VaporâLiquid Equilibria for the Binary and Ternary Systems of

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Vapor−Liquid Equilibria for the Binary and Ternary Systems of Difluoromethane (R32), 1,1-Difluoroethane (R152a), and 2,3,3,3Tetrafluoroprop-1-ene (R1234yf) Tao Yang, Xiaozhen Hu, Xianyang Meng, and Jiangtao Wu* Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, Xi’an Jiaotong University, Xi’an, 710049, China ABSTRACT: The combination of difluoromethane (R32), 1,1-difluoroethane (R152a), and 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) could be a potential substitute for hydrofluorocarbon refrigerants. Reliable vapor liquid equilibrium (VLE) data are important thermodynamic data in evaluating the performance of refrigeration cycles and determining their optimal compositions. In this work, we measured the VLE data for binary mixtures of R32 + R152a and R152a + R1234yf, and ternary system of R32 + R152a + R1234yf. The measurements were carried out by using the AnTLcirCapValVis analytical method over the temperature range from 283.15 to 323.15 K. The standard uncertainties of temperature, pressure, and mole fractions are 10 mK, 0.5 kPa, and 0.005, respectively. The Peng−Robinson−Stryjek−Vera equation of state combined with the Wong−Sandler mixing rule and the nonrandom two-liquid activity coefficient model was employed to correlate the parameters of binary mixtures and predict the ternary VLE property. The predicted VLE data and K-value for the ternary system show good agreement with the experimental results. and 323.15 K. Hu et al.12 obtained the isothermal vapor liquid equilibrium data for R1234yf + R152a at temperatures from 283.15 to 323.15 K using a recirculation apparatus. While for R32 + R1234yf, our group measured the isothermal VLE data and correlated the binary parameters by the Peng−Robinson− Stryjek−Vera + Wong−Sandler + nonrandom two-liquid (PRSV + WS + NRTL) model.13 However, for the ternary mixture of R32 + R152a + R1234yf, no literature reports the vapor liquid equilibrium data. The isothermal vapor liquid equilibrium measurements for binary system of R32 + R152a and R152a + R1234yf, and the ternary system of R32 + R152a + R1234yf were conducted at five different temperatures (283.15, 293.15, 303.15, 313.15 and 323.15 K) by an AnTLcirCapValVis analytical apparatus.16 The widely used PRSV + WS + NRTL model for vapor liquid equilibrium calculations in literature was used to correlate the parameters of binary mixtures and predict the ternary VLE property,17 and the K-value, one of the distribution coefficients, was proformed to analyze the VLE data.18

1. INTRODUCTION 2,3,3,3-Tetrafluoroprop-1-ene (R1234yf, CH2CFCF3, ozone depletion potential (ODP) = 0, GWP100 years = 4),1 with similar thermodynamic properties to R134a,2−5 has been widely regarded as one of the most suitable commercial alternative refrigerants. Owing to its good performance, there are many researchers who focus their interests on it. However, based on their findings, R1234yf is still not an ideal commercial candidate at every aspect, which is due to its flammability, lower evaporation, and smaller latent heat in comparison with R134a and R410 in series tests.5,6 One of the approaches to resolve this drawback is to blend with other refrigerants, such as R32, R134a, or R125, to obtain larger latent heat and higher COP.7,8 Difluoromethane (R32, CH2F2, ODP = 0, GWP100 years = 677),1 one of the most interesting components in mixtures of R1234yf,8 has superior thermodynamic properties and large latent heat. 1,1-Difluoroethane (R152a, CH3CHF2, ODP = 0, GWP100 years = 138)1 also has been considered as another highefficient alternative refrigerant, to replace R134a in domestic refrigerators.9 In addition, the ternary system of R32 + R152a + R1234yf would be developed as a replacement for R134a in heat transfer compositions for stationary refrigeration and air conditioning equipment. It is expected that such mixtures can meet the requirements of high cycle efficiency and environmental compatibility. In recent years, many researchers have conducted experiments on phase equilibrium properties for alternative refrigerant mixtures, containing R32, R152a, and R1234yf.10−15 As for R32 + R152a binary mixture, the only available reference is from Lee et al.,10 who measured the VLE data of R32 + R152a by a circulation-type apparatus at 303.15 © XXXX American Chemical Society

2. EXPERIMENTAL SECTION 2.1. Chemicals. All compounds were purchased from commercial sources. R32, R152a, and R1234yf were supplied by Zhejiang Lantian Environmental Protection Fluoro Material Co., Ltd., Dupont Trading (Shanghai) Co. Ltd., and Honeywell International Inc., respectively. Prior to the measurements, the freeze−pump−thaw cycles were applied to eliminate any noncondensable components in each sample. The gas Received: November 1, 2017 Accepted: February 1, 2018

A

DOI: 10.1021/acs.jced.7b00950 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Specification of the Samplea

a

chemical name

CAS no.

source

stated mass purity

GC area fraction

Tc/K

pc/MPa

ω

R32 R152a R1234yf

75-10-5 75-37-6 754-12-1

Lantian Dupont Honeywell

>0.998 >0.999 >0.995

>0.9993 >0.9995 >0.9995

351.26 386.41 367.85

5.782 4.5168 3.3822

0.2769 0.2752 0.276

The critical properties were obtained from NIST Refprop V9.1.19

Table 2. Experimental Vapor Pressure Data pexp, Calculated Vapor Pressure Data pcal, and Relative Deviations of Results δp over the Temperature T Range from 283.15 to 323.15 Ka

