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Vapor Liquid Equilibrium for the Binary of 1‑Methoxy-2-propanol +

1,2-Propanediol and 2‑Methoxy-1-propanol + 1,2-Propanediol at
101.3 kPa and 50.0 kPa
Bao Li, Feizhong Sun, Xusheng Mi, and Changsheng Yang*

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ABSTRACT: The isobaric vapor−liquid equilibrium (VLE) data of 1-methoxy-2-

propanol (PM) + 1,2-propanediol (PG) and 2-methoxy-1-propanol (MP) + 1,2-
propanediol (PG) was measured in this work by a modified Rose-Williams still under
pressures of 101.3 kPa and 50.0 kPa. The Wisniak test and the Van Ness test were
applied to confirm the thermodynamic consistency of the VLE data. The experimental
isobaric VLE data were correlated by the nonrandom two-liquid and universal
quasichemical models. The experiment results showed that these two models perfectly
correlate the measured VLE data.

1. INTRODUCTION
1-Methoxy-2-propanol (PM) is an excellent solvent and
dispersant used in industry because of both an ether group
and a hydroxyl group in its molecular structure. It is generally
used in coatings, inks, printing and dyeing, cellulose and other
industries.1,2 In addition, it is an intermediate of the herbicide
metolachlor. 2-Methoxy-1-propanol (MP) is an isomer of PM
and has the same chemical formula and a similar chemical
structure. Therefore, MP is also a solvent and chemical
intermediate. 1,2-Propanediol (PG) is a common organic economic and environmental benefits, greater effort should be
synthetic raw material, and a colorless, viscous liquid at room made to achieve better separation.
temperature, generally used as a solvent, dehydrating agent, As a mature and efficient separation technology, distillation
plasticizer, and antifreeze.3 has been widely used in large-scale chemical industrial
In recent years, hydrogen peroxide based propylene oxide production. The pressure of pure compounds and the VLE
(HPPO) applied to synthesize propylene oxide has received data of binary systems are very important for the design and
widespread attention due to its many advantages, such as less manufacture of distillation equipment. Researchers have
byproducts and less environmental pollution, and the reaction measured the VLE data of the byproduct system generated
equation is shown in scheme 1.4In addition, due to the use of a during the HPPO synthesis of propylene oxide. For instance,
Wilding et al.5 stated the binary isothermal vapor−liquid
equilibrium data for (PG + PM). Wang et al.6 reported binary
isobaric vapor−liquid equilibrium data for (water + PM),
(water + MP), and (PM + MP) at 101.3 kPa. However, the

Received: March 16, 2020

titanium silicon molecular sieve as a catalyst and methanol as a Accepted: October 12, 2020
solvent, two possible reactions may occur between propylene
oxide and water or methanol. (see scheme 2).4PM, MP, and
PG are three byproducts that are easily produced. Since
separating these products and byproducts brings significant

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jced.0c00246

A J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. Suppliers and Purities (Mass Fractions) of Chemical Reagents

initial mass fraction purification final mass fraction
chemical name abbreviation CASRN source purity method purity
1-methoxy-2- PM 107-98-2 Guangfu Technology Development 0.990a none 0.990a
propanol Co.
2-methoxy-1- MP 1589-47-5 Xiensi Biochemical Technology Co. 0.985a distillation 0.995a
propanol
1,2-propanediol PG 57-55-6 Tianjin Concord Technology Co. 0.995a none 0.995a
a
Gas chromatography.

binary vapor−liquid equilibrium data for (PG + PM) and (PG

+ MP) have not been found in the literature.
In this work, the VLE data for the binary system of (PG +
PM) and (PG + MP) were measured at pressures of 101.3 and
50.0 kPa by a modified Rose-Williams still.7 The nonrandom
two-liquid (NRTL)14 and universal quasichemical (UNI-
QUAC)15 activity models were employed to correlate and
regress the experimental data to obtain the corresponding
binary interaction parameters.

