Article

pubs.acs.org/jced

Isobaric Vapor−Liquid Equilibrium for Two Binary Systems{Propane-

1,2-diol + Ethane-1,2-diol and Propane-1,2-diol + Butane-1,2-diol} at
p = (10.0, 20.0, and 40.0) kPa
Changsheng Yang,* Xue Feng, Yankai Sun, Qian Yang, and Juan Zhi
Synergetic Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering and Technology,
Tianjin University, Tianjin 300072, China

ABSTRACT: Isobaric vapor−liquid equilibrium (VLE) data for the two

binary systems of {propane-1,2-diol + ethane-1,2-diol and propane-1,2-
diol + butane-1,2-diol} at p = (10.0, 20.0, and 40.0) kPa have been
determined using a modified Rose−Williams still with continuous
circulation of both vapor and liquid phases in this work. The
thermodynamic consistency tests of the experimental VLE data were
performed according to the methods of the Herington area test and Van
Ness point test. The experimental isobaric VLE data were then correlated
using the universal quasichemical (UNIQUAC), nonrandom two-liquid
(NRTL), Margules, and Wilson activity coefficient models. Consequently, the calculation values showed good agreements with
the experimental data measured in this study.

■ INTRODUCTION
Ethane-1,2-diol (EG) is considered as one of the most
important organic compounds with various applications,
which is extensively used in the fields of plasticizer, solvent,
antifreeze production and polymer ester manufacture.1 At
present, there exist several reaction routes well-known for the
synthesis of EG. The conventional synthesis process for
manufacturing EG is oil petroleum route which has obvious
drawbacks such as the high consumption of petroleum and the
negative impact on the environment. Therefore, it is necessary
to develop nonpetroleum reaction routes to substitute the
traditional process. In view of several promising nonpetroleum
EG production processes, the C1 process based on the
syngas2,3 mainly derived from coal shows great potential, as
the coal resource is relatively abundant compared with the
petroleum in China and many regions of the world. The C1
process based on the syngas consists of two steps: the synthesis
of dimethyl oxalate (DMO) as the first step, and the second
step being the conversion of DMO to EG by the process of
DMO hydrogenation.
In the process of DMO hydrogenation, propane-1,2-diol
(PG) and butane-1,2-diol (1,2-BD) are synthesized as the
byproducts due to the excessive DMO hydrogenation.
The accurate vapor−liquid equilibrium (VLE) data will make
great contribution to the design of the separation process of
propane-1,2-diol, ethane-1,2-diol, and butane-1,2-diol.
Until now, the isobaric VLE data of the propane-1,2-diol +
ethane-1,2-diol and propane-1,2-diol + butane-1,2-diol systems
are relatively scarce in published papers.2,6,7 Thus, in this work,
the isobaric vapor−liquid equilibrium data of propane-1,2-diol
+ ethane-1,2-diol and propane-1,2-diol + butane-1,2-diol
systems were measured at the pressures of (10.0, 20.0, and
40.0) kPa. Furthermore, the experimental VLE data of the two
systems at 10.0 kPa were compared with the previous data
measured by Zhang et al.2 The results indicated the accuracy
and reliability of the experimental data measured in this paper.
The thermodynamic consistency of the measured VLE data
of the two binary systems at three reduced pressures was
checked and verified according to the methods of the
Herington area test8 and Van Ness point test.9 And the
isobaric VLE data were correlated by four activity coefficient
models, which were the universal quasichemical (UNI-
QUAC)10 model, nonrandom two-liquid (NRTL)11 model,
Margules12 model, and Wilson13 model, respectively. The
calculation values derived from the four models showed good
agreements with the experimental data.

■
However, both the propane-1,2-diol and butane-1,2-diol have
a broad range of applications. For propane-1,2-diol, it has EXPERIMENTAL SECTION
aroused much interest from researchers in many fields owing to
its variety of industrial applications, such as antifreeze, Chemicals. EG (≥0.998, mass fraction purity) and PG
emulsifier, and pharmaceutical.4 For butane-1,2-diol, it is one (≥0.990, mass fraction purity) were purchased from Tianjin
of four isomerides of the butanediols which is an useful
chemical widely used in biotechnological processes with Received: November 28, 2014
enormous potential.5 Thus, a good separation between EG Accepted: February 18, 2015
and the byproducts will bring considerable economic benefits. Published: March 2, 2015

