J. Chem.

Thermodynamics 118 (2018) 43–50

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Vapor liquid equilibria for binary mixtures of difluoromethane (R32) +

fluoroethane (R161) and fluoroethane (R161) + trans-1,3,3,3-
tetrafluoropropene (R1234ze(E))
Xianyang Meng ⇑, Xiaozhen Hu, Tao Yang, Jiangtao Wu
Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, Xi’an Jiaotong University, Xi’an 710049, China

a r t i c l e i n f o a b s t r a c t

Article history: Developing new refrigerants with low global warming potential (GWP) is the major challenge for the
Received 30 June 2017 refrigeration industry with the Paris Agreement going into effect on 4 November 2016. In this work,
Received in revised form 14 September we reported the isothermal vapor liquid equilibrium (VLE) data for the low GWP binary refrigerants of
2017
difluoromethane (R32) + fluoroethane (R161) and fluoroethane (R161) + trans-1,3,3,3-tetrafluoropropene
Accepted 27 October 2017
Available online 28 October 2017
(R1234ze(E)). The measurements were carried out with a quasi-static analytical apparatus along five iso-
therms from (283.15 to 323.15) K. The experimental data were correlated by Peng-Robinson-Stryjek-Vera
equation of state combined with the Wong and Sandler mixing rule and the non-random two-liquid
Keywords:
Vapor liquid equilibrium
activity coefficient (PRSV + WS + NRTL) model. The correlated results and the experimental data show
R32 good consistency. The average absolute deviation of pressure (AAD(p)) and average absolute deviation
R161 of vapor phase mole fraction (AAD(y)) are 0.12% and 0.0011 for R32 + R161, 0.20% and 0.0014 for
R1234ze(E) R161 + R1234ze(E), respectively.
PRSV + WS + NRTL Ó 2017 Elsevier Ltd.

1. Introduction
According to the Montreal and Kyoto protocols, chlorofluorocar-
bons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluoro-
carbons (HFCs), commonly used in refrigeration and air
conditioning systems, were scheduled to phase out because of
their depletion of the ozone layer and contribution to global warm-
ing [1,2]. The Paris agreement was effective on 4 November 2016,
which makes it more urgent to develop alternatives that can meet
the requirements of both thermodynamic properties and environ-
mental performance. At present, trans-1,3,3,3-tetrafluoropropene
(R1234ze(E), ozone depletion potential (ODP) = 0, 100 years GWP
< 1 [3]) is one of the most suitable commercial candidates [4].
However, R1234ze(E) is still not an ideal replacement at every
aspect. It possessed low cooling capacity, low coefficient of perfor-
mance (COP) and low heat transfer performance than R32 and
R134a in series tests [5,6]. One of the proposed solutions is to blend
with other refrigerants to improve the COP and heat transfer char-
acteristic of R1234ze(E) [2]. R32 with superior thermodynamic
properties, large latent heat and relatively acceptable GWP (100
years GWP = 677 [3]) is a commonly studied component in mix-
tures containing R1234ze(E) [7–9]. R161 is also an environmental
⇑ Corresponding author.
E-mail address: xymeng@mail.xjtu.edu.cn (X. Meng).
friendly refrigerant with very low GWP (100 years GWP = 4 [7–9]).
Han and co-workers measured the VLE and cycle performance of
refrigerant blends containing R161, which indicates these blends
could be used to replace R410A, R407C and R22 [10–12].
Thermophysical properties, especially vapor liquid equilibria, of
refrigerant blends are essential to the optimum design and the
investigation of their performance in refrigeration or heat pump
cycles. The VLE of R32 + R1234ze(E), R32 + R1234yf and R161 +
R1234yf had already been reported in previously work of our
group [13,14]. For a more comprehensive study of these
refrigerants, in this work, we present new vapor liquid equilibrium
data, measured by a quasi-static analytical apparatus, for
R32 + R161 and R161 + R1234ze(E) in the temperature range of
(283.15–323.15) K. The PRSV + WS + NRTL model was used to
correlate the VLE data.
2. Experimental
2.1. Chemicals
R32 and R161 were purchased from Zhejiang Lantian Environ-
mental Protection Fluoro Material Co., Ltd. with a stated mass pur-
ity higher than 0.998 and 0.997, respectively. R1234ze(E) was
provided from Honeywell International Inc. with a declared mass
purity higher than 0.995. Freeze-pump-thaw cycles were used to

https://doi.org/10.1016/j.jct.2017.10.015
0021-9614/Ó 2017 Elsevier Ltd.
44 X. Meng et al. / J. Chem. Thermodynamics 118 (2018) 43–50

