J. Chem.

Thermodynamics 129 (2019) 36–43

Contents lists available at ScienceDirect

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

Thermodynamic properties of (R1234yf + R290): Isochoric pqTx and

specific heat capacity cv measurements and an equation of state
Quan Zhong a,b, Xueqiang Dong a,b,⇑, Yanxing Zhao a, Haiyang Zhang a, Jingzhou Wang a,b, Hao Guo a,
Jun Shen a,b, Maoqiong Gong a,b,⇑
a
Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

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

Article history: In this paper, isochoric pqTx and specific heat capacity cv for (R1234yf + R290) binary mixtures were
Received 27 June 2018 measured using an adiabatic batch calorimeter with intermittent heating. A total of 42 pqTx data points
Received in revised form 12 August 2018 over temperatures from (254.28 to 348.30) K and 89 isochoric specific heat capacity data points over
Accepted 13 September 2018
temperatures from (255.48 to 347.55) K were obtained for liquid (R1234yf + R290) with mole fractions
Available online 17 September 2018
of R1234yf at (0.825, 0.607, 0.521 and 0.285). The standard uncertainties were estimated to be 10 mK
for temperature, 5 kPa for pressure, 0.3% for density and 1.0% for isochoric specific heat capacity. The
Keywords:
experimental pqTx data were correlated by an empirical Tait equation with average absolute relative
Adiabatic calorimeter
Compressed liquid density
deviation of 0.19%. A Helmholtz energy equation of state based on the multi-fluid approximations model
Isochoric heat capacity was developed for (R1234yf + R290) using the present and available experimental data. Eleven mixture
(R1234yf + R290) rules are employed and the optimal Helmholtz energy equation of state calculates the density, VLE
Equation of state and isochoric specific heat capacity properties with sufficient accuracy. The compressed liquid density
and isochoric specific heat capacity data in this work are well represented with average absolute relative
deviation of 0.21% and 0.66%, respectively.
Ó 2018 Elsevier Ltd.

1. Introduction gaseous density at temperatures from (268.15 to 363.15) K by

In recent years, with global warming and ozone depletion, look-
ing for alternative refrigerants that are efficient and environmen-
tally friendly is of much significance. The positive azeotrope
(R1234yf + R290) mixtures [1] is a potential alternative refrigerant
for its zero ozone depletion potential, ultra-low global warming
potential, lower flammability than pure R290 and much better vol-
umetric refrigeration capacity than pure R1234yf. Knowledge of
reliable thermophysical property of refrigerant is essential for eval-
uating the performance in the refrigeration cycle. In our previous
work, we measured the gaseous pressure-density-temperature-m
ole fraction (pqTx) property from (265.546 to 300.268) K [2] and
saturated liquid pqTx property from (255.048 to 300.135) K [3]
for (R1234yf + R290) mixtures using a compact single-sinker den-
simeter. Additional, we studied the vapour–liquid equilibrium
(VLE) property [1] from (253.150 to 293.150) K using an apparatus
based on the recirculation method. Brown et al. [4] obtained its
⇑ Corresponding authors at: Key Laboratory of Cryogenics, Technical Institute of
Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
E-mail addresses: dxq@mail.ipc.ac.cn (X. Dong), gongmq@mail.ipc.ac.cn
(M. Gong).
the constant-volume method.
Among the above studies, truncated virial equation of state
(EOS), PR-VDW model (Peng-Robinson EOS [5] combined Van der
Waals [6] mixing rule) and PT-VDW (Patel-Teja EOS [7] model
combined Van der Waals mixing rule) were used to correlate the
gaseous density data [2,4], empirical VDNS [8] and modified Rack-
ett [9,10] equations were applied to fit the liquid density data [3],
and PR-VDW model and PR-HV-NRTL model (PR EOS with non-
random two liquids [11] activity coefficient model involving
Huron–Vidal [12] mixing rule) were used to present the VLE data
[1]. However, these equations are not accurate enough to present
the experimental data of many different properties simultane-
ously. The virial EOS is only suitable for gaseous state and the cubic
EOSs are hard to describe liquid properties.
This work measured the isochoric pqTx and specific heat capac-
ity cv of compressed liquid (R1234yf + R290) mixtures. The pqTx
data were obtained at temperatures from (254.28 to 348.30) K
and the cv data were obtained at temperatures from (255.48 to
347.55) K with mole fractions of R1234yf at (0.825, 0.607, 0.521
and 0.285). What’s more, a Helmholtz energy EOS based on the
multi-fluid approximations model was developed for (R1234yf

https://doi.org/10.1016/j.jct.2018.09.009
0021-9614/Ó 2018 Elsevier Ltd.
 Q. Zhong et al. / J. Chem. Thermodynamics 129 (2019) 36–43 37