© 2015 American Chemical Society 1126 DOI: 10.1021/je5010824

J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data
Table 1. Densities (ρ), Refractive Indexes (nD), and Boiling Points (Tb)a of Pure Components Compared with Literature Values
compound ρ(298.15 K)
g/cm−3
exptl lit
EG 1.10982 1.110b
PG 1.03190 1.033b
1,2-BD 0.99878 0.99886c
a
Standard uncertainties of ρ and nD are 0.00001 g/cm−3 and 0.0001, respectively. bRef 14. cRef 15. dRef 16.
Guangfu Technology Development Co. Ltd., China. 1,2-BD
(≥0.98, mass fraction purity) was provided by TCI (Tokyo
Chemical Industry Co. Ltd., Shanghai) Development Co., Ltd.
The purities of the three chemical substances were tested by gas
chromatography (GC-SP2100A) analysis with a thermal
conductivity detector (TCD). The impurity in EG was less
than 0.002 (mass fraction), so it was used without any further
purification. For obtaining a high purity, both PG and 1,2-BD
were further purified in order to decrease the experimental
errors. They were first dried by molecular sieves (type pore
diameter 0.3 nm, Guangfu) and then given purification in a
distillation column under the reduced pressure. After the
processes mentioned above, the purity of PG could reach 0.997
(mass fraction). However, the purity of 1,2-BD was not
improved obviously. The final purity of 1,2-BD was 0.992 (mass
fraction). This fact indicated that the conventional distillation
method used for the impurity removal in 1,2-BD cannot bring it
a high purity.
The densities (ρ), refractive indexes (nD), and the boiling
points (Tb) of the three pure substances were determined in
this work. The densities (ρ) were measured using an Anton-
Paar DMA-58 densimeter at (298.15 ± 0.01) K. The refractive
indexes (nD) were measured by a ATAGO NAR-3T Abbe
refractometer at (298.15 ± 0.01) K. The accuracies of the
densimeter and the refractometer are 0.00001 g·m−3 and
0.0001, respectively. The boiling points were measured at 101.3
kPa with an uncertainty of 0.1 K. All of the three pure substance
properties determined in this work are shown in Table 1 along
with the published values.14−16
Apparatus and Procedures. The measurements of the
isobaric VLE data were carried out in a modified Rose−
Williams still which was made up of a condenser and a boiling
chamber. This experimental device could guarantee the vapor
and liquid phases full contact by continuous circulation of the
two phases and reach equilibrium rapidly. The experimental
apparatus is presented in Figure 1. The operating pressure in
the experiments was regulated by a buffer tank and a vacuum
pump. The vacuum pump ran continuously, and a needle valve
linked with the vacuum pump was used to control the air
amount entering into the system and change the system
pressure slowly. By regulating the opening of the valve, the
pressure needed in the experiments can be obtained and kept
stable for a long time. We used a U-shaped differential
manometer to determine the system pressure with an
uncertainty of 0.13 kPa. The energy needed of the system
was provided by a heating rod under the control of a
thermocouple. The heating intensity was kept at a level that
could enable the system to produce 30 condensate drops per
minute. The equilibrium temperature was determined precisely
with a mercury thermometer accurate to 0.01 K. The ethanol
was chosen as the condensation liquid in the condenser whose
working temperature is (263.15 to 273.15) K. It aimed at
Article
nD (298.15 K) Tb (101.3 kPa)
K
exptl lit exptl lit
1.4310 1.4306b 470.40 470.45b
1.4320 1.4314b 460.69 460.75b
1.4378 1.4374c 469.71 469.575d
Figure 1. Rose−Williams still and other apparatus: (1) heating rod,
(2) liquid sample connection, (3) vapor (cooled to liquid) sample
connection, (4) condenser, (5) coolant inlet, (6) coolant outlet, (7)
U-shaped differential manometer, (8) vacuum pump, (9) a buffer tank,
(10) valve, (11) a precision mercury thermometer.
converting the vapor phase into the liquid phase quickly for
avoiding the mass loss in the solution. To ensure the precision
of the apparatus as much as possible, the vaseline was applied to
all of the ground-glass joints for achieving good sealing.
The equilibrium still had a total volumetric capacity of 140
cm3 approximately. About half of the volume was full of the
solution. The solutions were prepared gravimetrically with an
electronic balance accurate to 0.0001 g. In each experiment,
after putting the solutions into the still, we turned on the
vacuum pump, the heating equipment, and then adjusted the
opening of the needle valve until the system pressure arrived at
the desired value. The equilibrium was achieved with the
fluctuation of the vapor temperature within 0.1 K and then
both the liquid and vapor phase samples were taken out from
the sampling ports by employing a microsyringe for GC
analysis. The reliability of the experimental device has already
been verified in our previous work.17−20
Analysis. The equilibrium of the liquid and vapor
(condensed to liquid) samples were quantificationally analyzed
by a BFRL SP-2100A GC that was equipped with a flame
ionization detector used together with a SE-54 capillary column
(30 m × 0.32 mm × 0.5 μm). We used a N2000
chromatography station to treat the GC response peaks. High
purity nitrogen was used as the carrier gas whose flow velocity
was maintained constant at 20 mL·min−1. The flow rates of H2
(≥0.9999, mass fraction purity) and air (≥0.9999, mass fraction
purity) were both 20 mL·min−1. For the two binary systems,
they had the same chromatography operation condition. The
temperatures of the column, the injector, and the detector were
(473.15, 513.15, and 533.15) K, respectively. The injection
volume of each sample into the GC was 0.4 μL.
A series of standard solutions of known compositions was
prepared gravimetrically by using an analytical balance accurate
to 0.0001 g for the calibration of GC. The external standard was
1127 DOI: 10.1021/je5010824
J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data Article

chosen to obtain quantitative analysis results by using the Table 3. VLE Experimental Data and Calculated Activity
external standard curve to convert the peak areas into mole Coefficient (γ) for the PG (1) + 1,2-BD (2) system at p =
fractions of each sample. At least three measurements were (10.0, 20.0, and 40.0) kPaa
done of each sample to ensure the accuracy and reproducibility
T x1 y1 γ1 γ2
of the quantitative analysis results, and the final value was the
average of the most close three results. The uncertainties of the K
vapor and liquid mole fractions were within 0.005 and 0.002, 10 kPa 398.26 1.000 1.000 1.000
respectively.

