i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3

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Experimental measurement of vaporeliquid equilibrium

for (trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) D propane
(R290))

Xueqiang Dong a,b, Maoqiong Gong a,*, Jun Shen a, Jianfeng Wu a,**
a
Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, P.O. Box 2711, Beijing 100190,
China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, China

article info abstract

Article history: The VLE data for the binary system of R1234ze(E) þ R290 were measured with a recircula-
Received 21 November 2010 tion method at four temperatures (258.150, 263.150, 273.150 and 283.150 K). The measured
Received in revised form uncertainties of the temperature, pressure, and compositions are 5 mK, 0.0005 MPa,
19 February 2011 and 0.005, respectively. All the experimental data were correlated by the PengeRobinson
Accepted 16 March 2011 (PR) EoS with the HuroneVidal (HV) mixing rule involving the non-random two-liquid
Available online 24 March 2011 (NRTL) activity coefficient (PReHVeNRTL) model. Azeotropic behavior can be found at the
measured temperature range.
Keywords: ª 2011 Elsevier Ltd and IIR. All rights reserved.
R290
Azeotropic mixtures
Equilibrium
Refrigerant

Mesures expérimentales de l’équilibre vapeur-liquide du

trans-1,3,3,3-tétrafluoropropène (R1234ze[E]) et du propane
(R290)
Mots clés : Motsclés ; R290 ; Mélanges azéotropiques ; Équilibre ; Frigorigène

* Corresponding author. Tel./fax: þ86 10 82543728.

** Corresponding author. Tel.: þ86 10 82543739; fax: þ86 10 62627843.
E-mail addresses: gongmq@mail.ipc.ac.cn (M. Gong), jfwu@mail.ipc.ac.cn (J. Wu).
0140-7007/$ e see front matter ª 2011 Elsevier Ltd and IIR. All rights reserved.
doi:10.1016/j.ijrefrig.2011.03.007
 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3
Nomenclature
a parameter of the equation of state (energy
parameter)
A NRTL model parameter
b parameter of the equation of state (co-volume
parameter)
C a constant of HV mixing rules
F objective function
g Gibbs free energy
N number of the experimental data points
p pressure (Pa)
R gas constant (J mol1 K1)
T temperature (K)
V mole volume (m3 mol1)
x liquid mole fraction
y vapor mole fraction
1. Introduction
The use of the chlorofluorocarbon (CFC) and hydro-
chlorofluorocarbon (HCFC) refrigerants has been prohibited
with the implementation of the Montreal protocol and its
modifications because of their high ozone depletion poten-
tial (ODP) values. Searching for the high efficient and envi-
ronment friendly alternative refrigerants becomes one of the
most important tasks for the refrigeration industry. The
former investigations show that it is very hard to find
appropriate pure substance candidates. Therefore, mixed
refrigerants especially the azeotropes are becoming more
and more attractive for their behaviors are very nearly as
pure substance at their azeotropic compositions. The
performance and the optimal concentration of the mixed
refrigerants can be estimated by their thermodynamic
properties, such as the vaporeliquid equilibrium (VLE) data.
VLE data of some binary mixtures have been measured in
our previous work (Dong et al., 2010a, b, 2011). In this study,
isothermal VLE data for (trans-1,3,3,3-tetrafluoropropene
(R1234ze(E)) þ propane (R290)) systems were measured by
a recirculation apparatus with view windows at four
temperatures (258.150, 263.150, 273.150 and 283.150 K), and
the azeotropic behavior was found at each measured
temperature. R1234ze(E) and R290 are good components with
zero ODP and very low global warming potential (GWP)
values. Their mixtures are friendly to the environment.
2. Experimental section
2.1. Materials
R1234ze(E) was supplied by Nanjing Yuji Tuohao Co with
a declared mole fraction of 0.995. R290 was provided by Dalian
Special Gas Industry Company with a declared mole fraction
of >0.999. Both of the materials were used without further
purification.
1239
Greek letters
aij NRTL model parameter
sij NRTL model binary interaction parameter (J mol1)
u acentric factor
D deviation
Superscripts
E excess property
Subscripts
c critical property
cal calculated property
exp experimental property
i, j molecular species
1 R1234ze(E)
2 R290
2.2. Experimental apparatus
The apparatus used in this work is the same as used in our
previous work (Dong et al., 2011). It is based on the vapor-
phase recirculation method and shown in Fig. 1. A 150 ml
stainless steel cell equipped with two glasses was immerged
in the isothermal liquid bath. The bath is full with alcohol
which was cooled by a refrigerating machine and heated by an
electric heater. To obtain a uniform temperature distribution,
two stainless steel stirrers with speed controller were located
in the bottom of liquid bath. The Shimaden SR 253 digital
controllers were used to control the temperature of the bath
by changing the power of the electric heater. The liquid bath
was placed in a vacuum vessel to prevent the heat transfer to
the environment and frosting on the bath. The inner of the cell
can be seen through the glasses on the two sides of liquid bath
and vacuum vessel. A self-made magnetic pump outside the
vacuum vessel was used to accelerate the equilibrium
process. The vapor phase at the top of the equilibrium cell was
driven into the liquid phase by the pump. A copper tube with
distributed nozzles was located at the end of the recirculation
loop to make the return vapor phase mix evenly with the
liquid phase. The temperature in the equilibrium cell was
measured by a 25 U standard platinum resistance thermom-
eter which was inserted in the cell. It was calibrated by the
Cryogenic Metrology Station of the Chinese Academy of
Sciences based on the 1990 International Temperature Scale
(ITS 90) with an uncertainty less than 3 mK. The combined
standard uncertainty of the temperature measurement is
estimated to be less than 5 mK. A Mensor series 6000 digital
pressure transducer was used to measure the pressure in the
cell. The transducer has two full scales of 1.25 MPa and
2.5 MPa with uncertainties of 0.00025 MPa and 0.0005 MPa,
respectively. In this work, the full scale of 1.25 MPa was used.
The combined standard uncertainty of the pressure
measurement is estimated to be 0.0005 MPa. The composi-
tions of the vapor and liquid phase were analyzed by a Shi-
madzu GC2014 gas chromatograph equipped with a thermal
conductivity detector (TCD). The gas chromatograph was
1240 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3