+ R290) using the present and available experimental data. The

Helmholtz energy EOS calculates the density, VLE and isochoric
specific heat capacity properties with sufficient accuracy for tech-
nical applications.

2. Experimental

2.1. Chemicals

Table 1 contains the critical temperatures, critical pressures,

critical densities and acentric factors for the measured samples of
R1234yf [13] and R290 [14]. R1234yf was supplied by Honeywell
with a stated mole fraction purity of no less than 0.999, while
R290 was supplied by Beijing AP BAIF Gases Industry Co. Ltd. with Fig. 1. Schematic diagram of the experimental system: 1, refrigerating machine; 2,
a claimed mole fraction purity of no less than 0.999. All the scale; 3, gas cylinder; 4–6, vacuum pump; 7, DC power system; 8, multimeter; 9,
samples were used without further purification. pressure transducer; 10, computer; 11, outer adiabatic shield; 12, inner adiabatic
shield; 13, bomb; 14, thermometer.

2.2. Experimental apparatus and uncertainty

As shown in Fig. 1, the adiabatic batch calorimeter that was
used for these measurements has been described in our previous
work [15] and the accuracy was verified by measuring the liquid
cv of propane at temperatures from (236.31 to 339.76) K, it is only
briefly introduced here. The sample heat capacity is decided by:
cv ¼ ðQ  Q 0  W pv Þ=ðmDTÞ
where Q is the electric energy supplied to the sample bomb, Q0 is
the heat applied to the empty bomb, Wpv is the change-of-volume
work due to the slight dilation of the cell, m is the mass of sample,
and DT is the temperature rise during a heating process. In this
work, the compressed liquid density is obtained by:
q ¼ m=V bomb
where m is the mass of sample, Vbomb is the bomb volume and cal-
ibrated as a function of both temperature and pressure with the
uncertainty of 0.1 cm3 in our previous work [15]:
h i
V bomb ¼ 1:53  103 ðT  273:15Þ þ 71:80  ð1 þ ð2:80  104 ÞpÞ
The temperature was measured by a 25 X standard platinum
resistance thermometer (SPRT) with an uncertainty of 4 mK. An
81/2 multimeter (KEITHLEY 2002) was used to acquire the temper-
ature and the overall standard uncertainty of temperature was
estimated to be 10 mK. A Mensor CPT6010 digital pressure trans-
ducer (DPT) with a stated accuracy of 0.02% was used to measure
the pressure, and the range of 20 MPa was used in this experiment.
The overall standard uncertainty of pressure was estimated to be
5 kPa. The tested samples were filled by gravimetrically with a
10 mg resolution and the standard uncertainties in mole fraction
were estimated to be less than 0.002. Considering the uncertainties
from the mass, calibrated volume and mole fraction, the standard
uncertainty for the density was estimated to be 0.30%.
As for the specific heat capacity, the heat applied to the bomb
was supplied by a KEITHLEY 2230G-30–1 DC Power Supply and
the uncertainty in heat energy was estimated to be less than
0.15%. An empirical compressed liquid density equation was devel-
oped according the density measured above and the mass m in Eq.
(1) was calculated by the calibrated volume and the density values
derived by the empirical equation. The uncertainty for the m was
estimated to be less than 0.40%, including the uncertainties from
the calculated density and the volume. The derivative quantity in
Wpv calculation was also derived by the developed compressed liq-
ð1Þ uid density equation. The uncertainty was estimated to be less
than 0.40% as a consequence of the deviation of the calculated
pressure derivative and the uncertainty of the volume change. By
combining the various sources of experimental uncertainty, the
standard uncertainty in heat capacity is calculated to be less than
1.0%.
ð2Þ 3. Experimental results and discussion
3.1. Compressed liquid density and isochoric specific heat capacity
results
Compressed liquid density data for (R1234yf + R290) binary
mixtures are presented at temperatures ranging from (254.28 to
ð3Þ 348.30) K with mole fractions of R1234yf from (0.285 to 0.825).
The experimental results are listed in Table 2.
The Tait equation [16] was used to correlated the density data,
it has the following form:
  