■
398.55 0.942 0.954 1.000 1.076
399.14 0.832 0.859 0.993 1.109
RESULTS AND DISCUSSION 399.51 0.757 0.798 0.998 1.080
Experimental Data. The isobaric vapor−liquid equilibrium 399.92 0.667 0.721 1.005 1.069
(VLE) data for the two binary systems of {propane-1,2-diol + 400.37 0.570 0.637 1.019 1.055
401.06 0.436 0.511 1.038 1.051
Table 2. VLE Experimental Data and Calculated Activity 401.89 0.291 0.373 1.095 1.033
Coefficient (γ) for the PG (1) + EG (2) system at p = (10.0, 402.78 0.179 0.254 1.167 1.020
20.0, and 40.0) kPaa 403.58 0.107 0.164 1.218 1.014
404.96 0.020 0.031 1.162 1.008
T x1 y1 γ1 γ2 405.41 0.000 0.000 1.000
K 20 kPa 414.88 1.000 1.000 1.000
10 kPa 398.25 1.000 1.000 1.000 415.01 0.969 0.974 1.000 1.117
398.46 0.939 0.945 0.998 1.259 415.62 0.846 0.873 1.002 1.072
398.79 0.859 0.883 1.004 1.142 416.09 0.751 0.792 1.005 1.065
399.27 0.768 0.810 1.009 1.104 416.82 0.625 0.683 1.012 1.046
399.86 0.662 0.728 1.026 1.057 417.17 0.564 0.628 1.017 1.041
400.31 0.596 0.667 1.024 1.061 417.78 0.469 0.541 1.029 1.029
401.23 0.452 0.543 1.056 1.031 418.67 0.344 0.419 1.049 1.017
402.02 0.339 0.434 1.088 1.023 419.16 0.282 0.354 1.061 1.013
402.57 0.280 0.364 1.079 1.031 420.31 0.157 0.213 1.097 1.004
403.82 0.156 0.227 1.145 1.013 421.73 0.032 0.048 1.148 1.000
404.83 0.075 0.120 1.207 1.007 422.15 0.000 0.000 1.000
406.10 0.000 0.000 1.003 40 kPa 433.22 1.000 1.000 1.000
20 kPa 414.88 1.000 1.000 1.000 433.53 0.953 0.962 0.998 1.050
415.05 0.976 0.978 0.995 1.077 434.14 0.848 0.869 0.991 1.095
415.62 0.854 0.884 1.005 1.063 434.97 0.695 0.737 0.996 1.063
416.19 0.732 0.785 1.018 1.064 435.17 0.660 0.706 0.998 1.058
417.08 0.577 0.648 1.030 1.064 435.79 0.560 0.615 1.002 1.047
417.82 0.476 0.551 1.031 1.032 436.82 0.404 0.467 1.017 1.031
418.87 0.349 0.436 1.068 1.023 437.27 0.339 0.404 1.032 1.023
420.12 0.223 0.299 1.092 1.016 438.12 0.235 0.297 1.062 1.011
421.01 0.151 0.212 1.105 1.011 439.42 0.112 0.159 1.140 0.995
422.02 0.079 0.115 1.102 1.002 440.68 0.011 0.020 1.397 0.996
423.29 0.000 0.000 1.271 440.83 0.000 0.000 1.000
a
40 kPa 433.22 1.000 1.000 1.000 Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.13 kPa, u(x) =
433.64 0.928 0.933 0.990 1.265 0.002, and u(y) = 0.005.
434.27 0.796 0.825 0.998 1.140
434.77 0.699 0.747 1.011 1.096
435.14 0.629 0.693 1.028 1.065
435.54 0.561 0.632 1.037 1.063
the liquid phase (xi), the activity coefficient (γi) of each
436.19 0.468 0.543 1.043 1.064
component, and the equilibrium temperature (T).
436.59 0.417 0.497 1.057 1.054
Pure Component Vapor Pressure. For propane-1,2-diol
437.53 0.308 0.392 1.092 1.038 and ethane-1,2-diol, the saturation vapor pressures of the pure
438.61 0.205 0.284 1.144 1.023 components were calculated with Antoine eq 1 taken from
440.14 0.091 0.145 1.248 1.012 Yaws.14 For 1,2-butanediol, the pure component vapor pressure
440.91 0.051 0.084 1.256 1.011 was calculated with Antoine eq 2 obtained from literature.21
442.17 0.000 0.000 1.002 ⎛ 760ps ⎞
a
Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.13 kPa, u(x) = log⎜ i
/kPa⎟
0.002, and u(y) = 0.005. ⎝ 101.325 ⎠
B
=A+ + C log(T /K) + D(T /K) + E(T /K)2
T /K
ethane-1,2-diol, propane-1,2-diol + butane-1,2-diol} at p = (1)
(10.0, 20.0, and 40.0) kPa are presented in Tables 2 and 3,
B
separately. The VLE data listed consist of the equilibrium mole ln(pis /kPa) = A + + C ln(T /K) + D(T /K)E
fraction of the vapor phase (yi), the equilibrium mole fraction of T /K (2)

1128 DOI: 10.1021/je5010824

J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data Article

Table 4. Antoine Coefficient of Pure Components Used in This Study

Compound Antoine coefficients Range of T
A B C D E K
−09 −06
EG a
82.4062 −6347.2 −25.433 −2.37 × 10 8.75 × 10 260.15 to 645
PGa 90.2930 −6696.8 −28.109 −1.33 × 10−10 9.37 × 10−06 213.15 to 626
1,2-BDb 96.3722 −11548 −10.925 4.26 × 10−18 6 220 to 680
a
Ref 14. bRef 21.

