Fluid Phase Equilibria 432 (2017) 85e89

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Liquid-liquid equilibrium of the ternary system water propargyl

alcohol n-propyl acetate
Chong Sun, Wei Cao, Jia Wu, Xiaoping Hu*
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, PR China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 6 July 2016
Received in revised form
18 October 2016
Accepted 20 October 2016
Available online 22 October 2016

The liquid-liquid equilibrium of the water propargyl alcohol n-propyl acetate ternary system was
experimentally investigated in the temperature range (279.15e321.15) K under atmospheric pressure.
Five proles of isothermal liquid-liquid equilibrium data measured through gas chromatography were
provided. The extraction efciency was evaluated using the distribution coefcient and selectivity factor.
Binary interaction parameters were obtained by correlating the equilibrium data with the UNIQUAC and
NRTL models. The mutual solubility of both phases increased with rising temperature. Both models can
accurately describe the liquid-liquid equilibrium behavior of this system.
2016 Elsevier B.V. All rights reserved.

Keywords:
Liquid-liquid equilibrium
Propargyl alcohol
n-propyl acetate
UNIQUAC
NRTL

1. Introduction
Propargyl alcohol (PA) plays a signicant role as an intermediate
in the synthesis of pharmaceuticals [1,2]. As a typical acetylenic
compound, PA is extensively used as an additive in various applications, such as acidizing oil wells, chemical cleaning, acid pickling
of heat-transfer equipment and removal of scales in metallurgy [3].
In the anticorrosion protection of metals in acidic media, PA is an
efcient inhibitor, especially for iron and steel alloys [3e5].
Industrially, PA is a side product of 2-butyne-1,4-diol production
which is difcult to separate and purify, resulting in the large gap
between supply and demand. The azeotrope formed between PA
and water complicates the separation of PA. Thus, purifying PA
through direct distillation is not advisable. A suitable extractant is
highly necessary to separate PA from water and to subsequently
develop a novel extraction process for PA. This development inevitably requires fundamental research on the liquid-liquid equilibrium (LLE) behavior of a water-PA system.
Limited LLE data of the water PA extractant system are
available in open literature. K. Ye et al. [6] investigated the LLE of
diisopropyl ether (DIPE) as a solvent to extract PA from water. G.
Yuan et al. [7] applied butyl acetate (BA) as a substitute to

investigate the possibility of isolating PA from water. However, both

studies did not achieve the desired extraction efciency for PA
separation. Thus, the search of a suitable solvent is still continuous.
In general, esters are commonly used as solvents to separate
water-alcohol systems [8e10]. In the present work, the extraction
efciency for n-propyl acetate (NPA) separation was experimentally
investigated by measuring the LLE data for the water PA NPA
ternary system in the temperature range (279.15e321.15) K under
atmospheric pressure. The distribution coefcient and the selectivity factor were calculated to assess the separation efciency. The
UNIQUAC [11] and NRTL models [12] were used to correlate the LLE
data.
2. Experimental methods
2.1. Materials
The source and purity of each chemical used in this work are
listed in Table 1. The purity of each material was determined
through gas chromatography (GC). These chemicals were used
without further purication. Deionized water was used throughout
all experiments.
2.2. Experimental apparatus and procedures

* Corresponding author.
E-mail address: huxp@zju.edu.cn (X. Hu).
http://dx.doi.org/10.1016/j.uid.2016.10.023
0378-3812/ 2016 Elsevier B.V. All rights reserved.

The measurements were performed in the temperature range

86

C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89

Table 1
Sources and purities of chemicals.
Chemical name

Source

Initial mass fraction puritya

Final mass fraction purityb

Water
PAc
NPAd

Hangzhou Wahaha Group Co., Ltd.

Northeast Pharmaceutical Factory Fushun Branch, China
Sinopharm Chemical Reagent Co., Ltd.

>99.50%
98.50%

>99.73%
>96.68%
>99.90%

a
b
c
d

The purity labelled by the supplier.

The purity detected by GC.
IUPAC chemical name: 2-propyn-1-ol.
IUPAC chemical name: 1-propyl acetate.

3. Experimental data
The mass fractions of the components in each phase at a
particular temperature are shown in Table 3. Each composition is an
average value of three experimental replications. To evaluate the
capacity of NPA to separate PA from water, the distribution coefcient (D) and selectivity (S) are calculated as follows:

wII2


wI2 wI1


wII2 wII1

0.75

0.50

0.50

0.75

0.00

Samples from both phases were carefully extracted using

microsyringe and then injected into a GC apparatus (GC 1690T,
Kexiao
Science
Apparatus
Co.,
Ltd., China)
with
a
2 mm  2000 mm column (packed with Porapak Q, 80/100 Mesh,
USA).
The temperatures of the TCD, column and injection port of the
GC apparatus were xed at 453.15 K. The bridge current of the TCD
was 150 mA. The pre-column pressure of hydrogen as carrier gas
was 0.18 MPa.