Bþp
q  1 ¼ qs  1 1  C ln ð4Þ
B þ ps
with B given by Eq. (5). The saturation pressure ps and saturation
density qs were calculated from the developed PR-vdW model
and modified Rackett equation for (R1234yf + R290) mixtures in
reference [3], respectively.
B ¼ pc ½1 þ að1  T r Þ1=3 þ bð1  T r Þ2=3 þ dð1  T r Þ þ eð1  T r Þ4=3 
ð5Þ
T r ¼ T=T cm ð6Þ

Table 1
Information of the two samples used in this work.a

Materials CAS no. Mole fractionb Tc/K pc/MPa q/kgm3 x

c
R1234yf 754-12-1 >0.999 367.85 3.382 475.55 0.276
R290d 74-98-6 >0.999 369.89 4.251 220.48 0.152
a
Tc, pc and x were taken from reference [13] for R1234yf and reference [14] for R290.
b
As stated by the supplier, and used without further purification.
c
2,3,3,3-tetrafluoroprop-1-ene, supplied by Honeywell.
d
Propane, supplied by Beijing AP BAIF Gases Industry Co. Ltd.
38 Q. Zhong et al. / J. Chem. Thermodynamics 129 (2019) 36–43

Table 2
Values measured for the density of compressed liquid R1234yf (1) + R290 (2) at temperatures from (254.28 to 348.30) K and pressures up to 14.239 MPa.a

T/K p/MPa q/kgm3 x1 T/K p/MPa q/kgm3 x1

255.92 1.645 1109.8 0.825 301.86 7.296 819.7 0.521
258.25 3.241 1109.2 0.825 304.23 8.438 819.4 0.521
260.61 4.872 1108.7 0.825 306.62 9.582 819.1 0.521
262.96 6.492 1108.1 0.825 309.04 10.744 818.8 0.521
265.27 8.092 1107.6 0.825 311.50 11.920 818.5 0.521
267.59 9.690 1107.0 0.825 313.86 13.057 818.2 0.521
269.90 11.286 1106.5 0.825 313.73 1.699 626.0 0.285
272.22 12.888 1105.9 0.825 316.16 2.581 625.9 0.285
254.28 1.867 969.9 0.607 318.63 3.477 625.7 0.285
256.67 3.513 969.4 0.607 321.06 4.361 625.5 0.285
259.05 5.156 968.9 0.607 323.51 5.252 625.3 0.285
261.41 6.787 968.5 0.607 326.04 6.172 625.1 0.285
263.78 8.419 968.0 0.607 328.54 7.079 624.9 0.285
266.11 10.027 967.5 0.607 331.04 7.988 624.7 0.285
268.42 11.618 967.0 0.607 333.51 8.883 624.5 0.285
270.72 13.214 966.5 0.607 336.01 9.790 624.3 0.285
290.26 1.730 821.2 0.521 338.48 10.686 624.1 0.285
292.50 2.803 820.9 0.521 340.94 11.578 624.0 0.285
294.78 3.896 820.6 0.521 343.40 12.468 623.8 0.285
297.13 5.024 820.3 0.521 345.88 13.366 623.6 0.285
299.47 6.148 820.0 0.521 348.30 14.239 623.4 0.285
a
Standard uncertainties u are u(T) = 10 mK, u(p) = 5 kPa, u(x) = 0.002, u(q) = 0.3%.

The critical parameters of the mixtures were evaluated by the 0.7

following mixing rules [16]: 0.6
XX 0.5
T cm ¼ xi xj v c;ij T c;ij =v cm ð7Þ
i j
0.4
exp