Fig. 1 e Schematic diagram of the experimental system. 1, Temperature and pressure indicator; 2, digital controller; 3,
refrigerating machine; 4, evaporator; 5, stirrer; 6, electric heater; 7, equilibrium cell; 8, view windows; 9, vacuum pump; 10,
isothermal liquid bath; 11, vacuum vessel; 12, motor; 13, gas chromatograph; 14, feed system; 15, magnetic pump.

calibrated by the mixtures that were pre-prepared gravimet- At last, the content of the cell was evacuated and the satu-
rically. The uncertainty of the composition measurement is rated vapor pressure data of R290 were measured.
estimated to be less than 0.005 in mole fraction.

2.3. Experimental procedure 3. Results and correlations

The system was firstly evacuated to remove the residual The VLE data for the binary system of R1234ze(E) þ R290 were
impurities at room temperature. Small amounts of pure measured at four temperatures (258.150, 263.150, 273.150 and
R1234ze(E) were then driven into the cell and degassed from 283.150 K). All the experimental data were correlated by the
the cell for at least three times to purge the total system. While PengeRobinson (Peng and Robinson, 1976) equation of state
the temperature of the liquid bath was decreasing, the pure (PR EoS) incorporating the HuroneVidal (HV) mixing rule
R1234ze(E) was driven into the equilibrium cell. After the (Huron and Vidal, 1979) utilizing the non-random two-liquid
desired temperatures were reached and maintained for at (NRTL) activity coefficient model (Renon and Prausnitz, 1968).
least 1 h with the continuous work of the magnetic pump, and The critical temperatures, critical pressures, and acentric
the temperature fluctuation in the cell was less than 3 mK factors for R1234ze(E) and R290 used in the correlation are
for at least 10 min, the saturated vapor pressure data of shown in Table 1. The saturated vapor pressures data of R290
R1234ze(E) were obtained. Suitable amount of R290 was then
charged into the cell and mixed sufficiently with R1234ze(E)
under the work of magnetic pump. After the desired temper-
atures were reached and maintained for at least 1 h, and the Table 1 e Critical parameters and acentric factors for
fluctuation of the temperature in the cell was less than 3 mK R1234ze(E) and R290.
for at least 10 min, the equilibrium state was considered to be Compound Tc (K) Pc (MPa) u
reached. The pressure in the cell was recorded from the digital a a
R1234ze(E) 382.51 3.632 0.3086b
pressure transducer. The vapor and liquid mole fractions were R290c 369.89 4.251 0.1521
measured by the gas chromatograph at least three times, and
then the average value was recorded. Repeating this process a Values from Higashi and Tanaka (2010).
b Values from Akasaka (2010).
by adding the more volatile component (R290 in this work)
c Values from Refprop (Lemmon et al., 2007).
step by step, VLE data of other concentration were measured.
 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3 1241

Table 2 e Experimental and reference vapor pressure of aji ¼ aij (11)