2. EXPERIMENTAL SECTION
2.1. Materials. PM (≥99.0 mass%) was acquired from
Tianjin Guangfu Technology Development Co. Ltd., China.
MP (≥98.5 mass %) was supplied by Tianjin Xienen
Biochemical Technology Co., Ltd., China. PG (≥99.5 mass
%) was provided from Tianjin Concord Technology Co., Ltd.
Among them, the purity of the MP was not enough to
determine the phase behavior, so this sample was further
purified by a glass distillation column, and its concentration
was detected by the gas chromatograph (GC-SP2100A). The
chemical name, CAS number, source, and mass fraction purity
are listed in Table 1. After many times of chromatographic
analysis of the sample, pure acetone was selected to dilute each
sample, with a dilution factor of 10. To ensure the
dependability of the experimental device, the boiling point of
each substance at 101.3 kPa was measured using a modified
Rose-Williams still, the density of the three reagents at 298.15
K was measured applying a beaker, a measuring cylinder, and
an electronic balance (Sartorius BP210S). The obtained data
were compared with the literature values, which are listed in
Table 2.
Table 2. Boiling Points (Tb) of PM, MP, and PG at 101.3
kPaa
Tb/K (101.3 kPa) ρ (g/cm−3) (298.15 K)
component exp lit exp
PM 393.24 393.15 b
0.9173
MP 402.65 402.65b 0.9359
PG 460.87 460.22c 1.0338
a
Standard uncertainty u was u(T) = 0.05 K; u(ρ) = 0.0005 g·cm−3.
b
Reference 6. cReference 3. dReference 8 eFrom Aspen plus V8.6.
f
Reference 9.
2.2. Apparatus and Procedure. All the instruments and
equipment required are illustrated in Figure 1, comprising a
modified Rose-Williams still, a heating rod, a condenser, a U-
shaped mercury pressure gauge, a vacuum pump, a buffer tank,
and a needle valve. Experimental measurements of isobaric
vapor−liquid equilibrium data were performed in a modified
Rose-Williams still. The vapor and liquid phases were entirely
Figure 1. Rose-Williams still and auxiliary equipment: (1) heating
rod, (2) liquid sample connection, (3) vapor sample connection, (4)
condenser, (5) coolant inlets, (6) coolant outlets, (7) U-shaped
differential manometer, (8) vacuum pumps, (9) buffer tanks, (10)
valve, (11) precision mercury thermometer.
contacted by continuous circulation in the still and reached
equilibrium rapidly.
As shown in Figure 1, the energy of the whole system was
provided by a heating rod. The heat of the heating rod can be
controlled by adjusting the voltage of the transformer. At the
beginning, the voltage of the transformer was slowly adjusted
to make the liquid boil. When the liquid in the equilibrium cell
reached a stable circulation, we believed that it had reached the
vapor−liquid equilibrium state and kept the voltage unchanged
at this time. The temperature of the whole system was
measured by mercury thermometers, the uncertainty of which
was 0.05 K. The system pressure was measured by a U-type
pressure gauge. When the experiment was carried out at 101.3
kPa, the upper outlet of the condenser tube did not need to be
connected with a vacuum pump. When the experiment was
conducted at 50.0 kPa, the buffer tank, needle valve, vacuum
pump, and U-type manometer should be connected with
silicone tubing according to the sequence in Figure 1. Besides,
lit PTFE tape was applied to seal each connection interface to
0.9169d ensure the air tightness of the system. At last, the needle valve
0.9355e was adjusted slowly until the indication of the u-type pressure
1.0332f gauge reached a stable 50.0 kPa. The maximum volume of the
still is 130 cm3, of which 60 cm3 was filled with reagents.
Each sample was gravimetrically analyzed with an electronic
balance (Sartorius BP210S), which had an accuracy of 0.0001
g. After the vacuum pump started working, the needle valve
was slowly adjusted to ensure the stable system pressure. Only
when the system temperature and pressure remained stable for
more than 40 min were the vapor and liquid phases considered
at equilibrium. Afterward some vapor and liquid samples were
taken out for analysis. On the basis of the results of previous
experiments,16−19 it is confident that our experimental
apparatus and operating procedures are reliable.
2.3. Analysis. A BFRL SP-2100A gas chromatograph (GC)
equipped with a flame ionization detector (FID) was used for
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Table 3. Antoine Equation Coefficientsa