0.3
)/

( ! !) 0.2
exp

1 X X X
v cm ¼ xi v c;i þ 3 xi v c;i
2=3
xi v c;i
1=3
ð8Þ 0.1
- cal

4 i i i 0.0
100·(

-0.1
 1=2
v c;ij T c;ij ¼ v c;i T c;i v c;j T c;j ð9Þ -0.2
-0.3
pcm ¼ ð0:291  0:080wm ÞRT cm =v cm ð10Þ -0.4
-0.5
X 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
wm ¼ xi wi ð11Þ p/MPa
i
Fig. 2. Relative density deviations of the present data with values calculated from
where vc,i, Tc,i and Mi stand for critical mole volume (cm3mol1), the Tait equation for R1234yf (1) + R290 (2) system: d, x1 = 0.285; ▲, x1 = 0.521; ◆,
critical temperature (K) and mole mass (gmol1) of the correspond- x1 = 0.607; j, x1 = 0.825.
ing component i, respectively.
!2
X
N
qcal  qexp
O:F ¼ ð12Þ 3.2. Helmholtz equation of state
i¼1
qexp i
The multi-fluid approximations model was used to develop the
Objective function in Eq. (12) was used to obtain the constants
Helmholtz energy EOS in this work. A Helmholtz energy EOS for
based on the present liquid density data. The optimized values are
R290 + R134a [17] has been developed in our previous work, only
presented in Table 3 and the relative deviations of the present liq-
brief introduction was provided here. The dimensionless form of
uid density with Eq. (4) are shown in Fig. 2. The average absolute
Helmholtz energy can be expressed as:
relative deviation (AARD) and maximum absolute relative devia-
tion (MARD) for compressed liquid density are 0.19% and 0.64%, aðd; s; xÞ ¼ a0 ðq; T; xÞ þ ar ðd; s; xÞ ð13Þ
respectively.
Measurements on (R1234yf + R290) were carried out at temper- X
N
atures from (255.48 to 347.55) K and pressures up to 13.803 MPa. ao ðq; T; xÞ ¼ xi ½aoi ðq; TÞ þ lnxi  ð14Þ
The experimental data are listed in Table 4. i¼1

X
N
ar ðd; s; xÞ ¼ xi ari ðd; sÞ þ Dar ðd; s; xÞ ð15Þ
Table 3
i¼1
Constants for Eqs. (4) and (5).

Coefficient C a b d e where a0 (q, T, x) and ar (d, s, x) are the ideal-gas part and residual
part of the reduced Helmholtz energy for the mixture, respectively.
Value 0.12269 47.0005 274.1677 534.9952 294.6285
ai0 (q, T) is the ideal-gas part and air (d, s) is the residual part of
 Q. Zhong et al. / J. Chem. Thermodynamics 129 (2019) 36–43 39

Table 4
Values measured for the isochoric specific heat capacity of compressed liquid R1234yf (1) + R290 (2) at temperatures from (255.48 to 347.55) K and pressures up to 13.803 MPa.a