chromatograph analysis indicated that all of the sample area purities were higher than 0.9993. Table 1 lists the suppliers, purities, critical properties, and acentric factors of the studied compounds. 2.2. Apparatus. In this work, the vapor liquid equilibrium data were obtained by an AnTLcirCapValVis analytical apparatus which was already introduced in our previous work.13,20−22 Only a brief description of the experimental setup is given here. The temperature was measured by a 25 Ω standard platinum resistance (SPRT; model 5683, Fluke) connected to a precision thermometer (model F500, ASL). The standard temperature uncertainty is 10 mK. The equilibrium pressure was measured by a quartz-crystal pressure transducer (0−6.9 MPa, model 31K-101, Paroscientific) combined with a differential pressure transmitter (−60−60 kPa, model Rosemount 3051CD, Emerson). The standard uncertainty of pressure is 0.5 kPa. The sample was then analyzed by a gas chromatograph (model 7820A, Agilent) with a thermal conductivity detector (TCD) and a capillary column (GS-GasPro, 60 m × 0.32 mm). The GC was calibrated with the mixtures of known mole fraction of components (0.1 mg/220 g, model XS205, Mettler Toledo) that were prepared gravimetrically. The standard uncertainties of both vapor and liquid phase mole fractions are all 0.005, taking into account the calibration procedure and measurement repeatability. 2.3. Experimental Procedure. The experimental procedures include four processes: clean the apparatus, charge the refrigerants, and equilibrate and measure the VLE data. (1) The apparatus was thoroughly evacuated and charged with a small amount of refrigerant three times to eliminate any preexisting impurities. Then, (2) the estimated compound was filled into the cell. It is favorable to ensure that the vapor and liquid interface remains at the center of the cell to observe the liquidphase flow clearly. After that, (3) the thermostatic bath was set to the desired temperature and the recirculation pump was turned on to promote the equilibrium state. After 2 or 3 h, when the temperature fluctuation and pressure fluctuation were within 15 mK and 0.2 kPa, respectively, the equilibrium state was achieved. (4) The vapor and liquid samples were taken out by the sample valves and measured by the gas chromatograph. The measurement of each phase was repeated at least four times to acquire reliable results. After the measurement at all temperatures, the apparatus was evacuated and charged again to vary the total composition.

T/K

pexp/MPa

283.147 288.151 293.157 298.160 303.148 308.148 313.150 318.153 323.149

1.1062 1.2799 1.4737 1.6884 1.9253 2.1883 2.4759 2.7920 3.1376

283.154 288.159 293.146 298.147 303.142 308.137 313.152 318.152 323.168

0.3734 0.4393 0.5135 0.5969 0.6901 0.7941 0.9098 1.0374 1.1782

pcalb/MPa

δpc/%

1.1068 1.2808 1.4749 1.6901 1.9274 2.1897 2.4783 2.7950 3.1412

−0.05 −0.07 −0.08 −0.10 −0.11 −0.07 −0.10 −0.11 −0.11

0.3728 0.4387 0.5128 0.5964 0.6897 0.7936 0.9093 1.0369 1.1779

0.15 0.14 0.12 0.08 0.07 0.07 0.06 0.04 0.03

R32

R152a

a

The standard uncertainties u are u(T) = 10 mK, u(p) = 0.5 kPa. bThe vapor pressure of R32 was calculated by the Helmholtz Equations of State,24 and the vapor pressure of R152a was calculated by a modified Benedict−Webb−Rubin Equation of State.25 cδp = 100·(pexp − pcal)/ pexp.

R32 and R1234yf were obtained from Hu et al.13 The average absolute deviation AAD(p) and the maximum deviation MD(p) of R152a from the calculated results of the PRSV EOS are 0.11% and 0.19%, respectively. The experimental data from literature and this work, and the predicted data of the PRSV EOS were compared with the calculated results of the Helmholtz EOS24 and MBWR EOS25, respectively, which were depicted in Figure 1 and Figure 2. For R32, the experimental data of Hu et al.,13 a previous work of our group, and this work are in excellent agreement with deviations within 0.15%. These results show that the newly measured vapor pressure data are reliable. For R152a, the vapor pressure data of Park et al.,26 Higashi et al.,27 Defibaugh and Morrison,28 and Wu et al.29 show good agreement with the MBWR results, and the relative deviations are within 0.10%. Although the data of Seong et al.30 scatters around the baseline, it shows relative deviations larger than 0.30% above 310 K. The deviations of Hu et al.12 and this work show a decrease trend with the temperature. The data of Belyaeva et al.,31 Zhao et al.,32 Yin et al.,33 and Lim et al.34 locate under the baseline and show noticeable negative deviations within 0.50%. 3.2. Vapor Liquid Equilibria for Binary and Ternary Compounds. Vapor liquid equilibrium data for the binary mixtures of R32 + R152a and R152a + R1234yf were carried

3. RESULTS AND CORRELATIONS 3.1. Saturated Vapor Pressure for Pure Compounds. In this work, the saturated vapor pressures for R32 and R152a at an interval of 5 K over the temperature range of 283.15 to 323.15 K were measured, which is for verifying the reliability of apparatus and calculating the VLE property. The results are listed in Table 2 and reproduced by the PRSV EOS.23 The parameter κ1 for R152a (κ1, R152a = −0.0244) was fitted from the experimental data of this work, while the parameters κ1 of B



Article

with the constant C being:

C=

ln( 2 − 1) 2

(4)

where kij (i = j, kij = 0; i ≠ j, kij = kji) is a second virial coefficient binary interaction parameter and AE∞ is the excess Helmholtz free energy at infinite pressure. The NRTL activity coefficient model was used to calculate the excess Helmholtz free energy in the form as E A∞ = RT

Figure 1. Relative deviations of the experimental data pexp from the calculated results, pcal of the Helmholtz EOS for R32:24 △, Hu et al.;13 ■, this work; ---, PRSV EOS.