compound A B C D E Tmin/K Tmax/K
PM 47.30 −6812 −5.02 2.26 × 10−18 6 176.48 579.8
MP 55.51 7293.9 −6.24 8.30 × 10−18 6 216.3 588.4
PG 201.28 −15420 28.11 2.16 × 10−5 2 213.15 626
a
Antoine equation:9
B
ln(p /kPa) = A + + C ln(T /K) + D(T /K )E
T /K

from Aspen plus V8.6.

Table 4. VLE Data for the PM (1) + PG (2) at 101.3 kPaa

NRTL UNIQUAC
T/K x1 y1 γ1 γ2 α12 ΔT/K Δy1 ΔT/K Δy1
P = 101.3 kPa
460.87 0.0000 0.0000 1.0000 0.00 0.0000 0.00 0.0000
459.77 0.0036 0.0383 1.8761 0.9994 11.0228 0.01 0.0005 0.01 0.0005
459.04 0.0061 0.0622 1.8267 0.9998 10.8067 0.01 0.0002 0.02 0.0002
455.95 0.0175 0.1593 1.7447 1.0008 10.6382 0.02 0.0006 0.03 0.0007
445.86 0.0681 0.4225 1.4942 1.0108 10.0114 0.04 0.0002 0.03 0.0005
438.82 0.1201 0.5723 1.3561 1.0097 9.8034 0.04 0.0081 0.01 0.0093
435.94 0.1461 0.6228 1.3013 1.0155 9.6501 0.02 0.0092 0.00 0.0091
430.91 0.2006 0.7011 1.2092 1.0298 9.3473 0.12 0.0088 0.13 0.0095
420.06 0.3500 0.8268 1.0840 1.1020 8.8654 0.15 0.0045 0.21 0.0046
416.47 0.4104 0.8586 1.0582 1.1408 8.7235 0.15 0.0026 0.20 0.0026
408.20 0.5746 0.9206 1.0221 1.2392 8.5839 0.09 0.0007 0.11 0.0008
401.01 0.7543 0.9625 1.0054 1.3723 8.3605 0.03 0.0005 0.03 0.0005
395.93 0.9078 0.9878 1.0008 1.4860 8.2234 0.01 0.0003 0.01 0.0003
393.24 1.0000 1.0000 1.0000 0.00 0.0000 0.00 0.0000
P = 50.0 kPa
439.52 0.0000 0.0000 1.0000 0.01 0.0000 0.01 0.0000
437.70 0.0068 0.0859 1.8228 0.9811 13.7255 0.50 0.0000 0.50 0.0001
431.06 0.0283 0.2843 1.7086 0.9956 13.6393 0.08 0.0032 0.06 0.0038
427.71 0.0432 0.3778 1.6199 0.9939 13.4484 0.16 0.0037 0.14 0.0043
423.45 0.0632 0.4737 1.5510 1.0072 13.3414 0.14 0.0055 0.14 0.0058
419.77 0.0855 0.5529 1.4758 1.0090 13.2269 0.12 0.0069 0.11 0.0067
413.13 0.1381 0.6729 1.3339 1.0173 12.8391 0.15 0.0049 0.21 0.0042
402.93 0.2468 0.8016 1.1925 1.0764 12.3305 0.13 0.0007 0.18 0.0005
395.70 0.3545 0.8681 1.1193 1.1440 11.9841 0.12 0.0014 0.10 0.0009
388.11 0.5002 0.9216 1.0711 1.2412 11.7457 0.12 0.0012 0.20 0.0006
381.95 0.6466 0.9549 1.0523 1.3541 11.5721 0.53 0.0005 0.62 0.0001
376.56 0.8075 0.9795 1.0395 1.4750 11.3904 0.78 0.0000 0.82 0.0000
374.30 0.9201 0.9924 1.0005 1.4775 11.3393 0.04 0.0002 0.02 0.0001
372.18 1.0000 1.0000 1.0000 0.01 0.0000 0.01 0.0000
a
Standard uncertainties u were u(T) = 0.05 K, u(p) = 0.1 kPa, u(x1, y1) = 0.0006, ΔT = |Texp − Tcal|, Δy1 = |yexp
1 − y1 |.
cal