T/K p/MPa qb/kgm3 x1 cv/kJkg1K1 ur(cv)/%

257.09 2.443 1109.1 0.825 0.879 0.94
259.43 4.057 1109.4 0.825 0.879 0.94
261.79 5.682 1109.6 0.825 0.888 0.94
264.12 7.292 1109.8 0.825 0.892 0.95
266.43 8.891 1110.0 0.825 0.886 0.95
268.75 10.488 1110.1 0.825 0.899 0.95
271.06 12.087 1110.2 0.825 0.896 0.95
275.52 2.097 1057.3 0.825 0.914 0.95
277.84 3.440 1057.0 0.825 0.922 0.94
280.20 4.817 1056.7 0.825 0.930 0.93
282.57 6.197 1056.5 0.825 0.938 0.94
284.92 7.561 1056.2 0.825 0.935 0.94
287.24 8.908 1056.0 0.825 0.940 0.95
289.57 10.249 1055.7 0.825 0.944 0.94
291.90 11.593 1055.6 0.825 0.956 0.94
295.93 1.917 994.3 0.825 0.951 0.94
298.32 3.042 993.5 0.825 0.960 0.92
300.77 4.193 992.8 0.825 0.959 0.92
303.23 5.349 992.2 0.825 0.958 0.92
305.69 6.504 991.8 0.825 0.975 0.92
308.14 7.659 991.5 0.825 0.970 0.92
310.60 8.808 991.4 0.825 0.989 0.92
313.06 9.957 991.6 0.825 0.988 0.91
315.53 11.107 992.0 0.825 1.005 0.92
319.49 2.066 911.8 0.825 1.004 0.90
322.06 2.960 910.5 0.825 1.012 0.90
324.62 3.854 909.7 0.825 1.025 0.90
327.17 4.744 909.4 0.825 1.033 0.90
329.73 5.637 909.5 0.825 1.040 0.90
332.30 6.534 910.0 0.825 1.041 0.90
334.85 7.427 911.0 0.825 1.044 0.90
337.40 8.319 912.1 0.825 1.050 0.90
339.94 9.209 913.3 0.825 1.048 0.91
342.47 10.092 914.0 0.825 1.050 0.90
345.02 10.985 913.6 0.825 1.053 0.90
347.55 11.870 911.0 0.825 1.045 0.91
255.48 2.690 965.8 0.607 0.945 0.93
257.86 4.335 965.7 0.607 0.953 0.93
260.23 5.972 965.6 0.607 0.958 0.94
262.60 7.603 965.4 0.607 0.956 0.94
264.95 9.223 965.3 0.607 0.969 0.94
267.27 10.823 965.0 0.607 0.966 0.95
269.57 12.416 964.8 0.607 0.980 0.95
276.02 1.993 914.6 0.607 1.012 0.94
278.37 3.320 913.9 0.607 1.006 0.94
280.75 4.661 913.2 0.607 1.022 0.93
283.13 6.012 912.6 0.607 1.018 0.93
285.51 7.357 912.0 0.607 1.023 0.93
287.89 8.694 911.4 0.607 1.027 0.94
290.27 10.038 910.8 0.607 1.030 0.93
292.66 11.390 910.4 0.607 1.030 0.93
295.03 12.722 909.9 0.607 1.033 0.94
302.78 1.793 841.0 0.607 1.057 0.92
305.28 2.835 839.6 0.607 1.061 0.90
307.82 3.898 838.3 0.607 1.056 0.90
310.37 4.961 837.2 0.607 1.067 0.90
312.91 6.022 836.3 0.607 1.080 0.90
315.46 7.086 835.6 0.607 1.084 0.90
318.01 8.150 835.2 0.607 1.092 0.90
320.54 9.207 835.1 0.607 1.104 0.91
323.08 10.263 835.3 0.607 1.112 0.90
325.63 11.326 835.9 0.607 1.117 0.90
317.06 2.127 751.5 0.521 1.162 0.96
319.60 2.994 749.7 0.521 1.167 0.95
322.15 3.867 748.2 0.521 1.168 0.94
324.70 4.739 747.0 0.521 1.174 0.94
327.23 5.608 746.1 0.521 1.183 0.93
329.76 6.474 745.6 0.521 1.185 0.93
332.30 7.345 745.4 0.521 1.177 0.93
334.85 8.221 745.6 0.521 1.191 0.92
337.40 9.098 746.0 0.521 1.196 0.92
339.93 9.963 746.3 0.521 1.195 0.94
342.44 10.822 746.4 0.521 1.196 0.91
344.94 11.680 745.7 0.521 1.199 0.90

(continued on next page)

40 Q. Zhong et al. / J. Chem. Thermodynamics 129 (2019) 36–43

Table 4 (continued)

T/K p/MPa qb/kgm3 x1 cv/kJkg1K1 ur(cv)/%

347.44 12.532 743.6 0.521 1.203 0.90
314.95 2.140 629.2 0.285 1.321 0.90
317.40 3.029 627.8 0.285 1.335 0.91
319.85 3.919 626.5 0.285 1.353 0.90
322.29 4.807 625.4 0.285 1.361 0.90
324.78 5.712 624.6 0.285 1.366 0.90
327.29 6.626 624.0 0.285 1.370 0.90
329.79 7.534 623.7 0.285 1.367 0.91
332.28 8.436 623.6 0.285 1.374 0.91
334.76 9.337 623.8 0.285 1.380 0.91
337.25 10.238 624.2 0.285 1.387 0.91
339.71 11.132 624.6 0.285 1.388 0.92
342.17 12.023 624.9 0.285 1.391 0.92
344.64 12.917 624.7 0.285 1.393 0.92
347.09 13.803 623.4 0.285 1.395 0.92
a
Standard uncertainties u are u(T) = 10 mK, u(p) = 5 kPa, u(x) = 0.002, ur(cv) = 100u(cv)/cv %.
b
The values of density q are calculated from the developed Tait equation.