∑ xi i

∑j xjτjigji ∑k xkgki

(5)

gij = exp( −βijτij)

(6)

where τij (i = j, τij = 0; i ≠ j, τij ≠ τji), βij(i = j, βij = 0; i ≠ j, βij = βji) are the adjustable parameters. To simplify the thermodynamics model, βij is recommended to apply the value of 0.3 by Renon and Prausnitz.36 The K-value of component i in mixture Ki at vapor liquid equilibrium is given as y Ki = i xi (7) where xi and yi are the liquid and vapor mole fractions. Table 3 lists the detailed values of the k12, τ12 and τ21 for R32 + R152a, R1234yf + R152a and R32 + R1234yf binary systems. The experimental data and the predicted results by PRSV + WS + NRTL model are presented in Table 4 and Table 5, respectively, including the VLE data and the K-value at the studied range for R32(1) + R152a(2) and R1234yf(1) + R152a(2). The isothermal VLE data of ternary mixtures R32(1) + R152a(2) + R1234yf(3) were measured at six compositions in the temperature range of 283.15 to 323.15 K. Table 6 presents the VLE data and the K-values by the PRSV + WS + NRTL model.

Figure 2. Relative deviations of the experimental data pexp from the calculated results pcal of the MBWR EOS for R152a:25 △, Park et al.;26 ◁, Higashi et al.;27 ∗, Defibaugh and Morrison;28 ◇, Wu et al.;29 □, Seong et al.;30 ○, Belyeava et al.;31 ▷, Zhao et al.;32 +, Yin et al.;33 ▽, Lim et al.;34 ×, Hu et al.;12 ■, this work; ---, PRSV EOS.

out over the temperature range of 283.15 to 323.15 K at 10 K interval. The Wong and Sandler (WS) mixing rule and the nonrandom two-liquid (NRTL) activity coefficient model were used to correlate the vapor liquid equilibrium data. The VLE data were also evaluated through the use of K-value model. The WS mixing rule35 is given by am = bm

∑ xi i

ai AE + ∞ bi C

(

∑i ∑j xixj b − bm =

a

1 − ∑i xi b RTi − i

(

bi − ⎛ a ⎞⎟ ⎜b − = ⎝ RT ⎠ij

4. DISCUSSION 4.1. The VLE Properties for R32 + R152a and R152a + R1234yf Binary Systems. Figures 3 and 4 depict the experimental data of this work and literature along with the calculated data of the PRSV + WS + NRTL model and the Helmholtz model for R32 + R152a and R1234yf + R152a, respectively. For R32 + R152a, the VLE data of Lee et al.10 show relatively large deviation with this work at 303.15 and 323.15 K, while the data from Helmholtz EOS are in perfect agreement with those of this work. For R1234yf + R152a, the data of Hu et al.12 are in good agreement with this work over the temperature range from 283.15 to 323.15 K. Both the PRSV + WS + NRTL model and Helmholtz EOS could represent the experimental data very well.

(1) a RT ij

)

E A∞ CRT

ai RT

(2) aj

) + (bj − RT ) (1 − k ) ij

2

(3)

Table 3. Parameters k12, τ12, and τ21 of the PRSV + WS + NRTL Model for R32(1) + R152a(2), R32(1) + R1234yf(2) and R152a(1) + R1234yf(2)

a

chemicals

k12

τ12

τ21

AAD(p)a/%

AAD(y1)b

temp range/K

R32(1) + R152a(2) R1234yf(1) + R152a(2) R32(1) + R1234yf(2)c

−0.0936 −0.2206 0.1460

1.2756 0.8617 0.7784

−0.5064 0.3582 −0.1031

0.12 0.23 0.57

0.0024 0.0015 0.0018

283.15 to 323.15

N

N

AAD(p)/% = (100/N ) ∑i = 1 |(pexp, i − pcal, i )/pexp, i ″|. bAAD(y1) = (1/N ) ∑i = 1 |y1,exp, i − y1,cal, i |. cObtained from Hu et al.13 C



Article a

Table 4. Isothermal Vapor Liquid Equilibrium Data (p, x, y) and K-Value K1 for R32(1) + R152a(2) at Nine Compositions in the Temperature T Range of 283.15−323.15 K experimental data