wI2

0.25

1.00

0.25

1.00

2.3. Analysis

0.00

w2

(279.15e321.15) K under atmospheric pressure. An electronic balance (BS224S, accuracy 0.0001 g, Sartorious AG, Germany) was
used to weigh the required quantities of water, PA and NPA. The
weighed components were then mixed in a series of test tubes
according to the desired compositions of ternary mixtures. The
tubes were sealed with silicon rubber stops, and xed vertically
onto an oscillator which was installed in a thermostatic oven (with
a PID temperature controller of accuracy 0.1 K).
The tubes in the thermostatic oven were initially heated for
30 min to reach the expected and invariant temperature. Subsequently, they were oscillated for 50 min to achieve intensive mixing. After oscillation, the tubes were allowed to set for 75 min, in
order to facilitate the separation of the resultant liquid into two
phases.

(1)

(2)

where wI1 and wI2 are the mass fractions of water and PA in the
organic phase, respectively, and wII1 and wII2 are the mass fractions of
water and PA in the aqueous phase, respectively. Values of the
distribution coefcient and selectivity of PA at ve temperatures
are listed in Table 3.
Fig. 1 shows the tie-lines and the corresponding solution curves
at 279.15 and 321.15 K. At 279.15 K, the tie-lines are approximately
plain until the content of PA in the total compositions approaches
about 20%. As the PA concentration continues to increase in the
ternary mixture, the increase in PA concentration becomes faster in
the organic phase than in the conjugated aqueous phase. The

0.00
0.25

0.50

w1

0.75

1.00

Fig. 1. Tie-lines and solution curves of water (1) PA (2) NPA (3) at (C) 279.15 K
and ( ) 321.15 K. Black dashed line, solution curve at 279.15 K; red dashed line, solution curve at 321.15 K. (For interpretation of the references to colour in this gure
legend, the reader is referred to the web version of this article.)

splitting phases then merge into a single phase. This phenomenon

is also observed as the temperature rises to 321.15 K.
In Fig. 1, the co-existing region of the liquid-liquid phases
enveloped by the solution curves shrinks as temperature rises from
279.15 K to 321.15 K. This nding is different from that observed
from the LLE studies of ternary systems water PA DIPE [6] and
water PA BA [7]. The authors of these two articles reported a
similar nding in which an approximately single solution curve
could describe the phase compositions of the respective systems
within the investigated temperature ranges. Temperature exerts a
larger inuence on the LLE data of the water PA NPA system
than on that of the water PA DIPE and water PA BA systems.
Meanwhile, the shrinking co-existing region from 279.15 K to
321.15 K demonstrates that the mutual solubility of both phases
increases when the temperature increases.
As presented in Table 3, the distribution coefcients of PA
generally tend to increase when the PA content increases. The
distribution coefcient is relevant to the solubility of the solute (PA
in this study) in both co-existing phases, thus, it reects the slope of
the tie-line [13]. The distribution coefcients are not large enough,
which agrees with the slope of the tie-lines, as shown in Fig. 1. The
effectiveness of an extractant can be described by the selectivity.
Fig. 2 plots the selectivity of PA against the mass fraction in the
organic phase at the investigated temperature range. The selectivity of PA decreases slightly with rising temperature, indicating
that the extraction capacity of NPA decreases as the temperature
increases. The selectivity values of PA (values varying between 2
and 68) are greater than one, indicating the possibility of PA
extraction using NPA.

C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89

Table 3
Experimental liquid-liquid phase equilibrium data for the water (1) PA (2) NPA
(3) ternary system (mass fraction).a

70
60

Organic phase
w1

50

40
30
20
10
0
0.0

0.1

0.2

0.3

0.4

wI2
Fig. 2. Selectivity of PA plotted against the mass fraction of PA in the organic phase at
(C) 279.15 K, ( ) 291.15 K, ( ) 301.15 K, ( ) 311.15 K and ( ) 321.15 K.

Table 2
CAS number (CAS), molecular weights (M), boiling points (Tb), densities (r) and
refractive indices (nD) at 298.15 K under atmosphere pressure.
Chemical name

CAS

M (g mol1)

Tb (K)a

r (g cm3)a

nDb

Water
PA
NPA

7732-18-5
107-19-7
109-60-4

18.02
56.06
102.13

373.15
386.65
374.65

0.9971
0.9450
0.8823

1.3330
1.4302
1.3816

a
b

87

Obtained from ASPEN Properties Databank.

Obtained from DECHEMA.