quantitative analysis of the vapor and liquid samples of each set
of experiments. A DB-264 capillary column (30 m × 0.32 mm
× 1.8 μm) was selected to fit the gas chromatograph, and the
response peak was processed by an N-2000 chromatographic
workstation. High-purity nitrogen with a flow rate of 30 mL·
min−1 was employed as the carrier gas of the GC. The flow rate
of hydrogen as the combustion gas of the FID detector was 30
mL·min−1, and the flow rate of the air was 300 mL·min−1. The
split ratio of the (PM + PG) system was adjusted to 1:30, while
for the (MP + PG) system, it was adjusted to 1:40. To
completely separate the two binary system reagents in the gas
chromatograph, the following temperatures were determined
as optimal after trying various conditions several times,
(433.15, 453.15, and 458.15 K) for the column, injector, and
detector, respectively. The accuracy was estimated to be ±0.01
C https://dx.doi.org/10.1021/acs.jced.0c00246
K. A series of standard solutions of these two binary systems
was configured for the analysis of each experimental sample by
making a standard curve. To ensure the stability of the
experiment process, it is worth mentioning that the sample
injection volume during the standard curve process20 and the
experiment were guaranteed to be 0.1 μL unchanged. In
addition, each sample was injected at least five times to reduce
accidental errors in the experiment.
3. RESULTS AND DISCUSSION
3.1. Pure Component Vapor Pressures. The saturated
vapor pressures of PG, PM, and MP were obtained from the
Antoine equation in the Aspen plus 8.6. Antoine parameters A,
B, C, D and E are listed in Table 3.
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Table 5. VLE Data for the MP (1) + PG (2) at 101.3 kPaa