Table 7. Mathematical Forms of the Activity Coefficient

Equations Used in This Work
Wilson
⎛ Aij Aji ⎞
ln γ1 = − ln(x1 + Aijxj) + ⎜⎜ − ⎟
⎝ i
x + x A
j ij xj + xiAji ⎟⎠
Vj ⎛ gij − gii ⎞
Aij = exp⎜− ⎟
Vi ⎝ RT ⎠
RTci τi
Vi = Zci τi = 1 + (1 − T /Tci)2/7 T /Tci ≤ 0.75
Pci
NRTL
⎡ Gji2τji Gij2τij ⎤
ln γi = xj2⎢ + ⎥
⎢⎣ (xi + xjGji)2
(xj + xiGij) ⎥⎦
2

gij − gjj
τij = Gij = exp(− aijτij) aij = aji
Figure 2. Experimental saturation pressures of butane-1,2-diol (w = RT
0.992, mass fraction) compared with the literature values calculated by UNIQUAC
the Antoine eq 2. Figure: ●, experimental values; , literature values. ⎛ϕ⎞ ⎛
⎛Z⎞ ⎛θ ⎞ r ⎞
ln γi = ln⎜⎜ i ⎟⎟ + ⎜ ⎟qi ln⎜⎜ i ⎟⎟ + ϕj⎜⎜li − i l j⎟⎟ − qi(θi + θτ
j ji)
⎝ 2 ⎠ ⎝ϕ⎠
Table 5. Experimental Vapor Pressuresa of 1,2-Butanediol at ⎝ xi ⎠ i ⎝ rj ⎠
w = 0.992 Mass Fraction ⎛ τji τij ⎞
+ θjqi⎜⎜ − ⎟⎟
T P T P ⎝ i
θ + θτ
j ji θj + i ij ⎠
θτ
K kPa K kPa Z qixi rx
i i
li = (ri − qi) − (ri − 1) θi = φi =
392.06 5.62 432.29 29.56 2 qixi + qjxj rx
i i + rjxj
397.24 7.21 437.41 35.54 ⎛ gji − gii ⎞
402.31 8.86 442.77 41.92 τji = exp⎜− ⎟
⎝ RT ⎠
406.54 10.62 447.52 50.54
412.23 13.56 452.13 58.86 Margules
417.66 16.89 457.24 69.36 ln γi = xj2[Aij + 2xi(Aji − Aij)]
422.48 20.34 462.57 81.92
427.21 24.45 466.64 92.78 Table 8. Critical Constants (Tc, Pc, Zc), Molecule Volume
a
Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.13 kPa. Parameters r, and Area Parameters q for the UNIQUAC
Model
Table 6. Results of Thermodynamic Consistency Test for the
Two Systems at Three Pressures compound q r Tc Pc Zc
K kPa
system p area testa point testb
PG 2.784a 3.0824a 626b 6.1b 0.280b
kPa D−J |Δy1| EG 2.248c 2.4088c 645b 7.53b 0.268b
PG(1) 10 3.739 + 0.004 + 1,2-BD 3.324a 3.7568a 680d 5.21d 0.279a
+ 20 8.237 + 0.005 + a
Ref 21. bRef 14. cRef 24. dRef 25.
EG(2) 40 7.759 + 0.004 +
PG(1) 10 6.327 + 0.005 +
+ 20 1.604 + 0.001 + pressures of 1,2-butanediol (w = 0.992, mass fraction) were
1,2- BD(2) 40 4.900 + 0.004 + determined in this work in order to make a comparison with
a
Ref 8 and 23. bRef 9. the values calculated with Antoine eq 2, as shown in Figure 2.
The experimental vapor pressures of 1,2-butanediol are listed in
Table 5. The average deviation between the experimental
where A, B, C, D, and E are Antoine constants and T stands for saturation pressures and literature values calculated by the
the system temperature in Kelvin. The values of Antoine Antoine eq 2 was Δp = 0.013, so the experimental saturation
constants14,21 for all of the components are listed in Table 4. pressures fitted well with the literature values. Therefore,
To verify the reliability of the Antoine eq 2 from Aspen Antoine eq 2 was capable of accurately calculating the pressure
Physical Property System pure-component data bank, the vapor of 1,2-BD. Δp is defined as follows:
1129 DOI: 10.1021/je5010824
J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data Article