4. Thermodynamic modelling
4.1. Selection of thermodynamic models
In terms of LLE modelling, the NRTL, UNIQUAC and UNIFAC
models are frequently used to correlate equilibrium systems.
Previous studies on the water PA DIPE and water PA BA
systems have shown that the UNIFAC group contribution method
cannot describe the LLE behavior of these systems [6,7], but the
UNIQUAC model predicts the latter fairly well [7]. The UNIQUAC
model, which considers the effects of molecular size and shape [11],
has successfully correlated many LLE systems, including mixtures
containing ketones [14], alcohols [13,15,16] and esters [15,17].
Considering the differences in molecular sizes and shapes of the
three investigated compounds, we selected the UNIQUAC model to
correlate this system.
Meanwhile, the NRTL model can represent well many LLE
mixtures through the proper selection of the nonrandomness
parameter aij [12]. PA is a multifunctional molecule, with the
acetylenic carbons and the acidic hydrogen on the carbon serving
as a proton acceptor and donor sites, respectively [18]. Meanwhile,
water is a typical compound which is easily involved in the
hydrogen bonding network. To test the predictability of the system,
we also applied the NRTL model to correlate the experimental data.

4.2. Data correlation

Before the data correlation, the experimental mass compositions (wi) were converted to mole compositions (xi) using the
equation

w2

T 279.15 K
0.0141
0.0464
0.0251
0.0992
0.0465
0.1925
0.0622
0.2621
0.0853
0.3264
0.1131
0.3738
0.1464
0.4152
T 291.15 K
0.0161
0.0527
0.0302
0.1036
0.0524
0.1904
0.0754
0.2608
0.1045
0.3214
0.1398
0.3663
0.1812
0.4024
T 301.15 K
0.0233
0.0515
0.0280
0.1002
0.0558
0.1875
0.0825
0.2574
0.1201
0.3148
0.1507
0.3629
0.2101
0.3923
T 311.15 K
0.0272
0.0523
0.0346
0.0992
0.0589
0.1870
0.0899
0.2528
0.1149
0.3242
0.1592
0.3719
0.2288
0.4078
T 321.15 K
0.0313
0.0542
0.0403
0.1007
0.0658
0.1854
0.0927
0.2550
0.1211
0.3165
0.1618
0.3621
a

Aqueous phase

0.0263
0.0283
0.0291
0.0316
0.0371
0.0507
0.0600

1.02
1.07
1.22
1.35
1.42
1.37
1.33

67.24
37.45
21.34
16.76
12.23
8.18
5.74

0.0592
0.1068
0.1692
0.2172
0.2633
0.3022
0.3294

0.0232
0.0326
0.0315
0.0332
0.0413
0.0534
0.0727

0.89
0.97
1.12
1.20
1.22
1.21
1.22

50.62
27.62
17.15
11.95
8.13
5.59
4.03

0.9251
0.8627
0.7982
0.7404
0.6961
0.6386
0.5614

0.0537
0.1130
0.1699
0.2225
0.2593
0.3022
0.3499

0.0212
0.0243
0.0319
0.0371
0.0446
0.0592
0.0887

0.96
0.89
1.10
1.16
1.21
1.20
1.12

37.99
27.35
15.78
10.38
7.04
5.09
2.99

0.9205
0.8662
0.7541
0.6573
0.5609
0.4689
0.3634

0.9211
0.8750
0.8004
0.7306
0.6926
0.6260
0.5344

0.0595
0.1006
0.1690
0.2352
0.2632
0.3061
0.3584

0.0194
0.0244
0.0306
0.0342
0.0442
0.0679
0.1072

0.88
0.99
1.11
1.07
1.23
1.22
1.14

29.72
24.89
15.04
8.74
7.42
4.78
2.66

0.9145
0.8590
0.7488
0.6523
0.5624
0.4761

0.9208
0.8707
0.7973
0.7335
0.6798
0.6136

0.0573
0.1058
0.1707
0.2277
0.2680
0.3069

0.0219
0.0235
0.0320
0.0388
0.0522
0.0795

0.95
0.95
1.09
1.12
1.18
1.18

27.79
20.53
13.17
8.86
6.63
4.48

w3

w1

w2

w3

0.9395
0.8757
0.7610
0.6757
0.5883
0.5131
0.4384

0.9283
0.8789
0.8131
0.7737
0.7333
0.6763
0.6289

0.0454
0.0928
0.1578
0.1947
0.2296
0.2730
0.3111

0.9312
0.8662
0.7572
0.6638
0.5741
0.4939
0.4164

0.9176
0.8606
0.7993
0.7496
0.6954
0.6444
0.5979

0.9252
0.8718
0.7567
0.6601
0.5651
0.4864
0.3976

Standard uncertainties u are u(T) 0.1 K, u(w) 0.004.