NRTL UNIQUAC
T/K x1 y1 γ1 γ2 α12 ΔT/K Δy1 ΔT/K Δy1
P = 101.3 kPa
460.87 0.0000 0.0000 1.0000 0.00 0.0000 0.00 0.0000
458.49 0.0108 0.0841 1.8494 0.9984 8.4102 0.07 0.0005 0.03 0.0008
455.35 0.0285 0.1943 1.7365 0.9890 8.2205 0.36 0.0004 0.26 0.0037
444.18 0.1126 0.4918 1.4401 0.9888 7.6267 0.36 0.0118 0.17 0.0175
428.98 0.3119 0.7481 1.1526 1.0820 6.5519 0.12 0.0071 0.17 0.0094
423.00 0.4207 0.8197 1.0952 1.1502 6.2602 0.03 0.0045 0.06 0.0066
415.77 0.5896 0.8901 1.0334 1.3095 5.6376 0.03 0.0025 0.11 0.0004
409.98 0.7537 0.9415 1.0072 1.4658 5.2593 0.07 0.0028 0.11 0.0013
406.57 0.8645 0.9702 0.9990 1.5623 5.1029 0.09 0.0015 0.12 0.0006
403.76 0.9616 0.9922 0.9981 1.6239 5.0797 0.06 0.0002 0.07 0.0000
402.95 0.9920 0.9984 0.9974 1.6549 5.0323 0.07 0.0000 0.08 0.0000
402.65 1.0000 1.0000 1.0000 0.00 0.0000 0.00 0.0000
P = 50.0 kPa
439.52 0.0000 0.0000 1.0000 0.01 0.0000 0.01 0.0000
432.94 0.0281 0.2281 1.7396 1.0029 10.2207 0.04 0.0009 0.04 0.0009
422.03 0.1001 0.5141 1.4621 1.0217 9.5118 0.01 0.0002 0.01 0.0008
416.91 0.1498 0.6172 1.3484 1.0388 9.1509 0.04 0.0001 0.04 0.0009
411.89 0.2111 0.7065 1.2608 1.0484 8.9958 0.07 0.0049 0.08 0.0054
406.78 0.2881 0.7785 1.1797 1.0812 8.6848 0.08 0.0047 0.11 0.0050
401.16 0.3918 0.8416 1.1087 1.1481 8.2477 0.07 0.0019 0.09 0.0023
395.78 0.5129 0.8922 1.0595 1.2346 7.8601 0.05 0.0003 0.05 0.0006
391.61 0.6237 0.9265 1.0326 1.3149 7.6053 0.02 0.0000 0.01 0.0003
385.04 0.8340 0.9726 1.0052 1.5095 7.0652 0.01 0.0005 0.01 0.0005
383.22 0.9001 0.9845 1.0023 1.5481 7.0495 0.00 0.0000 0.01 0.0001
380.65 1.0000 1.0000 1.0000 0.01 0.0000 0.01 0.0000
a
Standard uncertainties u were u(T) = 0.05 K, u(p) = 0.1 kPa, u(x1, y1) = 0.0006, ΔT = |Texp − Tcal|, Δy1 = |yexp
1 − y1 |.
cal

3.2. Experimental Data. The VLE data of the two binary
systems of (PM + PG) and (MP + PG) at 101.3 and 50.0 kPa
are listed in Table 4 and Table 5. The presented VLE data
comprising xi, yi, γi, α12, and T, represent the liquid mole
fraction, the vapor phase mole fraction, the activity coefficient,
the relative volatility, and the temperature, respectively.
The relative volatility α12 was obtained from the following
equation:
y1(1 − x1)
α12 =
x1(1 − y1)
phase and pure vapor i at p and psi , respectively; xi and yi are the
mole fractions of the liquid and vapor phase, respectively. γi is
the activity coefficient; Vli is the liquid mole volume. Besides, psi
was calculated with the Antoine equation, and the Antoine
constants of all components were listed in Table 3.
Under low pressure conditions, the vapor phase can be
considered as an ideal gas, and the Poynting factor
exp(Vil(p − pis )/RT ), φî v , and φsi can be considered as 1, so
eq 4 can be simplified as
(3) pyi = pis γixi (5)

From Tables 4 and 5, it can be seen that the relative volatility
of the two systems under both pressures was always greater
than 5, which means that (PM + PG) and (MP + PG) can be
easily separated by distillation. Furthermore, it can also be seen
that as x1 (the mole fraction of the liquid phase of the
component with a lower boiling point) increases, the relative
volatility gradually decreases. And in each system, the smaller is
the pressure, the greater is the relative volatility, also proving
that the two substances are easier to separate by the distillation
method under low pressure conditions.
Because the system is nonideal, the VLE calculation formula
can be written as
ij V l(P − Pis) yz
Therefore, γi was obtained by eq 5, and the results of the
calculated activity coefficient are found in Tables 4 and 5. And
T−x−y relationships are shown in Figures 2−9.
3.3. Thermodynamic Consistency Tests. Two different
methods were used to verify the thermodynamic consistency of
the data obtained: The Wisniak area test10 and Van Ness point
test,11 which are based on the Gibbs−Duhem equation. The
Wisniak area test is defined in eqs 6−9
1 1
∫0 Lk dx1 − ∫0 Wk dx1
D = 100 × 1 1
∫0 Lk dx1 + ∫0 Wk dx1
(6)