PRSV + WS + NRTL

pexp/MPa

x1,exp

y1,exp

0.3734 0.4485 0.5017 0.5895 0.6530 0.7114 0.8262 0.8824 0.9364 1.0044 1.1062

0.0000 0.1100 0.1857 0.3105 0.3985 0.4801 0.6357 0.7100 0.7816 0.8698 1.0000

0.0000 0.2368 0.3631 0.5313 0.6223 0.6926 0.8069 0.8541 0.8938 0.9393 1.0000

2.1527 1.9553 1.7111 1.5616 1.4426 1.2693 1.2030 1.1436 1.0799 1.0000

0.5135 0.6137 0.6766 0.7893 0.8732 0.9476 1.0991 1.1725 1.2452 1.3353 1.4737

0.0000 0.1133 0.1814 0.3071 0.3965 0.4753 0.6322 0.7067 0.7794 0.8681 1.0000

0.0000 0.2348 0.3464 0.5116 0.6042 0.6777 0.7951 0.8443 0.8865 0.9349 1.0000

2.0724 1.9096 1.6659 1.5238 1.4258 1.2577 1.1947 1.1374 1.0769 1.0000

0.6901 0.8152 0.8942 1.0363 1.1434 1.2384 1.4295 1.5299 1.6258 1.7433 1.9253

0.0000 0.1119 0.1801 0.3043 0.3935 0.4717 0.6273 0.7040 0.7781 0.8668 1.0000

0.0000 0.2219 0.3312 0.4931 0.5870 0.6600 0.7819 0.8338 0.8791 0.9302 1.0000

1.9830 1.8390 1.6204 1.4917 1.3992 1.2465 1.1844 1.1298 1.0731 1.0000

0.9098 1.0611 1.1596 1.3362 1.4724 1.5916 1.8335 1.9590 2.0859 2.2358 2.4759

0.0000 0.1095 0.1782 0.3007 0.3916 0.4692 0.6225 0.7014 0.7767 0.8661 1.0000

0.0000 0.2075 0.3142 0.4731 0.5693 0.6432 0.7669 0.8224 0.8708 0.9245 1.0000

1.8950 1.7632 1.5733 1.4538 1.3708 1.2320 1.1725 1.1212 1.0674 1.0000

1.1782 1.3591 1.4800 1.6948 1.8647 2.0108 2.3115 2.4708 2.6351

0.0000 0.1071 0.1762 0.2968 0.3888 0.4674 0.6192 0.6980 0.7754

0.0000 0.1942 0.2985 0.4531 0.5511 0.6239 0.7510 0.8085 0.8614

1.8133 1.6941 1.5266 1.4174 1.3348 1.2129 1.1583 1.1109

K1,exp

pcal/MPa T= 0.3723 0.4484 0.5018 0.5908 0.6542 0.7134 0.8274 0.8824 0.9359 1.0026 1.1024 T= 0.5122 0.6128 0.6745 0.7903 0.8739 0.9484 1.0993 1.1724 1.2446 1.3343 1.4701 T= 0.6891 0.8142 0.8922 1.0370 1.1431 1.2377 1.4307 1.5285 1.6249 1.7429 1.9246 T= 0.9091 1.0605 1.1579 1.3357 1.4710 1.5890 1.8301 1.9589 2.0853 2.2398 2.4791 T= 1.1785 1.3590 1.4785 1.6928 1.8614 2.0094 2.3076 2.4700 2.6354

y1,cal 283.15 K 0.0000 0.2460 0.3740 0.5376 0.6283 0.6995 0.8110 0.8560 0.8958 0.9406 1.0000 293.15 K 0.0000 0.2402 0.3522 0.5166 0.6098 0.6803 0.7973 0.8449 0.8877 0.9357 1.0000 303.15 K 0.0000 0.2261 0.3353 0.4961 0.5898 0.6611 0.7815 0.8331 0.8793 0.9305 1.0000 313.15 K 0.0000 0.2108 0.3176 0.4742 0.5700 0.6418 0.7643 0.8200 0.8696 0.9247 1.0000 323.15 K 0.0000 0.1960 0.2999 0.4513 0.5481 0.6215 0.7461 0.8044 0.8584

D

δpb

Δyc

K1,cal

δK1d

0.30 0.01 −0.01 −0.22 −0.18 −0.28 −0.14 0.00 0.05 0.18 0.34

0.0000 −0.0092 −0.0109 −0.0063 −0.0060 −0.0069 −0.0041 −0.0019 −0.0020 −0.0013 0.0000

2.2364 2.0140 1.7314 1.5767 1.4570 1.2758 1.2056 1.1461 1.0814 1.0000

−3.89 −3.00 −1.19 −0.96 −1.00 −0.51 −0.22 −0.22 −0.14 0.00

0.26 0.14 0.31 −0.12 −0.07 −0.08 −0.02 0.01 0.04 0.08 0.24

0.0000 −0.0054 −0.0058 −0.0050 −0.0056 −0.0026 −0.0022 −0.0006 −0.0012 −0.0008 0.0000

2.1200 1.9416 1.6822 1.5380 1.4313 1.2612 1.1956 1.1390 1.0779 1.0000

−2.30 −1.67 −0.98 −0.93 −0.38 −0.28 −0.07 −0.14 −0.09 0.00

0.15 0.12 0.23 −0.07 0.02 0.05 −0.08 0.09 0.05 0.02 0.03

0.0000 −0.0042 −0.0041 −0.0030 −0.0028 −0.0011 0.0004 0.0007 −0.0002 −0.0003 0.0000

2.0206 1.8617 1.6303 1.4989 1.4015 1.2458 1.1834 1.1301 1.0735 1.0000

−1.89 −1.24 −0.61 −0.48 −0.17 0.05 0.08 −0.02 −0.03 0.00

0.08 0.05 0.15 0.04 0.10 0.16 0.19 0.00 0.03 −0.18 −0.13

0.0000 −0.0033 −0.0034 −0.0011 −0.0007 0.0014 0.0026 0.0024 0.0012 −0.0002 0.0000

1.9251 1.7823 1.5770 1.4556 1.3679 1.2278 1.1691 1.1196 1.0677 1.0000

−1.59 −1.08 −0.23 −0.12 0.22 0.34 0.29 0.14 −0.02 0.00

−0.03 0.01 0.10 0.12 0.18 0.07 0.17 0.03 −0.01

0.0000 −0.0018 −0.0014 0.0018 0.0030 0.0024 0.0049 0.0041 0.0030

1.8301 1.7020 1.5206 1.4097 1.3297 1.2049 1.1524 1.1070

−0.93 −0.47 0.40 0.54 0.38 0.65 0.51 0.35



Article

Table 4. continued experimental data

PRSV + WS + NRTL

pexp/MPa

x1,exp

y1,exp

K1,exp

2.8245 3.1376

0.8629 1.0000

0.9172 1.0000

1.0629 1.0000

pcal/MPa

y1,cal

T = 323.15 K 2.8296 0.9163 3.1478 1.0000

δpb

Δyc

−0.18 −0.32

K1,cal

0.0009 0.0000

1.0619 1.0000

δK1d 0.10 0.00

The standard uncertainties u are u(T) = 10 mK, u(p) = 0.5 kPa, u(x1) = u(y1) = 0.005. bδp = 100·(pexp − pcal)/pexp. cΔy = y1,exp − y1,cal. dδK1= 100· (K1,exp − K1,cal)/K1,exp. a