R290 (Lemmon et al., 2007).
where sii ¼ 0, aii ¼ 0, and aji, Aij, and Aji are adjustable param-
T (K) pexp (MPa) pref (MPa) Dpa (MPa) Dp/pb
eters. In this work, aji ¼ 0.3. The symbols Gji and Gij (or Gli and
258.150 0.2916 0.29162 0.00002 0.0069 Gil) are also NRTL parameters, and they can be calculated
263.150 0.3453 0.34528 0.00002 0.0058 by Eq. (10).
273.150 0.4745 0.47446 0.00004 0.0084
The adjustable parameters Aij and Aji were regressed from
283.150 0.6367 0.63660 0.00010 0.0157
the experimental data by minimizing the following objective
a Dp ¼ pexp  pref . function using the gradient method
pexp  pref
b Dp=p ¼ 100  .
pexp

were compared with the data calculated from Refprop 8.0

(Lemmon et al., 2007), and the results are shown in Table 2. Table 3 e Experimental data and correlated data for the
binary system of R1234ze(E) (1) D R290 (2).
The experimental data are in good agreement with the refer-
ence data. Experimental Calculated data
data with the PReHVeNRTL model
The PR EoS is used in the form
pexp (MPa) x1exp y1exp pcal (MPa) y1cal Dpa (MPa) Dyb
RT aðTÞ
p¼  (1) T ¼ 258.150 K
v  b vðv þ bÞ þ bðv  bÞ
0.2916 0.000 0.000 0.2910 0.0000 0.0006 0.0000
0.3021 0.122 0.131 0.3017 0.1305 0.0004 0.0005
where p is the pressure in Pa, R is the gas constant
0.3016 0.203 0.181 0.3014 0.1797 0.0002 0.0013
(R ¼ 8.314 J mol1 K1 in this work), v is the mole volume in 0.2918 0.387 0.251 0.2918 0.2548 0.0000 0.0038
m3 mol1, T is the temperature in K, and a and b are constants 0.2846 0.465 0.279 0.2850 0.2827 0.0004 0.0037
of EoS. 0.2632 0.622 0.346 0.2642 0.3480 0.0010 0.0020
The constants a and b of the PR EoS are defined as 0.2525 0.683 0.378 0.2522 0.3821 0.0003 0.0041
0.2249 0.786 0.460 0.2251 0.4621 0.0002 0.0021
R2 T2c aðTÞ 0.1810 0.901 0.619 0.1797 0.6289 0.0013 0.0099
aðTÞ ¼ 0:457235 (2)
pc 0.1194 1.000 1.000 0.1212 1.0000 0.0018 0.0000

T ¼ 263.150 K
RTc 0.3453 0.000 0.000 0.3444 0.0000 0.0009 0.0000
b ¼ 0:077796 (3)
pc 0.3576 0.120 0.131 0.3574 0.1303 0.0002 0.0007
0.3574 0.203 0.183 0.3572 0.1820 0.0002 0.0010
where 0.3458 0.388 0.257 0.3459 0.2613 0.0001 0.0043

  2 0.3374 0.463 0.287 0.3380 0.2902 0.0006 0.0032
aðTÞ ¼ 1 þ 0:37464 þ 1:54226u  0:26992u2 1  T0:5
r (4) 0.3111 0.627 0.357 0.3119 0.3628 0.0008 0.0058
0.2983 0.685 0.394 0.2982 0.3973 0.0001 0.0033
T 0.2670 0.785 0.476 0.2673 0.4777 0.0003 0.0017
Tr ¼ (5) 0.2153 0.902 0.639 0.2140 0.6489 0.0013 0.0099
Tc
0.1464 1.000 1.000 0.1486 1.0000 0.0022 0.0000
pc and Tc are the critical pressure and temperature, respec-
T ¼ 273.150 K
tively, and u is the acentric factor.
0.4745 0.000 0.000 0.4732 0.0000 0.0013 0.0000
The HV mixing rules are given as 0.4915 0.120 0.131 0.4915 0.1312 0.0000 0.0002
X   0.4918 0.203 0.187 0.4918 0.1858 0.0000 0.0012
aii gE 0.0001 0.0036
a¼b xi  N (6) 0.4762 0.390 0.270 0.4763 0.2736
bii C 0.4648 0.463 0.292 0.4653 0.3051 0.0005 0.0131
0.4267 0.626 0.388 0.4286 0.3864 0.0019 0.0016
X
b¼ xi bii (7) 0.4099 0.685 0.424 0.4098 0.4240 0.0001 0.0000
0.3697 0.784 0.505 0.3687 0.5089 0.0010 0.0039
where gEN is the excess Gibbs energy at infinite pressure and C 0.3000 0.904 0.678 0.2977 0.6866 0.0023 0.0086
is a constant. For the PR EoS, C is 0.623225. 0.2154 1.000 1.000 0.2177 1.0000 0.0023 0.0000
The NRTL activity coefficient model was used to calculate T ¼ 283.150 K
the excess Gibbs energy in the form 0.6367 0.000 0.000 0.6353 0.0000 0.0014 0.0000
P 0.6598 0.121 0.132 0.6592 0.1321 0.0006 0.0001
s G x 0.6601 0.205 0.191 0.6601 0.1904 0.0000 0.0006
gE X j ji ji j
¼ xi P (8) 0.6404 0.388 0.281 0.6402 0.2856 0.0002 0.0046
RT Gli xl 0.5735 0.629 0.412 0.5752 0.4124 0.0017 0.0004
l
0.4995 0.782 0.534 0.4996 0.5368 0.0001 0.0028
Aji 0.4097 0.909 0.705 0.4044 0.7237 0.0053 0.0187
sji ¼ (9) 0.3070 1.000 1.000 0.3095 1.0000 0.0025 0.0000
T
  a Dp ¼ pexp  pcal .
Gji ¼ exp  aji sji (10) b Dy ¼ y1exp  y1cal .
1242 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3