Table 1
Sample Specification.a

Chemical name CAS No. Source Stated mass purity GC area fraction Tc/K pc/MPa x
R32 75–10-5 Lantian >0.998 >0.9993 351.26 5.782 0.2769
R161 353–36-6 Lantian >0.997 >0.9996 375.25 5.046 0.217
R1234ze(E) 29118–24-9 Honeywell >0.995 >0.9995 382.51 3.6349 0.313
a
The critical properties are obtained from NIST Refprop V9.1 [15].

degas the non-condensable components of the refrigerants before
the experiments. The sample purity was subsequently checked at
least three times by gas chromatography and the tested results
were higher than 0.9993 for these chemicals. Table 1 lists the sam-
ple purities and critical properties in detail.
2.2. Apparatus
A quasi-static analytical apparatus as shown in Fig. 1 was used
to measure the vapor liquid equilibrium data. Details of this appa-
ratus had already been reported in our previous work [13,14], only
a brief introduction is given here. The equilibrium cell is a hollow
cylinder made of 316L stainless steel with a nominal volume of
192 mL. A gear pump (model: MG3012A, Pascal Micropump,
China) is used to circulate the liquid phase and promote the equi-
librium of the system. A four-port valve (model: 6I4UWE2, VICI
Valco) with 2 lL internal sample loop is used for liquid phase sam-
pling. While for the vapor phase sampling, a needle valve (model:
SS-31RS4, Swagelok) is used, which is connected to a six-port valve
with 250 lL sample loop by stainless steel capillary (0.38 mm I.D.,
1.6 mm O.D.). The equilibrium cell, gear pump, four-port valve and
needle valve are all located in a thermostatic water bath. The tem-
perature of the bath is regulated by a temperature controller
(model: 2200, Fluke) with temperature fluctuation within 15 mK
per 30 min. An auxiliary thermostatic ethanol bath (model:
DC4006, Shanghai Hengping, China) is used to provide sufficient
cooling capacity when temperature below 313.15 K.
The temperature was measured by a 25 X standard platinum
resistance (SPRT, model: 5683, Fluke) connected to a precision
thermometer (model: F500, ASL). The pressure was measured by
a quartz-crystal pressure transducer (0–6.9 MPa, model: 31 K-
101, Paroscientific) combined with differential pressure transmit-
ter (
60 to 60 kPa, model: Rosemount 3051CD, Emerson). Agilent
53131A and 34970A were used to measure the frequency of the
transducer and the DC current of the transmitter, respectively.
The mole fraction was measured by a gas chromatograph (model:
7820A, Agilent) equipped with a thermal conductivity detector
(TCD) and a capillary column (GS-GasPro, 60 m  0.32 mm). The
GC was calibrated with mixtures of known mole fraction prepared
gravimetrically using an electronic balance (0.1 mg/220 g, model:
XS205, Mettler Toledo). The standard uncertainties of temperature
and pressure are 10 mK and 0.5 kPa, respectively. The standard
uncertainties of both vapor and liquid phase mole fractions are
all 0.005, taking into account the calibration procedure and mea-
surement repeatability.
2.3. Experimental procedure
The apparatus was first cleaned by ethanol and acetone for sev-
eral times. Soon afterwards, it was vacuumed for at least two
hours. Then a small amount of refrigerant with relatively lower