Table 9. Parameters for the UNIQUAC, NRTL, Wilson, and Table 10. Parameters for the UNIQUAC, NRTL, Wilson,
Margules Equations, AADT/K, AADy1, RMSDT/K and and Margules Equations, AADT/K, AADy1, RMSDT/K, and
RMSDy1 for {PG (1) + EG (2)} at p = (10.0, 20.0, and 40.0) RMSDy1 for {PG (1) + 1,2-BD (2)} at p = (10.0, 20.0, and
kPa 40.0) kPa
10.0 kPa 20.0 kPa 40.0 kPa 10.0 kPa 20.0 kPa 40.0 kPa
UNIQUAC Parameters UNIQUAC Parameters
g12 − g22/J·mol−1 35.479 36.850 86.4096 g12 − g22/J·mol−1 103.385 24.125 8.726
g21 − g11/J·mol−1 249.606 250.302 264.852 g21 − g11/J·mol−1 103.675 125.375 118.349
AADT/K 0.07 0.04 0.17 AADT/K 0.27 0.06 0.12
AADy1 0.002 0.005 0.004 AADy1 0.005 0.004 0.005
RMSDT/K 0.09 0.05 0.20 RMSDT/K 0.31 0.07 0.13
RMSDy1 0.003 0.006 0.005 RMSDy1 0.008 0.004 0.005
NRTL Parameters NRTL Parameters
g12 − g22/J·mol−1 106.938 111.485 237.8216 g12 − g22/J·mol−1 80.196 200.000 68.373
g21 − g11/J·mol−1 518.451 520.148 538.281 g21 − g11/J·mol−1 508.002 199.203 261.463
AADT/K 0.08 0.06 0.18 AADT/K 0.21 0.04 0.09
AADy1 0.002 0.004 0.005 AADy1 0.006 0.001 0.005
RMSDT/K 0.01 0.07 0.22 RMSDT/K 0.26 0.05 0.11
RMSDy1 0.003 0.005 0.006 RMSDy1 0.007 0.002 0.007
Wilson Parameters Wilson Parameters
g12 − g11/J·mol−1 505.062 399.916 504.051 g12 − g11/J·mol−1 533.346 253.3156 275.423
g21 − g22/J·mol−1 289.867 524.030 296.727 g21 − g22/J·mol−1 67.161 208.741 102.902
AADT/K 0.06 0.03 0.15 AADT/K 0.23 0.05 0.10
AADy1 0.002 0.004 0.004 AADy1 0.006 0.002 0.006
RMSDT/K 0.07 0.04 0.18 RMSDT/K 0.28 0.07 0.12
RMSDy1 0.003 0.005 0.005 RMSDy1 0.008 0.003 0.007
Margules Parameters Margules Parameters
A12 0.2384 0.2153 0.3313 A12 0.3488 0.1453 0.1518
A21 0.1328 0.1394 0.1001 A21 0.0136 0.0851 0.0334
AADT/K 0.05 0.03 0.05 AADT/K 0.03 0.01 0.02
AADy1 0.004 0.005 0.005 AADy1 0.005 0.001 0.002
RMSDT/K 0.06 0.04 0.06 RMSDT/K 0.03 0.01 0.02
RMSDy1 0.005 0.006 0.007 RMSDy1 0.007 0.001 0.003
AADT = (1/N)Σi N= 1|Tcal
i − Ti |, AADy1 = (1/N)Σi = 1|yi − yi |,
exp N cal exp
AADT = (1/N)Σi N= 1|Tcal
i − Ti |, AADy1 = ((1/N))Σi = 1|yi − yi |,
exp N cal exp

RMSDT = ((Σi = 1(Ti − Ti ) )/N) , RMSDy1 = ((Σi = 1(yi −

N cal exp 2 1/2 N cal
RMSD T = ((Σi = 1(Ti − Ti ) )/N) , RMSD y1 = ((Σi = 1(yi −
N cal exp 2 1/2 N cal

yexp 2 1/2
i ) )/N) . yexp 2 1/2
i ) )/N) .