0.7 0.005

0.6 0.000

0.5
-0.005

y1exp-y1cal
p/MPa

0.4
-0.010

0.3
-0.015
0.2

-0.020
0.1 0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0 x1
x1, y1
Fig. 4 e Deviations of the mole fraction of the vapor phase
Fig. 2 e Vaporeliquid equilibrium diagram for the between the experimental data and the calculated data. -,
R1234ze(E) (1) D R290 (2) system at four temperatures. -, 258.150 K; C, 263.150 K; :, 273.150 K; ;, 283.150 K.
258.150 K; C, 263.150 K; :, 273.150 K; ;, 283.150 K. Solid
lines, calculated using the PReHVeNRTL model.

!
X
N jpexp  pcal j Table 4 e Binary parameters and deviations for
F¼ (12) R1234ze(E) D R290 system.
i¼1
pexp
T (K) 258.150 263.150 273.150 283.150
where N is the number of the experimental data points and
Aij (K) 105.211 97.998 77.891 74.871
pexp and pcal are the pressures obtained from the experiment
Aji (K) 333.125 336.863 349.255 339.361
and calculation, respectively.
AARD pa 0.33 0.30 0.30 0.35
The experimental and calculated VLE data are reported in AAD yb 0.0028 0.0030 0.0032 0.0033
Table 3 and plotted in Fig. 2. The symbols pexp refers to the P
a AARD p ¼ ð100=NÞ ni¼1 ðjPexp  Pcal j=Pexp Þ.
pressures of the systems; x1exp and y1exp represent the mole P
b AAD y ¼ N i¼1 ðjy iexp  yical j=NÞ.
fractions of the liquid and vapor phases for R1234ze(E),
respectively; y1cal refers to the calculated mole fraction of the
vapor phase; Dp and Dy represent the deviations between the
experimental data and the calculated values. Fig. 2 shows are shown in Figs. 3 and 4, respectively. The average absolute
that the correlated results agree well with the experimental deviations (AAD) of vapor-phase mole fraction and the
data at each temperature. The relative deviations of the average absolute relative deviations (AARD) of pressure are
pressures and the deviations of vapor-phase mole fraction presented in Table 4. The values of the adjustable parameters
Aij and Aji in the NRTL model are also shown in Table 4.
Azeotropic behavior can be found at these four temperatures.
2.0 The azeotropic pressure and composition at each tempera-
ture can be determined by solving the following equation
1.5 (Bejan, 1997):
1.0 dp
( Pexp-Pcal) /Pexp×100

¼0 (13)
dx1
0.5
The results are shown in Table 5. The symbols x1,az and paz
0.0 represent the calculated azeotropic compositions of
-0.5 R1234ze(E) and pressures, respectively.

-1.0

-1.5

-2.0 Table 5 e The azeotropic composition x1,az and pressure

0.0 0.2 0.4 0.6 0.8 1.0 paz for R1234ze(E) (1) D R290 (2) at each experimental
x temperature.
1
T (K) x1,az paz (MPa) T (K) x1,az paz (MPa)
Fig. 3 e Deviations of the pressure between the
258.150 0.153 0.3020 273.150 0.164 0.4924
experimental data and the calculated data. -, 258.150 K;
263.150 0.157 0.3579 283.150 0.170 0.6607
C, 263.150 K; :, 273.150 K; ;, 283.150 K.
 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3
4. Conclusions
In this work, the VLE data for the binary system of
R1234ze(E) þ R290 were measured with a recirculation method
at four temperatures. All the data were correlated by the PR
EoS with the HV mixing rule involving the NRTL activity
coefficient model. The correlated results show good agree-
ment with the experimental data at each temperature. The
maximum average relative deviation of pressure is 0.35%,
while the maximum average absolute deviation of vapor
phase mole fraction is 0.0033. The azeotropic behavior can be
found in the measured temperature range.
Acknowledgement
This work is financially supported by the National Natural
Sciences Foundation of China (GS1) under the contract
number of 50890183.
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