component i and they were taken from reference [13] for R1234yf where Fij is constant binary interaction parameters for the ij binary
and reference [14] for R290 in this work. T, q and x is the temper- pair, aijr is a binary specific or generalized departure function. To
ature (K), mole density (molcm3) and the vector of the mole com- find a good description for the thermophysical properties of
position (x1, x2, . . ., xn), respectively. Dar is departure function of (R1234yf + R290) mixtures, eleven binary specific or generalized
multi-component mixtures, which used to describe the behaviour departure functions combined with KW reducing functions were
of non-ideal mixtures. d and s are reduced mixtures density and used to present the available data. Table 5 shows experimental data
inverse mixtures temperature according to: of (R1234yf + R290) mixtures in available studies and Fig. 3 shows
q the distribution on temperature–pressure plane. The five binary
d¼ ð16Þ parameters (bT,12, cT,12, bv,12, cv,12 and F12) were determined using
qr ðxÞ
the Levenberg-Marquardt algorithm [20] by minimizing the follow-
T r ðxÞ ing object function:
s¼ ð17Þ
 2   2 2
T P pb;cal pb;exp P P
pd;cal pd;exp
p p
v2 ¼ N1pb W pb pb;exp
þ N1 þ N1pg W pg g;calpg;expg;exp
W pd pd;exp
where qr(x) and Tr(x) are reducing functions for density and tem-  2 
pd
2  2
P p p P q q P q q
perature, respectively. þ N1 W pl l;calp l;exp þ N1 W qcal sl;calq sl;exp þ N1qg W pg g;calq g;exp
pl l;exp qsl sl;exp g;cal
The combination of reducing functions with departure function P  2 P  2
q q c
W cv v ;calcv ;expv ;exp
c
is defined as the mixing rule for the Helmholtz energy EOS. KW þ N1 W pl l;calq l;exp þ N1c
pl 1;exp v

reducing functions [18,19] are used and can be expressed as the ð26Þ
following form:
where N is the number of experimental data points; Subscripts b, d,
X
N X
N
xi þ xj g, l, sl, v, cal and exp stand for bubble point, dew point, gaseous, liq-
T r ðxÞ ¼ xi xj bT;ij cT;ij   T c;ij ð18Þ
i¼1 j¼1 b2T;ij xi þ xj uid, saturated liquid, constant volume, calculated value and exper-
imental value, respectively. W is the corresponding weighting
X
N X N coefficients, which were determined by the type, experimental
1 xi þ xj 1
¼ xxb c   ð19Þ region and uncertainty [21,22]. In the present work, typical values
qr ðxÞ i¼1 j¼1 i j v ;ij v ;ij b2v ;ij xi þ xj qc;ij for W were 5 for the bubble point pressure, 0.5 for the dew point
pressure, 10 for gas densities, 5 for liquid densities, 2 for the iso-
 0:5
T c;ij ¼ T c;i  T c;j ð20Þ choric specific heat capacity.
Table 6 lists the binary parameters and the objective function
!3 values for the eleven KW mixing rules. The Helmholtz energy
1 1 1 1
¼ þ ð21Þ equation combined with KW4 mixing rule gives the best descrip-
qc;ij 8 q1=3 q1=3
c;i c;j tion of the experimental data and the fitted parameters are used
in subsequent calculations. The detailed AARDs for different prop-
bT;ii ¼ cT;ii ¼ bv ;ii ¼ cv ;ii ¼ 1 ð22Þ erties of different sources are shown in Table 7.
Fig. 4 shows the VLE plot of pressure against mole fraction from
cT;ji ¼ cT;ij ; cv ;ji ¼ cv ;ij ð23Þ the mixture model and experimental data [1] at temperatures from
(253.150 to 293.150) K. Good consistency can be found between
bT;ji ¼ 1=bT;ij ; bv ;ji ¼ 1=bv ;ij ð24Þ the calculated values from the developed equation and the exper-
imental data. Positive azeotropic behaviour can be observed and
where bT,12, cT,12, bv,12 and cv,12 are constant binary interaction the azeotropic fractions and pressures of the mixtures have been
parameters. The critical temperatures Tc,ii and densities qc,ii for listed in Table 8. Fig. 5 shows the relative deviations of experimen-
R1234yf and R290 are provided in Table 1. tal data [1,3] for bubble and dew point pressures from the present
The departure function Dar of multi-component mixtures is Helmholtz equation. The experimental bubble point pressures
given by: from Zhong et al. [1], dew point pressures from Zhong et al. [1],
X
N 1 X
N and bubble point pressures from Zhong et al. [3] are presented
Dar ðd; s; xÞ ¼ xi xj F ij arij ðd; sÞ ð25Þ with AARDs of 0.43%, 0.39%, and 0.40%, respectively. Deviations
i¼1 j¼iþ1 in the experimental gaseous densities by Zhong et al. [2] and
 Q. Zhong et al. / J. Chem. Thermodynamics 129 (2019) 36–43 41