∑N |(pexp − pcal )/pexp |

Δp =
N (3)
where N is the number of the experimental data points. pexp and
pcal represent the experimental and calculated saturation
pressures, respectively.
Thermodynamic Consistency Test. The thermodynamic
consistency tests of the experimental VLE data were treated for
the two binary systems by the methods of the Herington area
test and Van Ness point test so as to check the reliability of the
experimental data.
According to the method of the Herington area test, the
isobaric VLE data was considered consistent if |D − J| < 10.
S+ − S−
D= ·100
S+ + S− (4)
Figure 3. VLE data for the system {PG (1) + EG (2)} at 10.0 kPa: △,
where S+ and S− are obtained from the ln (γ1/γ2) − x1 plot. S+ experimental data for T−x; ▲, experimental data for T−y; ○,
is the area of the plot above the x axis. S− is the area of the plot literature data for T−x; ●, literature data for T−y; , calculated data
below the x axis by the UNIQUAC equation for T−x−y; ···, calculated data by the
Wilson equation; ---, calculated data by the NRTL equation; -·-·-,
(Tmax − Tmin) calculated data by the Margules equation. x1 and y1 are the mole
J = 150· fractions of PG in the liquid and vapor phases, respectively.
Tmin (5)
where Tmax and Tmin represent the maximum and minimum For the Van Ness point test, Gmehling and Onken21
temperatures of the system, respectively. suggested the isobaric VLE data were thermodynamically
1130 DOI: 10.1021/je5010824
J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data
Figure 4. VLE data for the system {PG (1) + EG (2)} at 20.0 kPa: △,
experimental data for T−x; ▲, experimental data for T−y; ,
calculated data by the UNIQUAC equation for T−x−y; ···, calculated
data by the Wilson equation; ---, calculated data by the NRTL
equation; -·-·-, calculated data by the Margules equation; x1 and y1 are
the mole fractions of PG in the liquid and vapor phases, respectively.
Figure 5. VLE data for the system {PG (1) + EG (2)} at 40.0 kPa: △,
experimental data for T−x; ▲, experimental data for T−y; ,
calculated data by the UNIQUAC equation for T−x−y; ···, calculated
data by the Wilson equation; ---, calculated data by the NRTL
equation; -·-·-, calculated data by the Margules equation. x1 and y1 are
the mole fractions of PG in the liquid and vapor phases, respectively.
consistent, if the average deviation of the vapor mole fractions
was less than or equal to 0.01.
A four-parameter Legendre polynomial was used to express
the excess Gibbs free energy
k Therefore, the experimental data were consistent and reliable.
GE
g= = x1(1 − x1) ∑ ak Lk (x1)
RT
and a nonlinear optimization method was chosen to minimize
the following objective function:
F= ∑ (y1cal + y2cal − 1) (6)
where y1cal and y2cal represent the calculated values of vapor-
phase mole fractions of component 1 and 2, respectively.
The results of the thermodynamic consistency tests of the
two systems are presented in Table 6. As it could be seen
directly, all of the |D − J| values and the average deviations in
1131
Article
Figure 6. VLE data for the system {PG (1) + 1,2-BD (2)} at 10.0 kPa:
△, experimental data for T−x; ▲, experimental data for T−y; ○,
literature data for T−x; ●, literature data for T−y; , calculated data
by the UNIQUAC equation for T−x−y; ···, calculated data by the
Wilson equation; ---, calculated data by the NRTL equation; -·-·-,
calculated data by the Margules equation. x1 and y1 are the mole
fractions of PG in the liquid and vapor phases, respectively.
Figure 7. VLE data for the system {PG (1) + 1,2-BD (2)} at 20.0 kPa:
△, experimental data for T−x; ▲, experimental data for T−y;
calculated data by the UNIQUAC equation for T−x−y; ···, calculated
data by the Wilson equation; ---, calculated data by the NRTL
equation; -·-·-, calculated data by the Margules equation. x1 and y1 are
the mole fractions of PG in the liquid and vapor phases, respectively.
vapor mole fractions were less than 10 and 0.01, respectively.
Data Correlation. At experimental pressures of (10.0, 20.0,
and 40.0) kPa, the vapor phase could be assumed as an ideal
phase. Therefore, the VLE equation can be simplified as
follows:
γ1x1pis = yp
i
(i = 1, 2) (7)
where xi and yi are the mole fractions of component i in the
liquid and vapor phases, respectively; p stands for the system
pressure; and pis represents the saturation vapor pressure of
pure component i. In this way, the experimental values of the
activity coefficients of component i of the liquid phase can be
calculated and also listed in Tables 2 and 3.
DOI: 10.1021/je5010824
J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data
Figure 8. VLE data for the system {PG (1) + 1,2-BD (2)} at 40.0 kPa:
△, experimental data for T−x; ▲, experimental data for T−y;
calculated data by the UNIQUAC equation for T−x−y; ···, calculated
data by the Wilson equation; ---, calculated data by the NRTL
equation; -·-·-, calculated data by the Margules equation. x1 and y1 are
the mole fractions of PG in the liquid and vapor phases, respectively.
