequately express the interactions between the chain
7). Thus, in the ethanol/water system at 100 kPa, the existence segments of the fluids.
■
of the azeotrope in this mixture is not predicted, and identical
deficiencies in predicting the singular point at high pressures AUTHOR INFORMATION
are observed (see Table 10), although by using the PC-SAFT
Corresponding Author
parameters obtained by us (see the PC-SAFT28 (TW) in Table
12), the azeotropic data at 100 kPa are well predicted. Perhaps, Pedro Susial Badajoz − Escuela de Ingenierías Industriales y
not using an additional parameter of the polar contribution, Civiles, Universidad de Las Palmas de Gran Canaria, Las
due to the dipolar substances water and ethanol, may be the Palmas de Gran Canaria, Canary Islands 35017, Spain;
cause of the insufficient predictive ability of PC-SAFT28,65 for orcid.org/0000-0002-6719-3084; Phone: 34928451489;
the specific data of the binary systems of this work. Email: psusial@dip.ulpgc.es; Fax: 34928458658
When considering the predictions made by all the EOSs Authors
used, it is observed (see Table 10) that the PRSVWS29−31 EOS
Diego García-Vera − Escuela de Ingenierías Industriales y
reproduces the data better for all the systems of this work,
Civiles, Universidad de Las Palmas de Gran Canaria, Las
which gives an orientation about the quality of the WS31
Palmas de Gran Canaria, Canary Islands 35017, Spain
mixing rules.
Patricia Herrera-Vega − Escuela de Ingenierías Industriales y
However, the predictions made by the PRSV29,30 EOS show
the proper interpretation that this EOS makes regarding the
molecular interactions in the mixture due to the polarity of the
Anibal Marrero-Pérez − Escuela de Ingenierías Industriales y
substances. Consequently, the use of the specific parameter
(κ1) of Stryjek−Vera30 in the PR29 EOS and the two
parameters in the quadratic mixing rules can be suitable to
represent the properties in this kind of substance. On the other Complete contact information is available at:
hand, it should be mentioned that the PC-SAFT28,65 model https://pubs.acs.org/10.1021/acs.jced.0c00686
uses only one correlation parameter in the mixtures, while
PRSV29,30 and PRSVWS29−31 EOSs use two and three Notes
parameters, respectively. Therefore, this is a worthy aspect of The authors declare no competing financial interest.
the model that must be highlighted over the previous ones.
4. CONCLUSIONS
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Badajoz Et Al 2021 High Pressure Phase Equilibria in An Ethanol Water Binary System Experimental Data and Modeling

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© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.jced.0c00686

ν E = x1(1 − x1) ∑ Ak jjj zz

Table 4. Experimental Vapor Pressuresa

Table 5. Calculated Antoine Constants for Ethanol and Wateri

Table 6. Isobaric VLE Data of Ethanol (1) + Water (2)a

corresponding to 101 kPa have been presented in the form of

Figure 5. Three-dimensional plot of the bibliographic20 (blue solid

Table 7. Veriﬁcation of Azeotropic Data of This Worka

x1,az paz/kPa PAD(x1,az) PAD(paz/ x1,az paz/kPa PAD(x1,az) PAD(paz/

ij bp yz 2 ÅÅÅÅ a(T )p ij bp yz ÑÑÑÑ

− ÅÅ Å − jjj zzz − jjj zzz ÑÑ

1 ijj ∂nbm yzz

bm jjk ∂ni zz{ k RT {

ÅÅ ∂n ÑÑo ÅÅ Z + (1 + 2 ) bmp ÑÑÑo o

Table 11. High-Pressure Consistency Test Results

%ΔA = 0.8 %EA = 14.9 %ΔA = 0.6 %EA = 11.8

Table 11. continued

%ΔA = 0.6 %EA = 17.9 %ΔA = 0.4 %EA = 15.8

Aϕ , j + 1 − Aϕ , j Aϕ , j + 1 − Aϕ , j suﬃcient quality when considered both individually and

Table 12. PC-SAFT Pure Substance Parameters

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