Pφî v yi = Pisφisγixi expjjjj i zzz

z
∑ Ti0xiΔsi0
k {
Lk = −T
RT (4) ∑ xiΔsi0 (7)

RT ijj y yz
0j
j∑ xi ln γi− ∑ xi ln i zzz
where i represents different components in all systems; p and psi
∑ xiΔsi jk xi z{
are the total system pressure and the saturated vapor pressure, Wk =
respectively; φ̂i v and φsi are the fugacity coefficient of the vapor (8)

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Figure 5. x1−ln(γ1/γ2) diagrams for PM (1) + PG (2) at 50.0 kPa.

Figure 2. T−x−y diagram for PM (1) + PG (2) at 101.3 kPa: (■)
data for x1−T; (□) data for y1−T; () NRTL model; (---)
UNIQUAC model.

Figure 6. T−x−y diagram for MP (1) + PG (2) at 101.3 kPa: (■)

data for x1−T; (□) data for y1−T; () NRTL model; (---)
Figure 3. x1−ln(γ1/γ2) diagrams for PM (1) + PG (2) at 101.3 kPa. UNIQUAC model.

Figure 7. x1−ln(γ1/γ2) diagrams for MP (1) + PG (2) at 101.3 kPa.

Figure 4. T−x−y diagram for PM (1) + PG (2) at 50.0 kPa: (■) data
for x1−T; (□) data for y1−T; () NRTL model; (---) UNIQUAC
model. Δhi0
Δsi0 =
Ti0 (9)

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Van Ness test is a point-by-point method. The thermody-

namic consistency is testified by using the NRTL model. In
this work, the modified Van Ness method by Fredenslund et
al.12 was used to test the thermodynamic consistencies of the
VLE data using the Legendre polynomial to obtain excess
Gibbs energy. The formula is shown as
N
1
Δy = ∑ 100|yiexp − yical |
N i=1 (10)

Figure 8. T−x−y diagram for MP (1) + PG (2) at 50.0 kPa: (■) data
for x1−T; (□) data for y1−T; () NRTL model; (---) UNIQUAC
model.
1
N
piexp − pical
Δp = ∑ 100
N i=1
piexp (11)
where N is the data points’ number. If the mean absolute
deviation of the vapor phase mole fraction (Δy) is less than
0.01,13 and the average absolute deviation of the pressure (Δp)
is less than 1.0 kPa, the VLE data are considered as passing the
Van Ness test.
The calculated results were listed in Table 7. On the basis of
the above illustration, the results proved that the measured
VLE data all passed the Wisniak area test and the Van Ness
test.
3.4. Data Correlation. The VLE data of (PM + PG) and
(MP + PG) systems were correlated by using the activity
model of NRTL14 and UNIQUAC.15 The nonrandom
parameter for the NRTL equation was set at 0.3 according
to the recommendations of Renon.9 The objective function

ÄÅ 2 Ñ
É
ÅÅ exp ij P exp − P cal yz ÑÑÑÑ
(OF) is written as

ÅÅij Ti − Tical yz j z
ÅÅÅjjj zzz + jjj zz ÑÑÑ
zz ÑÑ
Åj z
2

N Å ÅÅk j
{ k { ÑÑÑ
i i

OF = ∑ ÅÅ Å
Å ÑÑ
Ñ
δT δ
ÅÅ cal y2 Ñ ÑÑ
p

i=1 Å j Å i xi − xi zy i
j z
ÅÅ+jj
ÅÅ jj zz + jjj i
z
i z zz ÑÑÑÑ
z jj zz ÑÑ
2 exp