Table 5. Isothermal Vapor Liquid Equilibrium Data (p, x, y) and K-Value K1 for R1234yf(1) + R152a(2)a at Three Compositions in the Temperature T Range of 283.15−323.15 K experimental data pexp/MPa

x1,exp

y1,exp

0.3728 0.4114 0.4330 0.4433 0.4374

0.0000 0.2247 0.4637 0.7543 1.0000

0.0000 0.2702 0.4984 0.7541 1.0000

0.5128 0.5613 0.5882 0.6006 0.5917

0.0000 0.2243 0.4634 0.7538 1.0000

0.0000 0.2671 0.4933 0.7532 1.0000

0.6897 0.7494 0.7824 0.7965 0.7825

0.0000 0.2237 0.4631 0.7535 1.0000

0.0000 0.2608 0.4889 0.7519 1.0000

0.9093 0.9810 1.0216 1.0372 1.0178

0.0000 0.2235 0.4631 0.7534 1.0000

0.0000 0.2573 0.4844 0.7504 1.0000

1.1779 1.2631 1.3110 1.3279 1.3014

0.0000 0.2227 0.4626 0.7534 1.0000

0.0000 0.2518 0.4803 0.7495 1.0000

PRSV + WS + NRTL K1,exp

1.2025 1.0748 0.9997 1.0000

1.1908 1.0645 0.9992 1.0000

1.1658 1.0557 0.9979 1.0000

1.1512 1.0460 0.9960 1.0000

1.1307 1.0383 0.9948 1.0000

pcal/MPa T = 283.15 0.3724 0.4102 0.4319 0.4409 0.4358 T = 293.15 0.5125 0.5601 0.5875 0.5976 0.5894 T = 303.15 0.6896 0.7486 0.7824 0.7935 0.7812 T = 313.15 0.9098 0.9818 1.0227 1.0344 1.0168 T = 323.15 1.1795 1.2660 1.3150 1.3267 1.3025

y1,cal

δp

Δyc

K1,cal

δK1d

0.0000 0.2763 0.4980 0.7550 1.0000

0.10 0.30 0.25 0.54 0.37

0.0000 −0.0061 0.0004 −0.0009 0.0000

1.2296 1.0740 1.0009 1.0000

−2.26 0.08 −0.12 0.00

0.0000 0.2698 0.4926 0.7529 1.0000

0.07 0.21 0.12 0.49 0.38

0.0000 −0.0027 0.0007 0.0003 0.0000

1.2029 1.0630 0.9988 1.0000

−1.01 0.14 0.04 0.00

0.0000 0.2635 0.4876 0.7513 1.0000

0.02 0.10 0.01 0.38 0.17

0.0000 −0.0027 0.0013 0.0006 0.0000

1.1779 1.0529 0.9971 1.0000

−1.04 0.27 0.08 0.00

0.0000 0.2580 0.4833 0.7503 1.0000

−0.05 −0.09 −0.11 0.27 0.10

0.0000 −0.0007 0.0011 0.0001 0.0000

1.1544 1.0436 0.9959 1.0000

−0.27 0.23 0.01 0.00

0.0000 0.2522 0.4790 0.7497 1.0000

−0.13 −0.23 −0.30 0.09 −0.08

0.0000 −0.0004 0.0013 −0.0002 0.0000

1.1325 1.0355 0.9951 1.0000

−0.16 0.27 −0.03 0.00

b

K

K

K

K

K

The standard uncertainties u are u(T) = 10 mK, u(p) = 0.5 kPa, u(x1) = u(y1) = 0.005. bδp = 100·(pexp − pcal)/pexp. cΔy = y1,exp − y1,cal. dδK1= 100· (K1,exp − K1,cal)/K1,exp. a

Figure 5 and Figure 6 show the relative and standard deviations for the pressures and vapor phase mole fractions of the experimental data and this work from the calculated results of the PRSV + WS + NRTL model at the studied range. In Figure 5, we can see that the deviations of pressure are within 0.40% and the deviations of the vapor phase mole fraction are within 0.010, except one data point. The AAD(p) and AAD(y) are 0.12% and 0.0024 for R32 + R152a, respectively. From Figure 6, the deviations of pressure are in the range of 1.00% and those of vapor phase mole fraction are in the range of 0.075. The AAD(p) and AAD(y) are 0.32% and 0.0015 for R152a + R1234yf, respectively. Figures 7 and 8 show the relative deviations for the K-value of the experimental data and the calculated results of the PRSV + WS + NRTL model at the studied range for R32(1) +

R152a(2) and R1234yf(1) + R152a(2), respectively. As shown in Figure 7, the data of this work agree with the PRSV + WS + NRTL model to about ±5% for R32(1) + R152a(2). Figure 8 is similar to Figure 7 in that the deviations of the K-values are within the range of ±5% for R1234yf(1) + R152a(2). Both of these two figures obviously show that the discrepancy with the experimental data and the calculated data are large in low mole fractions, sometimes exceeding 5%. 4.2. The VLE Property for R32 + R152a + R1234yf Ternary System. Figure 9 shows the distribution of the experimental and predicted data at 303.15 K. It clearly presents that the experimental data disperse in the concentration triangle, which means that the data presented here have a good representativeness. Meanwhile, the predicted results almost overlap with the experimental data. This manifests E