All of the experimental VLE data were correlated by using
the UNIQUAC, NRTL, Margules, and Wilson activity
coefficient models. The equation forms are listed in Table 7.
For UNIQUAC model, Z stands for the lattice coordination
number whose value is 10; gij represents the interaction energy
between the molecules i and j; the van der Waals area
parameters (qi) and the volume parameters (ri) are presented in
Table 8; gij − gjj are the binary interaction parameters. As to
NRTL model, the nonrandomness parameter (aij) is fixed to
0.3; and gij − gjj are the binary interaction energy parameters. Aij
and Aji stand for the Margules parameters. For Wilson model,
gij − gii are the binary interaction energy parameters; the values
of the critical temperature (T ci ), pressure (P ci ), and
compressibility factor of component i are also presented in
Table 8.
The values of the binary interaction energy parameters of the
four models studied in this work were obtained by minimizing
the following objective function:
⎡⎛ ⎞2 ⎤
⎢⎜ γexp − γcal ⎟ ⎥
OF = ∑ ⎢⎜
γexp ⎟⎠ ⎥
⎣⎝ ⎦ (8)
where γexp and γcal are the experimental and calculated activity
coefficients, respectively.
The average absolute deviations (AAD) and the root-mean-
square deviations (RMSD) of the equilibrium temperatures and
vapor-phase mole fractions of the two binary systems at three
reduced pressures were both calculated to measure the
agreement between the experimental and calculated values.
The AAD and RMSD are given as follows:
N reasonably small (less than 0.008 in vapor-phase mole fraction
1 and 0.31 K in boiling temperature). The results indicated that
AAD = ∑ |Uiexp − Uical|
N i=1 (9)
N this work will be a valuable reference to the chemical
∑i = 1 (Uiexp − Uical)2
RMSD =
N (10)
1132
Article
where U is a variable quantity, which stands for the equilibrium
temperature and vapor-phase mole fraction in this work; N is
the number of experimental data points.
The values of the binary interaction energy parameters,
AADT, AADy1, RMSDT, and RMSDy1 for each system at three
pressures are presented in Tables 9 and 10.
The experimental VLE data as symbols together with the
calculated values as lines are plotted as T−x1−y1 diagrams for
the systems of {propane-1,2-diol + ethane-1,2-diol} and
{propane-1,2-diol + butane-1,2-diol} at p = (10.0, 20.0, and
40.0) kPa in Figures 3 to 8. Besides, the published data2 for the
two systems at 10.0 kPa are also plotted in Figures 3 and 6. A
comparison was made between the experimental data and the
published values. On the whole, the data measured in this work
agreed well with the literature data. The quality of the fit was
good.
For the two binary systems of {propane-1,2-diol + ethane-
1,2-diol} and {propane-1,2-diol + butane-1,2-diol}, the
maximum absolute deviations of the temperatures |ΔT|max
between the correlated values derived from the four activity
coefficient models and experimental values were (0.22, 0.13,
and 0.45) K and (0.50, 0.12, and 0.21) K at p = (10.0, 20.0, and
40.0) kPa, respectively. The maximum absolute deviations of
the vapor-phase mole fraction|Δy1|max between the correlated
values derived from the four activity coefficient models and the
experimental values were (0.007, 0.009, and 0.009) and (0.009,
0.006, and 0.011), respectively. As it can be seen from the
results in Tables 9 and 10, the deviations of the regression are
reasonably small. Therefore, the UNIQUAC, NRTL, Margules,
and Wilson models were able to correlate the experimental data
determined in this study accurately and the four models had
similar accuracies.
■ CONCLUSION
The isobaric vapor−liquid equilibrium data of two binary
systems of {propane-1,2-diol + ethane-1,2-diol} and {propane-
1,2-diol + butane-1,2-diol} were determined at p = (10.0, 20.0,
and 40.0) kPa in a modified Rose−Williams still. The saturation
vapor pressures of 1,2-BD were determined at the temperatures
T = (392.06 to 466.64) K. The experimental vapor pressures
indicated that the Antoine eq 2 from Aspen data bank was able
to calculate the saturation vapor pressures of 1,2-BD at certain
temperatures accurately. All of the experimental data passed the
thermodynamic consistency tests by means of the Herington
area test and Van Ness point test. The UNIQUAC, Wilson,
Margules, and NRTL activity coefficient equations were used to
correlate the experimental VLE data. For the two binary
systems, the absolute average deviations of the boiling
temperature AADT were below (0.27, 0.15, and 0.18) K, and
the absolute average deviations of the vapor-phase mole
fraction AADy1 were below (0.006, 0.005, and 0.006) at p =
(10.0, 20.0, and 40.0) kPa, respectively. In addition, the root-
mean-square deviations (RMSD) of the regression were also
the four models were capable of correlating the measured
systems accurately. The experimental binary data measured in
engineering systems including ethane-1,2-diol, propane-1,2-
diol, and butane-1,2-diol in the future.
DOI: 10.1021/je5010824
J. Chem. Eng. Data 2015, 60, 1126−1133
Journal of Chemical & Engineering Data