Fig. 1. Schematic diagram of the vapor-liquid equilibria apparatus. (1) equilibrium cell; (2) gear pump; (3) four-port valve; (4) six-port valve; (5) sample needle valve; (6)
differential pressure transmitter; (7) pressure transducer; (8) digital acquisition; (9) standard platinum resistance; (10) thermometer; (11) stirrer; (12) heater; (13)
temperature controller; (14) auxiliary thermostatic bath; (15) vacuum pump; (16) sample cylinder; (17) gas chromatograph.
 X. Meng et al. / J. Chem. Thermodynamics 118 (2018) 43–50 45

vapor pressure (R161 or R1234ze(E)) was charged into the equilib-
rium cell. About two hours later, the refrigerant was discharged
and the apparatus was vacuumed again. This vacuum-charge-
discharge procedure was repeated three times to eliminate any
preexist impurities. Later, the relatively lower vapor pressure com-
ponent was filled about half of the cell. Then the relatively higher
vapor pressure component (R32 or R161) was introduced appropri-
ately. The thermostatic bath was set to the desired temperature
and the gear pump was turned on to promote the equilibrium. Sev-
eral hours later, the system pressure was steady and then the vapor
and liquid samples were taken out by sample valves and measured
by gas chromatograph. The measurement of each phase was
repeated at least four times to acquire reliable results. After the
measurement at 323.15 K, the temperature was dropped to
283.15 K again and additional amount of the relatively higher
vapor pressure component was loaded to vary the total composi-
tion. When necessary, moderate samples were discharged to
ensure the proper level of vapor and liquid interface.
3. Results
VLE data for R32 + R161 and R161 + R1234ze(E) were measured
along five isotherms from (283.15 to 323.15) K at nine
compositions. The experimental data and the calculated results
from PRSV + WS + NRTL model in section 4 for R32 + R161 and
R161 + R1234ze(E) are both listed in Tables 2 and 3, respectively.

Table 2
Vapor liquid equilibrium data for R32(1) + R161.a

Experimental Data PRSV + WS + NRTL

pexp/MPa x1,exp y1,exp pcal/MPa y1,cal dpb Dy c
T = 283.15 K
0.6014d 0.0000 0.0000 0.5995 0.0000 0.32 0.0000
0.6482 0.0913 0.1457 0.6470 0.1493 0.18
0.0036
0.7179 0.2248 0.3326 0.7181 0.3349
0.03
0.0023
0.7532 0.2905 0.4123 0.7533 0.4143
0.01
0.0020
0.8146 0.4060 0.5371 0.8148 0.5383
0.03
0.0012
0.8573 0.4875 0.6127 0.8576 0.6159
0.04
0.0032
0.9218 0.6124 0.7195 0.9217 0.7225 0.01
0.0030
0.9586 0.6862 0.7786 0.9584 0.7799 0.02
0.0013
1.0260 0.8242 0.8784 1.0243 0.8797 0.16
0.0013
1.0811 0.9427 0.9591 1.0778 0.9609 0.31
0.0018
1.1073e 1.0000 1.0000 1.1024 1.0000 0.44 0.0000
T = 293.15 K
0.8056d 0.0000 0.0000 0.8036 0.0000 0.25 0.0000
0.8662 0.0906 0.1415 0.8649 0.1444 0.15
0.0029
0.9579 0.2236 0.3248 0.9571 0.3261 0.09
0.0013
1.0035 0.2894 0.4032 1.0031 0.4049 0.04
0.0017
1.0832 0.4041 0.5268 1.0834 0.5279
0.02
0.0011
1.1400 0.4856 0.6038 1.1399 0.6061 0.01
0.0022
1.2301 0.6108 0.7131 1.2253 0.7145 0.39
0.0014
1.2744 0.6837 0.7723 1.2738 0.7725 0.05
0.0002
1.3649 0.8235 0.8754 1.3638 0.8763 0.08
0.0008
1.4388 0.9414 0.9583 1.4358 0.9592 0.21
0.0009
1.4740e 1.0000 1.0000 1.4701 1.0000 0.26 0.0000
T = 303.15 K
1.0574d 0.0000 0.0000 1.0564 0.0000 0.09 0.0000
1.1351 0.0902 0.1384 1.1342 0.1397 0.08
0.0013
1.2519 0.2226 0.3171 1.2515 0.3171 0.03 0.0000
1.3103 0.2875 0.3937 1.3098 0.3940 0.04
0.0003
1.4133 0.4016 0.5162 1.4127 0.5160 0.05 0.0002
1.4871 0.4841 0.5952 1.4869 0.5956 0.02
0.0004
1.5994 0.6096 0.7057 1.5986 0.7059 0.05
0.0002
1.6615 0.6823 0.7646 1.6623 0.7650
0.05
0.0004
1.7815 0.8223 0.8715 1.7817 0.8719
0.01
0.0004
1.8787 0.9407 0.9574 1.8782 0.9577 0.03
0.0003
1.9258e 1.0000 1.0000 1.9246 1.0000 0.06 0.0000
T = 313.15 K
1.3636d 0.0000 0.0000 1.3651 0.0000
0.11 0.0000
1.4614 0.0899 0.1346 1.4623 0.1350
0.06
0.0004
1.6078 0.2218 0.3079 1.6091 0.3078
0.08 0.0002
1.6811 0.2858 0.3834 1.6816 0.3825
0.03 0.0009
1.8113 0.3992 0.5045 1.8112 0.5032 0.00 0.0013
1.9055 0.4820 0.5851 1.9062 0.5834
0.04 0.0017
2.0503 0.6081 0.6967 2.0505 0.6958
0.01 0.0009
2.1297 0.6801 0.7566 2.1322 0.7557
0.12 0.0009
2.2862 0.8220 0.8667 2.2903 0.8674
0.18
0.0007
2.4117 0.9393 0.9544 2.4163 0.9553
0.19
0.0009
2.4762e 1.0000 1.0000 2.4791 1.0000
0.12 0.0000
T = 323.15 K
1.7306d 0.0000 0.0000 1.7373 0.0000
0.38 0.0000
1.8520 0.0896 0.1307 1.8568 0.1300
0.26 0.0007
2.0329 0.2197 0.2982 2.0360 0.2961
0.15 0.0021
2.1244 0.2843 0.3727 2.1269 0.3703
0.12 0.0024