Table 4
UNIQUAC structural parameters of the three pure components.
Component

Water
PA
NPA

0.920
2.471
4.153

1.400
2.154
3.656

Table 5
Temperature-dependent coefcients of the binary interaction parameters of the
UNIQUAC and NRTL models for the water (1) PA (2) NPA (3) ternary system.
iej

1e2
2e1
1e3
3e1
2e3
3e2
RMSD

UNIQUAC

NRTL

Aij

Bij

aij

bij

aij

1.38
1.88
1.86
3.47
2.08
3.06
0.0139

236.68
482.33
420.44
1533.42
525.52
690.12

5.06
3.81
9.03
3.67
3.08
2.36
0.0124

169.03
546.22
1282.70
1539.69
1094.92
656.07

0.14
0.14
0.23
0.23
0.47
0.47

88

C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89

Fig. 3. Ternary phase diagram for the water (1) PA (2) NPA (3) system with tie-lines of the experimental and calculated data at (a) 279.15 K, (b) 291.15 K, (c) 301.15 K, (d) 311.15 K
and (e) 321.15 K. (C) experimental data; ( ) data calculated by the UNIQUAC model; ( ) data calculated by the NRTL model; blue dashed lines, solution curves predicted by the
UNIQUAC model; red dashed lines, solution curves predicted by the NRTL model. (For interpretation of the references to colour in this gure legend, the reader is referred to the web
version of this article.)

w =M
xi P i
i
wj Mj

(3)

where Mi is the molecular weight of component i, with values of the

three compounds listed in Table 2.
The values of temperature-dependent parameters (Appendices
A and B, and Eqs. (A.5) and (B.3)) for the UNIQUAC and NRTL
models can be determined through the correlation of the experimental data. To simplify the data correlation, we considered only
four nonzero coefcients: Aji and Bji for the UNIQUAC model, and aji
and bji for the NRTL model. In addition to the temperaturedependent binary parameters, another adjustable parameter, aji,

was included in the NRTL model. The commonly recommended aji

values for different mixtures are between 0.1 and 0.47.
The UNIQUAC structural parameters for the pure components
were obtained from the ASPEN Properties Databank and are listed
in Table 4. The coordination number zi was set to 10. The binary
interaction parameters for both models were obtained by minimizing the objective function Q [19]:

N X
2 X
3
X
k1 j1 i1

2
4

exp

Tk

 Tkcal

sT

!2

xexp
 xcal
ijk
ijk

sx

!2 3
5

(4)

where N is the number of the tie-lines, and x is the mole fraction.

The subscripts i, j and k refer to the components, phases and tie-

C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89

lines, respectively. The superscripts exp and cal denote the experimental data and the data calculated by the models, respectively. In
the correlation, sT and sx were set to 0.01 K and 0.001, respectively.
The data were correlated by using the commercial software ASPEN
Properties.
To quantify the deviation between the calculated and experimental compositions, the root-mean-square deviation (RMSD) was
calculated by Eq. (5).

v


u
u N 2 3 xexp  xcal 2
uX X X ijk
ijk
RMSD t
6N
j1 i3

(5)

89

Superscripts
I
organic phase identier
II
aqueous phase identier
Exp
experimental
Cal
calculated

Subscripts
I
component index
J
phase index
K
tie-line data index

k1

The temperature-dependent coefcients of the binary interaction parameters for both models are listed in Table 5. The calculated
data through the UNIQUAC and NRTL models are plotted in Fig. 3.
The results are in good agreement with the experimental compositions. The RMSD values for both models are 1.39% and 1.24%,
respectively, demonstrating that both models are qualied to predict the LLE behavior of this system.
5. Conclusions
The LLE data of the ternary system water propargyl
alcohol n-propyl acetate were measured in the temperature
range (279.15e321.15) K under atmospheric pressure. It is possible
to use NPA as an extractant to separate PA from water. The experimental data were correlated using the UNIQUAC and NRTL models
with small RMSD values. Both models can provide an adequate
method to describe the LLE behavior of this system.
Appendix A. Supplementary information
Supplementary information related to this article can be found
at http://dx.doi.org/10.1016/j.uid.2016.10.023.
List of symbols
molecular weight [g mol1]
boiling temperature [K]
density [g cm3]
refractive index
distribution coefcient
selectivity
mass fraction of i
mole fraction of i
absolute temperature [K]
gi
activity coefcient of i
tji
binary interaction parameter of a j-i pair [J mol1]
Fi
average segment fraction of i for UNIQUAC model
qi
average area fraction of i for UNIQUAC model
zi
coordination number of i for UNIQUAC model
qi
pure component surface area number of i for UNIQUAC
model
ri
pure component volume number of i for UNIQUAC model
aji
nonrandomness parameter of a j-i pair for NRTL model
Aji, Bji, Cji, Dji temperature-dependent coefcients of UNIQUAC
binary interaction parameter
aji, bji, cji, dji temperature-dependent coefcients of NRTL binary
interaction parameter
Q
objective function
N
number of tie-line data sets

M
Tb

nD
D
S
wi
xi
T

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