Table 5
A summary of properties of R1234yf (1) + R290 (2) mixtures in available studies.

Author Properties State Data points Ranges

T/K p/MPa x1
Brown et al. [4] pqTx GAS 86a 268.15–363.15 0.3330–1.0396 0.291–0.770
Zhong et al. [2] pqTx GAS 136 265.546–300.268 0.1015–0.7025 0.0906–0.8116
Zhong et al. [1] Tpxy VLE 45 253.150–293.150 0.1911–0.9121 0.113–0.896
Zhong et al. [3] pqTx VLE 50 255.048–300.135 0.2827–1.0519 0.113–0.625
This paper pqTx LIQUID 42 254.28–348.30 1.645–14.239 0.285–0.825
This paper pTxcv LIQUID 89 255.48–347.55 1.793–13.803 0.285–0.825
a
14 data points were not used in the Helmholtz equation fit.

15
14
13 0.9
12
11 0.8
10 0.7
9
8 0.6
p/MPa

p/MPa
6 0.5
5
4 0.4
3
0.3
2
1 0.2
0
240 260 280 300 320 340 360 380 0.1
T/K 0.0 0.2 0.4 0.6 0.8 1.0
x1
Fig. 3. Distribution of experimental data for (R1234yf + R290) binary system on
temperature-pressure plane: , Brown et al. [4]; , Zhong et al. [2]; , Zhong et al. Fig. 4. Calculation of isothermal bubble point and dew point curves for R1234yf (1)
[1]; , Zhong et al. [3]; , , this work; red solid line, saturation curve of R1234yf + R290 (2) at five temperatures. Experimental data [1]: (◆, e), T = 253.150 K; (.,
[13]; black solid line, saturation curve of R290 [14]; q, critical point of R1234yf; , 5), T = 263.150 K; (▲, 4), T = 273.150 K; (d, s) T = 283.150 K ; (j, h),
critical point of R290. (For interpretation of the references to colour in this figure T = 293.150 K. Symbol interior: solid, liquid phase; hollow, vapor phase. Solid lines
legend, the reader is referred to the web version of this article.) represent calculated curves with the developed equation.

Table 6
Binary parameters and objective function values for R1234yf (1) + R290 (2).

Mixing rules bT,12 cT,12 bv,12 cv,12 F12 v2

KW0 (hydrocarbon mixtures)a 0.99372491 0.93684503 0.98322649 1.01090479 0.03993208 0.00319
KW1 (Methane + Ethane)a 0.99372570 0.93657222 0.98320313 1.01106787 0.09705849 0.00320
KW2 (Methane + Propane)a 0.99389730 0.93619181 0.98243133 1.01150539 0.00981130 0.00320
KW3 (Methane + Nitrogen)a 0.99392448 0.93649798 0.98247059 1.01126931 0.04785194 0.00320
KW4 (Methane + Carbon dioxide)a 0.99454023 0.94248028 0.98050260 1.00507834 0.34943843 0.00285
KW5 (Nitrogen + Carbon dioxide)a 0.99404508 0.93675333 0.98192989 1.01172522 0.03158267 0.00320
KW6 (Nitrogen + Ethane)a 0.99380237 0.93620660 0.98279378 1.01150007 0.01899386 0.00320
KW7 (Methane + Hydrogen)a 0.99384971 0.93348781 0.98173915 1.01403954 0.04114683 0.00320
KWR (R32 + R125)b 0.99108892 0.88545062 0.97994847 1.01631778 0.86494654 0.00288
KWS (R32 + R134a)b 0.99347713 0.92196057 0.97953819 1.00844621 0.86757732 0.00304
KWT (R-125 + R134a, R-125 + R143a, R-134a + R143a, R-134a + R152a)b 0.99381911 0.93614897 0.98279154 1.01155861 0.14099640 0.00320
a
Taken from Kunz et al. [18].
b
Taken from Lemmon et al. [23].