(continued on next page)

46 X. Meng et al. / J. Chem. Thermodynamics 118 (2018) 43–50

Table 2 (continued)

Experimental Data PRSV + WS + NRTL

pexp/MPa x1,exp y1,exp pcal/MPa y1,cal dpb Dy c
2.2856 0.3970 0.4922 2.2876 0.4892
0.09 0.0030
2.4051 0.4797 0.5725 2.4068 0.5695
0.07 0.0030
2.5894 0.6069 0.6871 2.5912 0.6843
0.07 0.0028
2.6896 0.6785 0.7473 2.6951 0.7453
0.21 0.0020
2.8930 0.8206 0.8612 2.8995 0.8610
0.23 0.0002
3.0542 0.9382 0.9521 3.0641 0.9528
0.33
0.0007
3.1380e 1.0000 1.0000 3.1478 1.0000
0.31 0.0000
a
Standard uncertainty (u), u(T) = 10 mK, u(p) = 0.5 kPa, u(x1) = u(y1) = 0.005.
b
dp = 100(pexp
pcal)/pexp.
c
Dy = y1,exp
y1,cal.
d
Vapor pressure data were obtained from Hu et al. [14].
e
Vapor pressure data were obtained from Hu et al. [13].

Table 3
Vapor liquid equilibrium data for R161(1) + R1234ze(E)(2).a.