F

0.1306 0.1462 0.1697 0.3629 0.4253 0.5589

0.1291 0.1444 0.1674 0.3603 0.4215 0.5561

0.1272 0.1429 0.1659 0.3574 0.4165 0.5536

0.1247 0.1410 0.1641 0.3548 0.4113 0.5506

0.1232 0.1387 0.1618 0.3510 0.4058 0.5465

0.5321 0.5002 0.5940 0.6632 0.7830 0.8339

0.7136 0.6743 0.7891 0.8840 1.0344 1.1058

0.9370 0.8901 1.0295 1.1539 1.3398 1.4379

1.2087 1.1531 1.3190 1.4808 1.7040 1.8376

1.5354 1.4688 1.6648 1.8695 2.1331 2.3099

0.4858 0.7524 0.2060 0.5332 0.1656 0.2598

0.4843 0.7503 0.2050 0.5297 0.1636 0.2573

0.4802 0.7482 0.2052 0.5274 0.1622 0.2552

0.4792 0.7467 0.2044 0.5246 0.1604 0.2534

0.4791 0.7446 0.2039 0.5223 0.1587 0.2513

x2,exp

0.2107 0.2384 0.2776 0.5017 0.5496 0.6733

0.2243 0.2510 0.2954 0.5213 0.5695 0.6906

0.2373 0.2647 0.3132 0.5394 0.5895 0.7052

0.2516 0.2800 0.3300 0.5572 0.6083 0.7180

0.2646 0.2984 0.3468 0.5741 0.6279 0.7274

y1,exp

experimental data

0.4183 0.6453 0.1750 0.3915 0.1170 0.1714

0.4069 0.6318 0.1692 0.3731 0.1096 0.1589

0.3961 0.6167 0.1634 0.3558 0.1025 0.1483

0.3852 0.6012 0.1574 0.3384 0.0961 0.1388

0.3801 0.5891 0.1513 0.3219 0.0981 0.1315

y2,exp

1.7102 1.7188 1.7157 1.4293 1.3544 1.2320

1.7987 1.7801 1.8001 1.4693 1.3846 1.2543

1.8656 1.8523 1.8879 1.5092 1.4154 1.2738

1.9489 1.9391 1.9713 1.5465 1.4432 1.2911

2.0260 2.0410 2.0436 1.5820 1.4764 1.3015

K1,exp

0.8611 0.8577 0.8495 0.7342 0.7065 0.6597

0.8402 0.8421 0.8254 0.7044 0.6699 0.6176

0.8249 0.8242 0.7963 0.6746 0.6319 0.5811

0.8038 0.8051 0.7701 0.6451 0.5991 0.5478

0.7934 0.7912 0.7420 0.6163 0.6181 0.5233

K2,exp

1.5337 1.4687 1.6609 1.8638 2.1376 2.3104

1.2049 1.1513 1.3132 1.4756 1.7022 1.8343

0.9332 0.8876 1.0209 1.1482 1.3327 1.4321

0.7090 0.6715 0.7794 0.8780 1.0252 1.0985

0.5273 0.4979 0.5838 0.6579 0.7724 0.8264

pcal/MPa T = 283.15 0.2660 0.2995 0.3421 0.5758 0.6277 0.7334 T = 293.15 0.2519 0.2837 0.3249 0.5575 0.6110 0.7201 T = 303.15 0.2370 0.2686 0.3082 0.5383 0.5916 0.7057 T = 313.15 0.2209 0.2530 0.2902 0.5182 0.5699 0.6892 T = 323.15 0.2059 0.2367 0.2702 0.4955 0.5451 0.6693