■
Article

AUTHOR INFORMATION of Methanol, Diethylamine, and N,N-Diethylethanolamine at p = (60.0

and 101.3) kPa. J. Chem. Eng. Data 2013, 58, 482−487.
Corresponding Author
(19) Yang, C. S.; Zhang, P.; Qin, Z. L.; Feng, Y.; Zeng, H.; Sun, F. Z.
*E-mail: changshengyangtju@163.com. Fax: 022-2740-3389. Isobaric Vapor−Liquid Equilibrium for the Binary Systems (Diethyl-
Telephone: 022-2789-0907. amine + Ethanol), (Ethanol + N,N-Diethylethanolamine), and
Notes (Diethylamine + N,N-Diethylethanolamine) at p = (80.0 and 40.0)
The authors declare no competing financial interest. kPa. J. Chem. Eng. Data 2014, 59, 750−756.

■
(20) Yang, C. S.; Sun, Y. K.; Qin, Z. L.; Feng, Y.; Zhang, P.; Feng, X.
REFERENCES Isobaric Vapor−Liquid Equilibrium for Four Binary Systems of
Ethane-1,2-diol, Butane-1,4-diol, 2-(2-Hydroxyethoxy)ethan-1-ol, and
(1) Yue, H. R.; Zhao, Y. J.; Ma, X. B.; Gong, J. L. Ethylene glycol: 2-[2-(2-Hydroxyethoxy)ethoxy]ethanol at 10.0 kPa, 20.0 kPa, and 40.0
properties, synthesis, and applications. Chem. Soc. Rev. 2012, 41, kPa. J. Chem. Eng. Data 2014, 59, 1273−1280.
4218−4244. (21) Aspen Plus, version 7.0; Aspen Technology, Inc.: Burlington,
(2) Zhang, L. H.; Wu, W. H.; Sun, Y. L.; Li, L. Q.; Jiang, B.; Li, X. G. MA, 2011.
Isobaric Vapor−Liquid Equilibria for the Binary Mixtures Composed (22) Gmehling, J.; Onken, U. Vapor-Liquid Equilibrium Data
of Ethylene Glycol, 1,2-Propylene Glycol, 1,2-Butanediol, and 1,3- Collection; Chemistry Data Series; DECHEMA: Frankfurt, Germany,
Butanediol at 10.00 kPa. J. Chem. Eng. Data 2013, 58, 1308−1315. 1977.
(3) Sun, L.; Fu, J.-Y.; Li, W.; Zhan, X.-L.; Xiao, W.-D. Binary vapor− (23) Redlich, O.; Kister, A. T. Algebraic Representation of
liquid equilibrium of methyl glycolate and ethylene glycol. Fluid Phase Thermodynamic Properties and the Classification of Solutions. Ind.
Equilib. 2006, 250, 33−36. Eng. Chem. 1948, 40, 345−348.
(4) Garcia-Chavez, L. Y.; Shazad, M.; Schuur, B.; de Hann, A. B. (24) Kamihama, N.; Matsuda, H.; Kurihara, K.; Tochigi, K.; Oba, S.
(Liquid + liquid) equilibrium data for the system (propylene glycol + Isobaric Vapor−Liquid Equilibria for Ethanol + Water + Ethylene
water + tetraoctyl ammonium 2-methyl-1-naphthoate). J. Chem. Glycol and Its Constituent Three Binary Systems. J. Chem. Eng. Data
Thermodyn. 2012, 54, 238−244. 2012, 57, 339−344.
(5) Nakajima, T.; Sawai, S.; Sato, S.; Nakahara, T. Production of 2- (25) Steele, W. V.; Chirico, R. D.; Knipmeyer, S. E.; Nguyen, A.
Hydroxybutyric Acid from 1,2-butanediol by Resting Cells of Vapor Pressure of Acetophenone, (±)-1,2-butanediol, (±)-1,3-
Rhodococcus sp. Strain TB-42. Biosci., Biotechnol., Biochem. 1994, 58, Butanediol, Diethylene Glycol Monopropyl Ether, 1,3-Dimethylada-
683−686. mantane, 2-Ethoxyethyl Acetate, Ethyl Octyl Sulfide, and Pentyl
(6) Zhang, J. W.; Bai, P.; Zhang, W. Isobaric Vapor Liquid Acetate. J. Chem. Eng. Data 1996, 41, 1255−1268.
Equilibrium (VLE) Data of the Systems Ethylene Glycol-Glycerol
and 1, 2-Propylene Glycol-Ethylene Glycol at 20 Pa. Adv. Mater. Res.
2011, 301, 235−240.
(7) Z, Y.; W, Y. Y.; Z, J. W.; C, K.; W, B.; J, L. J. Thermodynamics in
separation for the ternary system 1,2-ethanediol + 1,2-propanediol +
2,3-butanediol. Ind. Eng. Chem. Res. 2014, 53, 12143−12148.
(8) Herington, E. F. G. Tests for the Consistency of Experimental
Isobaric Vapor-Liquid Equilibrium Data. J. Inst. Petrol. 1951, 37, 457−
470.
(9) Van Ness, H. C.; Byer, S. M.; Gibbs, R. E. Vapor-Liquid
Equilibrium: Part I. An Appraisal of Data Reduction Methods. AIChE
J. 1973, 19, 238−244.
(10) Abrams, D. S.; Prausnitz, J. M. Statistical Thermodynamics of
Liquid Mixtures: A New Expression for the Excess Gibbs Energy of
Partly or Completely Miscible Systems. AIChE J. 1975, 21, 116−128.
(11) Renon, H.; Prausnitz, J. M. Local Compositions in
Thermodynamic Excess Functions for Liquid Mixtures. AIChE J.
1968, 14, 135−144.
(12) Gess, M.; Danner, A. R. P.; Nagvekar, M. Thermodynamic
Analysis of Vapor−Liquid Equilibria: Recommended Models AND A
Standard Data Base; DIPPR, AIChE: New York, 1991.
(13) Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New Expression
for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86,
127−130.
(14) Yaws, C. L. Chemical Properties Handbook, 1st ed.; McGraw-Hill
Yaws Co.: New York, 1999.
(15) George, J.; Sastry, V. N. Densities, Dynamic Viscosities, Speeds
of Sound, and Relative Permittivities for Water + Alkanediols
(Propane-1,2- and -1,3-diol and Butane-1,2-, -1,3-, -1,4-, and -2,3-
Diol) at Different Temperatures. J. Chem. Eng. Data 2013, 48, 1529−
1539.
(16) Mamedov, M. K.; Piraliev, A. G.; Rasulova, R. A. Synthesis of
bicyclo [2.2.1] heptyl monoethers of aliphatic diols. Russ, J. Appl.
Chem. 2009, 82, 518−520.
(17) Yang, C. S.; Feng, Y.; Cheng, B.; Zhang, P.; Qin, Z. L.; Zeng, H.;
Sun, F. Z. Vapor−Liquid Equilibria for Three Binary Systems of N-
Methylethanolamine, N-Methyldiethanoliamine, and Ethylene Glycol
at P = (40.0, 30.0, and 20.0) kPa. J. Chem. Eng. Data 2013, 58, 2272−
2279.
(18) Yang, C. S.; Qin, Z. L.; Xu, Y. L.; Zeng, H.; Sun, F. Z.; Zhang,
P.; Feng, Y. Isobaric Vapor−Liquid Equilibrium for the Binary Systems

1133 DOI: 10.1021/je5010824

J. Chem. Eng. Data 2015, 60, 1126−1133