Experimental Data PRSV + WS + NRTL

pexp/MPa x1,exp y1,exp pcal/MPa y1,cal dpb Dy c
T = 283.15 K
0.3086d 0.0000 0.0000 0.3081 0.0000 0.17 0.0000
0.3408 0.1416 0.2123 0.3421 0.2190 -0.38 -0.0067
0.3596 0.2200 0.3193 0.3615 0.3252 -0.53 -0.0059
0.3868 0.3322 0.4574 0.3905 0.4624 -0.95 -0.0050
0.4158 0.4382 0.5746 0.4194 0.5781 -0.86 -0.0035
0.4571 0.5782 0.7049 0.4601 0.7121 -0.66 -0.0072
0.4743 0.6335 0.7596 0.4771 0.7595 -0.58 0.0001
0.5022 0.7184 0.8233 0.5040 0.8264 -0.35 -0.0031
0.5364 0.8152 0.8949 0.5358 0.8942 0.10 0.0007
0.5659 0.9026 0.9483 0.5656 0.9481 0.05 0.0003
0.6014e 1.0000 1.0000 0.5995 1.0000 0.32 0.0000
T = 293.15 K
0.4280d 0.0000 0.0000 0.4270 0.0000 0.24 0.0000
0.4692 0.1396 0.2049 0.4698 0.2085 -0.13 -0.0036
0.4936 0.2181 0.3098 0.4947 0.3128 -0.23 -0.0030
0.5289 0.3287 0.4446 0.5313 0.4468 -0.45 -0.0022
0.5661 0.4340 0.5615 0.5681 0.5620 -0.35 -0.0005
0.6196 0.5750 0.6952 0.6209 0.6990 -0.21 -0.0038
0.6414 0.6298 0.7480 0.6425 0.7471 -0.17 0.0009
0.6769 0.7154 0.8160 0.6776 0.8166 -0.10 -0.0006
0.7208 0.8132 0.8879 0.7194 0.8878 0.19 0.0001
0.7594 0.9024 0.9448 0.7591 0.9452 0.05 -0.0004
0.8056e 1.0000 1.0000 0.8036 1.0000 0.25 0.0000
T = 303.15 K
0.5789d 0.0000 0.0000 0.5782 0.0000 0.12 0.0000
0.6312 0.1381 0.1985 0.6314 0.1994 -0.03 -0.0009
0.6626 0.2172 0.3011 0.6629 0.3023 -0.05 -0.0012
0.7073 0.3266 0.4324 0.7084 0.4334 -0.16 -0.0010
0.7547 0.4321 0.5482 0.7549 0.5488 -0.03 -0.0006
0.8224 0.5738 0.6840 0.8220 0.6878 0.05 -0.0038
0.8495 0.6282 0.7363 0.8493 0.7365 0.03 -0.0002
0.8943 0.7133 0.8066 0.8936 0.8074 0.08 -0.0008
0.9494 0.8127 0.8812 0.9479 0.8822 0.16 -0.0010
0.9990 0.9022 0.9411 0.9989 0.9423 0.01 -0.0012
1.0574e 1.0000 1.0000 1.0564 1.0000 0.09 0.0000
T = 313.15 K
0.7674d 0.0000 0.0000 0.7671 0.0000 0.04 0.0000
0.8324 0.1375 0.1914 0.8325 0.1921 -0.01 -0.0007
0.8715 0.2156 0.2918 0.8710 0.2915 0.06 0.0003
0.9270 0.3237 0.4196 0.9267 0.4195 0.04 0.0001
0.9857 0.4300 0.5352 0.9848 0.5356 0.09 -0.0004
1.0701 0.5726 0.6755 1.0689 0.6767 0.12 -0.0012
1.1040 0.6260 0.7244 1.1023 0.7253 0.16 -0.0009
1.1603 0.7117 0.7972 1.1582 0.7984 0.18 -0.0012
1.2275 0.8111 0.8737 1.2264 0.8757 0.09 -0.0020
1.2901 0.9009 0.9370 1.2911 0.9385 -0.07 -0.0015
1.3636e 1.0000 1.0000 1.3651 1.0000 -0.11 0.0000
T = 323.15 K
0.9978d 0.0000 0.0000 0.9994 0.0000 -0.16 0.0000
1.0784 0.1364 0.1852 1.0784 0.1844 0.00 0.0008
 X. Meng et al. / J. Chem. Thermodynamics 118 (2018) 43–50 47

Table 3 (continued)

Experimental Data PRSV + WS + NRTL

pexp/MPa x1,exp y1,exp pcal/MPa y1,cal dpb Dyc
1.1266 0.2141 0.2830 1.1251 0.2812 0.14 0.0018
1.1949 0.3218 0.4082 1.1928 0.4071 0.17 0.0011
1.2668 0.4269 0.5223 1.2631 0.5215 0.29 0.0008
1.3708 0.5700 0.6635 1.3667 0.6642 0.30 -0.0007
1.4118 0.6244 0.7126 1.4086 0.7145 0.23 -0.0019
1.4809 0.7110 0.7878 1.4783 0.7900 0.17 -0.0022
1.5629 0.8096 0.8670 1.5624 0.8690 0.04 -0.0020
1.6406 0.9002 0.9330 1.6437 0.9349 -0.19 -0.0019
1.7306e 1.0000 1.0000 1.7373 1.0000 -0.38 0.0000
a
Standard uncertainty (u), u(T) = 10 mK, u(p) = 0.5 kPa, u(x1) = u(y1) = 0.005.
b
dp = 100(pexp
pcal)/pexp.
c
Dy = y1,exp
y1,cal.
d
Vapor pressure data were obtained from Hu et al. [13].
e
Vapor pressure data were obtained from Hu et al. [14].