Table 7
AARD of property X for different experimental data from the present Helmholtz equation.a

Author AARDpg AARDqg AARDpb AARDpd AARDqs AARDpl AARDql AARDcv

% % % % % % % %
Brown et al. [4] 1.12 1.21
Zhong et al. [2] 0.14 0.15
Zhong et al. [1] 0.43 0.39
Zhong et al. [3] 0.40 0.39
This paper 5.01 0.21 0.66
a
Subscripts b, d, g, l, sl, v, cal and exp stand for bubble point, dew point, gaseous, liquid, saturated liquid, constant volume, calculated value and experimental value,
respectively.
42 Q. Zhong et al. / J. Chem. Thermodynamics 129 (2019) 36–43

Table 8 2.0
The calculated azeotropic fractions and pressures for R1234yf (1) + R290 (2) at
temperatures from (253.150 to 293.150) K. 1.5
T/K x1,az paz/MPa
1.0
253.150 0.269 0.2670

100·(cvcal-cvexp)/cvexp
263.150 0.273 0.3762
0.5
273.150 0.278 0.5160
283.150 0.283 0.6915
0.0
293.150 0.289 0.9079

-0.5

-1.0
1.5
-1.5

1.0 -2.0
250 260 270 280 290 300 310 320 330 340 350
T/K
100·(pcal-pexp)/pexp

0.5
Fig. 7. Relative deviations of experimental data for isochoric specific heat capacity
from the present Helmholtz equation in this work.
0.0
energy equation can present the experimental data of different
-0.5 properties with reasonable precision simultaneously.

4. Conclusions
-1.0
250 260 270 280 290 300
In this work, isochoric pqTx and specific heat capacity cv for
T/K
(R1234yf + R290) binary mixtures were experimentally deter-
Fig. 5. Relative deviations of experimental data for bubble and dew point pressures mined by an adiabatic batch calorimeter. The compressed liquid
from the present Helmholtz equation: j, bubble point pressures from Zhong et al. density data were measured at temperatures ranging from
[1]; h, dew point pressures from Zhong et al. [1]; d, bubble point pressures from (254.28 to 348.30) K and pressures up to 14.239 MPa, while the
Zhong et al. [3].
isochoric specific heat capacity data were obtained at tempera-
tures from (255.48 to 347.55) K and pressures up to 13.803 MPa.
The compressed liquid density data, isochoric specific heat capac-
1.0 ity data and currently available experimental data for (R1234yf
+ R290) mixtures were used to developed the Helmholtz energy
EOS. Eleven mixture models are compared and the optimal Helm-
0.5
holtz model gives good description of the density, VLE and iso-
choric specific heat capacity properties. It is expected that the
0.0
exp

developed Helmholtz model will be useful for engineering

calculations.
)/ exp

-0.5
- cal

Acknowledgement
100·(

-1.0
-1.5
-2.0
250 260 270 280 290 300 310 320 330 340 350 360 370
T/K
Fig. 6. Relative deviations of experimental data for densities from the present
Helmholtz equation: +, gaseous densities from Zhong et al. [2]; s, gaseous densities
from Brown et al. [4]; j, saturated liquid densities from Zhong et al. [3]; w,
compressed liquid densities of this work.
Brown et al. [4], saturated liquid densities by Zhong et al. [3], and
compressed liquid densities in this work are shown in Fig. 6. It can
be seen that the gaseous densities deviations of Brown et al. [4] are
larger than that of Zhong et al. [2], mainly because it have a relative
larger experimental uncertainty. Fig. 7 shows the relative devia-
tions of experimental data for isochoric specific heat capacity in
this work from the present Helmholtz equation. The AARD and
MARD for isochoric specific heat capacity data are 0.66% and
1.85%, respectively. As described above, the developed Helmholtz
The supports provided by the National Natural Science Founda-
tion of China (Grant No. 51676200), Beijing Nova Program (Grant
No. Z181100006218022) and Beijing Natural Science Foundation
(Grant No. 3171002) for the completion of the present work are
gratefully acknowledged.
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JCT 2018-544