y1,cal

K

K

K

K

K

0.4222 0.6478 0.1761 0.3989 0.1177 0.1749

0.4096 0.6306 0.1696 0.3777 0.1089 0.1613

0.3948 0.6137 0.1644 0.3589 0.1015 0.1498

0.3828 0.5973 0.1585 0.3406 0.0947 0.1397

0.3716 0.5799 0.1528 0.3235 0.0885 0.1303

y2,cal

−0.22 −0.33 −0.07 0.04 −0.45 −0.24

−0.10 −0.28 0.06 0.02 −0.18 −0.09

−0.13 −0.29 0.35 0.06 0.16 0.05

−0.06 −0.32 0.60 0.11 0.41 0.21

−0.03 −0.55 0.88 0.04 0.72 0.30

δpb

0.0048 0.0017 0.0074 0.0062 0.0045 0.0040

0.0034 −0.0020 0.0052 0.0031 −0.0004 0.0014

0.0003 −0.0039 0.0050 0.0011 −0.0021 −0.0005

−0.0003 −0.0037 0.0051 −0.0003 −0.0027 −0.0021

−0.0014 −0.0020 0.0047 −0.0017 0.0002 −0.0060

Δy1c

−0.0039 −0.0025 −0.0011 −0.0074 −0.0007 −0.0035

−0.0027 0.0012 −0.0004 −0.0046 0.0007 −0.0024

0.0013 0.0030 −0.0010 −0.0031 0.0010 −0.0015

0.0024 0.0039 −0.0011 −0.0022 0.0014 −0.0009

0.0085 0.0083 −0.0015 −0.0016 0.0096 0.0012

Δy2c

PRSV + WS + NRTL

1.6713 1.7066 1.6700 1.4117 1.3433 1.2247

1.7715 1.7943 1.7684 1.4605 1.3856 1.2517

1.8632 1.8796 1.8577 1.5062 1.4204 1.2747

1.9512 1.9647 1.9409 1.5473 1.4496 1.2949

2.0368 2.0486 2.0159 1.5867 1.4759 1.3122

K1,cal

0.8691 0.8610 0.8549 0.7481 0.7107 0.6732

0.8458 0.8405 0.8273 0.7130 0.6656 0.6269

0.8222 0.8202 0.8012 0.6805 0.6258 0.5870

0.7988 0.7999 0.7754 0.6493 0.5904 0.5513

0.7756 0.7788 0.7494 0.6194 0.5577 0.5185

K2,cal

2.28 0.71 2.67 1.24 0.82 0.59

1.52 −0.80 1.76 0.59 −0.07 0.20

0.13 −1.47 1.60 0.20 −0.36 −0.07

−0.12 −1.32 1.55 −0.05 −0.44 −0.29

−0.53 −0.37 1.36 −0.30 0.03 −0.82

δK1d

−0.93 −0.39 −0.63 −1.89 −0.60 −2.04

−0.66 0.19 −0.24 −1.23 0.64 −1.51

0.33 0.49 −0.61 −0.87 0.98 −1.01

0.62 0.65 −0.70 −0.65 1.46 −0.65

2.24 1.56 −0.99 −0.50 9.79 0.91

δK2d

The standard uncertainties u are u(T) = 10 mK, u(p) = 0.5 kPa, u(x1) = u(y1) = 0.005. bδp = 100·(pexp - pcal)/pexp. cΔy1 = y1,exp - y1,cal, Δy2 = y2,exp - y2,cal. dδK1= 100·(K1,exp - K1,cal)/ K1,exp. δK2= 100·(K2,exp K2,cal)/ K2,exp.

a

x1,exp

pexp/MPa

Table 6. Isothermal Vapor Liquid Equilibrium Data (p, x1, x2, y1, y2) and K-Value K1, K2 for R32(1) + R152a(2) + R1234yf(3)a at Six Compositions in the Temperature T Range of 283.15−323.15 K

Journal of Chemical & Engineering Data Article



Article

Figure 3. Vapor liquid equilibrium data for R32(1) + R152a(2) from 283.15 to 323.15 K; ▲, liquid, Lee et al.;10△, vapor, Lee et al.;10 ■, liquid, this work; □, vapor, this work; , PRSV + WS + NRTL; ---, Refprop V9.1.

Figure 5. Deviations of the experimental data pexp from the calculated results of the PRSV + WS + NRTL model pcal and y1, cal for R32(1)+R152a(2): □, this work.

Figure 6. Deviations of the experimental data pexp from the calculated results of the PRSV + WS + NRTL model pcal and y1, cal for R1234yf(1)+R152a(2): ▽, Hu et al.;12 □, this work.

Figure 4. Vapor liquid equilibrium data for R1234yf(1) + R152a(2) from 283.15 to 323.15 K; ▼, liquid, Hu et al.;12 ▽, vapor, Hu et al.;12 ■, liquid, this work; □, vapor, this work; , PRSV + WS + NRTL.

ing ternary mixture. These correlated results can provide certain guidance for future studies. Figure 11 gives another analogous chart where the calculated K-value for R32(1) + R152a(2) + R1234yf(3) ternary mixtures are compared with the experimental data from this work. The relative deviations of the K-values are all within the range of ±5% for R32(1) + R152a(2) + R1234yf(3), except for one data point from the K2-value. Figure 12 shows the isothermal−isobaric properties of R32 + R152a + R1234yf at 303.15 K along with three different pressures (0.8, 1.2, and 1.6 MPa), respectively. The area between the solid and dashed lines is the vapor liquid equilibrium region (denoted as L+V). The left area is the liquid phase, while the right area is the vapor phase. The phase equilibrium diagrams show that changing the components of

once again the good performance of PRSV + WS + NRTL model. Figure 10 presents the deviations of experimental pressure and vapor phase mole fractions from the predicted data. The maximum and average relative deviations of pressure are 0.92% and 0.24%, respectively. The maximum absolute vapor composition deviations are 0.0075 for R32 and 0.0098 for R152a, respectively. The average absolute deviations of vapor composition are 0.0029 and 0.0027, respectively. All results are distributed around the baseline, which means the PRSV + WS + NRTL model with the parameters correlated by the binary VLE data (R32 + R152a, R1234yf + R152a and R32 + R1234yf) has a powerful prediction ability for the correspondG



Article

Figure 7. Deviations of the experimental data K1,exp from the calculated results of the PRSV + WS + NRTL model K1,cal for R32(1) + R152a(2): □, this work.

Figure 10. Deviations of the experimental pressure pexp from the calculated results of PRSV + WS + NRTL model pcal and y1, cal for R32(1) + R152a(2) + R1234yf(3) at temperatures from 283.15 to 323.15 K: □, δp; △, y1; red ▽, y2.

Figure 8. Deviations of the experimental data K1,exp from the calculated results of the PRSV + WS + NRTL model K1,cal for R1234yf(1)+R152a(2): ▽, Hu et al.;12 □, this work.

Figure 11. Deviations of the experimental data Ki,exp from the calculated results of the PRSV + WS + NRTL model Ki,cal for R32(1) + R152a(2) + R1234yf(3): □, δK1; red ○, δK2.

Figure 9. Liquid and vapor mole fractions for R32(1) + R152a(2) + R1234yf(3) at 303.15 K: ■, experimental liquid phase; red ○, experimental vapor phase; red △, calculated vapor phase.

R32 + R152a + R1234yf ternary system can achieve a wide range of pressure.