4. Correlation and discussion j ¼ j0 þ j1 ð1 þ T 0:5

r Þð0:7
T r Þ; ð5Þ

Equation of state (EOS) combined with mixing rule method is a j0 ¼ 0:378893 þ 1:4897153x
0:17131848x2 þ 0:0196554x3 ;
commonly used model to correlated the vapor liquid equilibrium ð6Þ
data [16]. Lots of different models were applied in literatures, for
example, PR + vdW model [17], PR + HV + NRTL model [18], PR + where T and p are the equilibrium temperature and pressure, R
WS + NRTL model [19], RK + HV + NRTL model [20], etc. The PR is the universal gas constant, v is the molar volume, a is a function
EOS is a universal model, which makes it easy to use, but at the of temperature, b is a constant, x is the acentric factor, j1 is a
same time, it has relatively lower accuracy for polar compounds. parameter fitted from the saturated vapor pressure of pure
Stryjek and Vera modified the PR EOS by introducing a single pure substance.
compound parameter to increase its accuracy for reproduction of The j1 of R32, R161 and R1234ze(E) were obtained from Hu
the vapor pressure data [21]. After a comparison of different mod- et al. [13,14], which has been listed in Table 4.
els, here, we chose the PRSV EOS combined with the WS mixing
The WS mixing rule is expressed in the form:
rule [22] and the NRTL activity coefficient model [23] to correlate
the vapor liquid equilibrium data, which is the most accurate am X ai AE1
¼ xi þ ; ð7Þ
one for R32 + R161 and R161 + R1234ze systems. bm i
bi C

The PRSV equation of state is given by:

XX  
i
xx
j i j
b
RT
a
ij
RT a bm ¼ X ; ð8Þ
p¼
; ð1Þ A1 E

v
b v 2 þ 2bv
b2 1
x ai
i i bi RT

CRT

    a 
a
ai
with bi
RT þ bj
RTj
b
¼ ð1
kij Þ; ð9Þ
aR2 T 2c RT ij 2
a ¼ 0:457235 ; ð2Þ
pc with the constant C being:
pffiffiffi
RT c lnð 2
1Þ
b ¼ 0:077796 ; ð3Þ C¼ pffiffiffi ; ð10Þ
pc 2
h i2 where AE1 is the excess Helmholtz free energy at infinite pres-
a ¼ 1 þ jð1
T 0:5
r Þ ; ð4Þ sure, kij is a second virial coefficient binary interaction parameter,
kii = 0 and kij = kji.
The NRTL model is applied to calculate the excess Helmholtz
Table 4 free energy given by:
j1 of PRSV equation of state for R32, R161 and R1234ze(E).a X
Chemicals j1 AAD(p)b/% Temperature range/K AE1 X xs g
j j ji ji
¼ xi X ; ð11Þ
R32
0.06592 0.20 283.15–323.15 RT xg
i k k ki
R161
0.04364 0.20

0.001067
g ij ¼ expð
bij sij Þ;
R1234ze(E) 0.10
ð12Þ
a
Obtained from Hu et al. [13,14].
P
b
AADðpÞ=% ¼ ð100=NÞ N i¼1 jðpexp;i
pcal;i Þ=pexp;i j:

Table 5
Parameters of PRSV + WS + NRTL model for R32(1) + R161(2) and R161(1) + R1234ze(E)(2).