ÅÅÅ k
exp cal y − y

ÅÇ { k { ÑÑÑÖ
δx δy
(12)
where N is the number of experimental points; Texp exp exp
i , P i , xi ,
Figure 9. x1−ln(γ1/γ2) diagrams for MP (1) + PG (2) at 50.0 kPa. and yexp
i are the experimental values, respectively; T cal
i , P cal cal
i , xi ,
cal
and yi are calculated values of temperature, pressure, liquid
mole fractions and vapor mole fractions, respectively; δT, δp, δx,
where T0i is the boiling point of the pure component i at the
and δy are the deviations of temperature, pressure, liquid mole
equilibrium pressure p of the system, k represents each
fraction, and vapor mole fraction.
experimental point, and Δhi0 represents the enthalpy of
For the binary system of PM (1) + PG (2), as can be seen
vaporization of pure component i. which was taken from the
from Table 4, the maximum values of Δy1 are 0.0092, and
Aspen Plus V8.6 physical properties databanks. The molar
0.0069 with the NRTL model and 0.0095, and 0.0058 with the
entropy changes of each substance at 50 and 101.3 kPa are
UNIQUAC model at pressures of 101.3 and 50.0 kPa,
obtained by formula 9. These data are listed in Table 6. The
respectively. The maximum values of ΔT are 0.15 and 0.78
criterion for the Wisniak test is that the coefficient D should be
K with the NRTL model, as well as 0.21 and 0.80 K with the
less than 3. The calculated values of D for the two systems at
UNIQUAC model at pressures of 101.3, and 50.0 kPa,
two pressures are given in Table 7, indicating that the obtained
respectively. From Table 5, it can be seen that the maximum
data are reliable.
values of Δy1 are 0.0118, and 0.0049 with the NRTL model, as
well as 0.0175, and 0.0054 with the UNIQUAC model at
Table 6. Molar Evaporation Enthalpy (Δh0), Boiling Point pressures of 101.3 and 50.0 kPa, respectively. Besides, the
(T0) and Molar Evaporation Entropy (Δs0) of PM, MP, and maximum values of ΔT are 0.36 and 0.08 K with the NRTL
PG at 101.3 and 50.0 kPa model and 0.26 and 0.11 K with the UNIQUAC model at
pressures of 101.3 and 50.0 kPa, respectively. In summary,
Δh0 (J·mol−1) T0 (K) Δs0 (J·mol−1·K−1)
these data showed that the correlation values agreed well with
50.0 and 101.3 101.3 101.3 those of experimental.
component kPa 50.0 kPa kPa 50.0 kPa kPa
Furthermore, the fit of correlation was also shown by
PM 38976 372.18 393.24 104.72 99.11 calculating the root means square deviation (RMSD) and
MP 38977 380.65 402.65 102.40 96.56 average absolute deviation (AAD) of the VLE data in the two
PG 52147 439.52 460.87 118.65 113.17 models which are written as follows:
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Journal of Chemical & Engineering Data pubs.acs.org/jced Article

Table 7. Results of Thermodynamic Consistency Test

Wisniak test Van Ness test
system pressure (kPa) L W D Δy Δp
PM (1) + PG (2) 101.3 13.797 14.089 1.047 0.259 0.16
50.0 15.978 16.322 1.065 0.217 0.65
MP (1) + PG (2) 101.3 10.790 11.071 1.280 0.261 0.33

ÄÅ N É
50.0 12.833 13.181 1.337 0.113 0.24

ÅÅ ∑ (T exp − T cal)2 ÑÑÑ0.5

ÅÅ i = 1 i ÑÑ
RMSD(Ti ) = ÅÅÅ ÑÑ
ÑÑ
Table 9. Interaction Parameters, RMSD(T1), RMSD(y1),

ÅÅ ÑÑÖ
ÅÇ
i
AAD(T1), and AAD(y1) for the Systems of MP (1) + PG (2)
N
ÄÅ N É
with Two Models

ÅÅ ∑ (y exp − y cal )2 ÑÑÑ0.5

(13)

