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J. Chem. Thermodynamics
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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.
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
2. Experimental
2.1. Chemicals
Table 1
Information of the two samples used in this work.a
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
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
Table 4 (continued)
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.
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).
Table 7
AARD of property X for different experimental data from the present Helmholtz equation.a
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
-0.5
- cal
Acknowledgement
100·(
-1.0
The supports provided by the National Natural Science Founda-
tion of China (Grant No. 51676200), Beijing Nova Program (Grant
-1.5
No. Z181100006218022) and Beijing Natural Science Foundation
(Grant No. 3171002) for the completion of the present work are
-2.0 gratefully acknowledged.
250 260 270 280 290 300 310 320 330 340 350 360 370
T/K
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