Chemicals k12 s12 s21 AAD(p)a/% AAD(y1)b Temperature range/K

R32(1) + R161(2)
0.1122 1.227
0.4497 0.12 0.0011 283.15–323.15
R161(1) + R1234ze(E)(2)
0.01255
0.7577 0.9727 0.20 0.0014
P
a
AADðpÞ=% ¼ ð100=NÞ N i¼1 jðpexp;i
pcal;i Þ=pexp;i j:
b PN
AADðy1 Þ ¼ ð1=NÞ i¼1 jy1;exp;i
y1;cal;i j:
48 X. Meng et al. / J. Chem. Thermodynamics 118 (2018) 43–50

where sii = 0, bii = 0, bij = bji. It was recommended to use the

5
value of 0.3 for bij by Renon and Prausnitz [23].
Table 5 shows the value of k12, s12 and s21 for R32 + R161 and
4
R161 + R1234ze(E), which were regressed by minimizing the fol-

100·(pexp-pcal)/pexp
lowing objective function: 3
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
!2 ffi
u
1 XN u
p
p 2
F¼ t exp;i cal;i
þ ðy1;exp;i
y1;cal;i Þ2 ; ð13Þ
N i¼1 pexp;i 1
where N is the number of the experimental points, the sub- 0
scripts ‘‘exp” and ‘‘cal” represent the experimental and calculated
results, respectively. -1
The experimental data of this work and literatures along with
the calculated data of PRSV + WS + NRTL model are presented in
Figs. 2 and 4 for R32 + R161 and R161 + R1234ze(E), respectively. 0.04
Only one set of experimental data from Han et al. [10] for R32 +
R161 were found, while there were no literature data for R161 + 0.02
R1234ze(E). Within the studied temperature range (283.15–

y1,exp-y1,cal
323.15 K), these two binary systems both show zeotropic behavior, 0.00
similar to our previously studied systems (R32 + R1234ze(E), R32
+ R1234yf and R161 + R1234yf) [13,14]. The red dashed line in
-0.02
Figs. 2 and 4 show the p-x relation of Raoult’s law. R32 + R161 sys-
tem shows slightly positive deviation from Raoult’s law, while
R161 + R1234ze(E) system shows relatively large negative devia- -0.04
tion from Raoult’s law, which is the only one that shows negative
deviation among our studied systems. 0.0 0.2 0.4 0.6 0.8 1.0
This could also be confirmed from the sij values of PRSV + WS + x1
NRTL model. Only R161 + R1234ze(E) has a negative s12 and posi-
tive s21. All the other systems have a positive s12 and negative s21 Fig. 3. Deviations of the experimental data, pexp, and y1,exp from the calculated
(See detailed values in Table 5 of this work, Table 4 of Hu et al. [13] results of PRSV + + WS + NRTL model, pcal and y1,cal, for R32(1) + R161(2). j, 283.15
and Table 7 of Hu et al. [14]). K; s, 293.15 K; N, 303.15 K; 5, 323.15 K; r, 323.15 K. Black, this work; Red, Han
et al. [10].

2.5 1.5

2.0 313.15 K 1.2

p/MPa

313.15 K
p/MPa

1.5 0.9

293.15 K
1.0 0.6
293.15 K
0.5
0.3
3.0 2.0

2.5 323.15 K
1.5
323.15 K
p/MPa

2.0
p/MPa

1.5 303.15 K 1.0

303.15 K
1.0
283.15 K 0.5
0.5 283.15 K
0.0 0.2 0.4 0.6 0.8 1.0
x1,y1 0.0 0.2 0.4 0.6 0.8 1.0
x1,y1
Fig. 2. Vapor liquid equilibrium data for R32(1) + R161(2) from 283.15 K to 323.15
K. 4, Han et al. [10]; d, This work; —, PRSV + WS + NRTL; —, p-x relation for Raoult’s Fig. 4. Vapor liquid equilibrium data for R161(1) + R1234ze(E)(2) from 283.15 K to
law. 323.15 K. d, This work; —, PRSV + WS + NRTL; —, p-x relation for Raoult’s law.
 X. Meng et al. / J. Chem. Thermodynamics 118 (2018) 43–50 49

the Doctoral Program of Higher Education of China (No.

0.9 20130201110046).

0.6
100·(pexp-pcal)/pexp

Notes
0.3
The authors declare no competing financial interest.
0.0

-0.3 References

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5. Conclusion
This work presents new vapor liquid equilibrium data for R32 +
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JCT 17-560