ÅÅ i = 1 i ÑÑ
RMSD(yi ) = ÅÅÅ ÑÑ
50.0 kPa−101.3 kPa

ÅÅ ÑÑ
ÅÇ ÑÑÖ
i system NRTLa parameters UNIQUACa parameters
N (14) MP (1) + PG aij −3.96 aij 1.52
(2) aji 5.87 aji −2.03
1
N bij /K 1386.30 bij/K −474.01
AAD(Ti ) = ∑ |Tiexp − Tical| bji /K −1857.82 bji/K 558.74
N i=1 (15) cij 0.30
N RMSD(T1/K) 0.38 RMSD(T1/K) 0.37
1
AAD(yi ) = ∑ |yiexp − yical | RMSD(y1) 0.0085 RMSD(y1) 0.0084
N i=1 (16) AAD(T1/K) 0.23 AAD(T1/K) 0.22
AAD(y1) 0.0067 AAD(y1) 0.0067
In brief, AAD describes the closeness of experimental data to a
NRTL, τij = aij + bij/T; UNIQUAC, ln τij = aij + bij/T.
model-determined data, while RMSD reflects the extent of data
scattering. The adjustable parameters of two activity models as
well as the RMSD and AAD of the equilibrium temperature the Van Ness test were adopted to check the reliability of the
and the vapor mole fraction are listed in Table 8 and Table 9. VLE data. NRTL and UNIQUAC activity coefficient models
were successfully correlated with the VLE data of the binary
Table 8. Interaction Parameters, RMSD(T1), RMSD(y1), systems, PM (1) + PG (2) and MP (1) + PG (2). The binary
AAD(T1), and AAD(y1) for the Systems of PM (1) + PG (2) interaction parameters derived from the VLE data obtained
with Two Models from this experiment will serve as an important basis for the
industrial separation of three substances.

system
PM (1) + PG aij
NRTLa parameters
50.0 kPa−101.3 kPa

−4.19
UNIQUACa parameters
aij 1.63
■ AUTHOR INFORMATION
Corresponding Author
(2) aji 7.04 aji −2.48 Changsheng Yang − Key Laboratory for Green Chemical
bij/K 1378.44 bij/K −463.42 Technology of State Education Ministry, School of Chemical
bji/K −2181.82 bji/K 668.36 Engineering and Technology, Tianjin University, Tianjin
cij 0.30 300072, China; orcid.org/0000-0002-3226-8517;
RMSD(T1/K) 0.34 RMSD(T1/K) 0.35 Email: changshengyangtju@163.com
RMSD(y1) 0.0046 RMSD(y1) 0.0046
Authors
AAD(T1/K) 0.22 AAD(T1/K) 0.24
Bao Li − Key Laboratory for Green Chemical Technology of
AAD(y1) 0.0038 AAD(y1) 0.0040
State Education Ministry, School of Chemical Engineering and
a
NRTL, τij = aij + bij/T; UNIQUAC, ln τij = aij + bij/T. Technology, Tianjin University, Tianjin 300072, China
Feizhong Sun − Key Laboratory for Green Chemical Technology
It is simple to see that the AAD(T1/K) of the two systems does of State Education Ministry, School of Chemical Engineering
not exceed 0.24, while the RMSD value does not exceed 0.38. and Technology, Tianjin University, Tianjin 300072, China
For the vapor phase molar fraction y1, the RMSD does not Xusheng Mi − Key Laboratory for Green Chemical Technology
exceed 0.0084 and the AAD neither exceeds 0.0067. Moreover, of State Education Ministry, School of Chemical Engineering
the RMSD and AAD values associated with the NRTL model and Technology, Tianjin University, Tianjin 300072, China
and UNIQUAC model are basically the same, the RMSD(T1) Complete contact information is available at:
and AAD(T1) values are both less than 0.5, at the same time, https://pubs.acs.org/10.1021/acs.jced.0c00246
the RMSD(y1) and AAD(y1) are both less than 0.01, so we can
conclude that both models are suitable for both systems. Notes
The authors declare no competing financial interest.

■
4. CONCLUSIONS
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