5. CONCLUSION In this work, new vapor liquid equilibrium data for the binary mixtures of R32 + R152a and R152a + R1234yf, and the ternary system of R32 + R152a + R1234yf over the temperature range from 283.15 to 323.15 K, were measured by the AnTLcirCapValVis analytical apparatus. With the fitted parameters of binary systems (R32 + R152a, R1234yf + R152a, and R32 + R1234yf), the ternary VLE property were predicted by the PRSV + WS + NRTL model. The calculated results show good agreement

Figure 12. Calculated isothermal−isobaric property by PRSV + WS + NRTL model for R32 + R152a + R1234yf at 303.15 K and 0.8, 1.2, and 1.6 MPa: , liquid line; red -·-, vapor line.

with the experimental data. The AAD(p) and AAD(y) are 0.12% and 0.0024 for R32+R152a, and 0.32% and 0.0015 for R152a+R1234yf. While for the ternary mixture R32 + R152a + R1234yf, the AAD(p), AAD(y1, R32), and AAD(y2, R152a) are 0.24%, 0.0029, and 0.0027, respectively. H



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(E)) and difluoromethane + 2,3,3,3-tetrafluoropropene (R-1234yf) mixtures. Fluid Phase Equilib. 2013, 358, 98−104. (16) Fonseca, J. M. S.; Dohrn, R.; Peper, S. High-pressure fluid-phase equilibria: Experimental methods and systems investigated (2005− 2008). Fluid Phase Equilib. 2010, 288, 1−54. (17) Ohta, T. Representation of excess enthalpies by the PRSV equation of state with the modified Huron-Vidal first order and WongSandler mixing rules. Fluid Phase Equilib. 1997, 129, 89−103. (18) Mathias, P. M. Guidelines for the analysis of vapor-liquid equilibrium data. J. Chem. Eng. Data 2017, 62, 2231−2233. (19) Lemmon, E. W.; Huber, M. L.; McLinden, M. O. NIST Reference Fluid Thermodynamic and Transport Properties Database, Refprop V9.1.; Standard Reference Data Program; National Institute of Standards and Technology: Gaithersburg, MD, 2013. (20) Hu, X. Z.; Meng, X. Y.; Wu, J. T. Isothermal vapor liquid equilibrium measurements for difluoromethane (R32) + trans-1,3,3,3tetrafluoropropene (R1234ze(E)). Fluid Phase Equilib. 2017, 431, 58− 65. (21) Meng, X. Y.; Hu, X. Z.; Yang, T.; Wu, J. T. Vapor liquid equilibria for difluoromethane (R32) + fluoroethane (R161) and fluoroethane (R161) + trans- 1,3,3,3-tetrafluoropropene (R1234ze(E)) binary mixtures. J. Chem. Thermodyn. 2017, 118, 43. (22) Hu, X. Z.; Yang, T.; Meng, X. Y.; Wu, J. T. Isothermal vapor liquid equilibrium measurements for difluoromethane (R32) + fluoroethane (R161) + trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) ternary mixtures. Int. J. Refrig. 2017, 79, 49−56. (23) Stryjek, R.; Vera, J. H. PRSV: An improved Peng-Robinson equation of state for pure compounds and mixtures. Can. J. Chem. Eng. 1986, 64, 323−333. (24) Tillnerroth, R.; Yokozeki, A. An International Standard Equation of State for Difluoromethane (R-32) for Temperatures from the Triple Point at 136.34 to 435 K and Pressures up to 70 MPa. J. Phys. Chem. Ref. Data 1997, 26, 1273−1328. (25) Outcalt, S. L.; Mclinden, M. O. A Modified Benedict−Webb− Rubin Equation of State for the Thermodynamic Properties of R152a (1,1-difluoroethane). J. Phys. Chem. Ref. Data 1996, 25, 605−636. (26) Park, Y.; Kang, J.; Choi, J.; Kim, H.; Yoo, J. k. Vapor-Liquid Equilibria for the 1,1-Difluoroethane (HFC-152a) + Propane (R-290) System. J. Chem. Eng. Data 2007, 52, 1203−1208. (27) Higashi, Y.; Ashizawa, M.; Kabata, Y.; Majima, T.; Uematsu, M.; Watanabe, K. Measurements of vapor pressure, vapor-liquid coexistence curve and critical parameters of Refrigerant 152a. JSME Int. J. 1987, 30, 1106−12. (28) Defibaugh, D. R.; Morrison, G. Compressed Liquid Densities, Saturated Liquid Densities, and Vapor Pressures of 1,1-Difluoroethane. J. Chem. Eng. Data 1996, 41, 376−381. (29) Wu, J. T.; Liu, Z. G.; Huang, H. H.; Pan, J.; Zhao, X. M.; He, M. G. Development of New High Accuracy PVTx Measurement Experimental System. J. Xi’an Jiaotong University 2003, 37, 5−9. (30) Seong, G.; Kim, A. R.; Yoo, K. P.; Lim, J. S. Measurement of VLE data for propane+1,1-difluoroethane at various temperatures from 268.15 to 333.15K. Korean J. Chem. Eng. 2009, 26, 206−213. (31) Belyaeva, O. V.; Grebenkov, A. J.; Zayats, T. A.; Timofeev, B. D. Speed of Sound and Thermodynamic Properties of Ozone Safe Refrigerants in the Liquid Phase. Dokl. Akad. Nauk BSSR. 1995, 39, 108−11. (32) Zhao, Z. Y.; Yin, J. M.; Tan, L. C. Measurements of PVT properties and vapor pressure for HFC152a. Fluid Phase Equilib. 1992, 80, 191−202. (33) Yin, J. M.; Zhao, Z. Y.; Guo, J. X.; Tan, L. C. Measurements of Vapor Pressure for HFC152a in the low Temperature Region. J. Eng. Thermophys. 1991, 12, 122−125. (34) Lim, J. S.; Seong, G.; Byun, H. S. Vapor liquid equilibria for the binary system of 1,1-difluoroethane (HFC-152a) + n-butane (R-600) at various temperatures. Fluid Phase Equilib. 2007, 259, 165−172. (35) Wong, D. S. H.; Sandler, S. I. A theoretically correct mixing rule for cubic equations of state. AIChE J. 1992, 38, 671−680.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: +86-29-82666875. ORCID

Xianyang Meng: 0000-0002-9327-2720 Jiangtao Wu: 0000-0003-1123-4307 Funding

This work was supported by the National Natural Science Foundation of China (No. 51476130). Notes

The authors declare no competing financial interest.

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