Article pubs.acs.org/jced
Gaseous PVT Property Measurements of cis-1,3,3,3Tetrafluoropropene Naoya Sakoda,*,†,‡,§ Jiang Shiheng,† Masamichi Kohno,†,‡,§ Shigeru Koyama,‡,∥ Yukihiro Higashi,‡ and Yasuyuki Takata†,‡,§ †
Department of Mechanical Engineering, ‡Research Center for Next Generation Refrigerant Properties (NEXT-RP), International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), and §Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS), Kyushu University, Fukuoka, 819-0395, Japan ∥ Department of Energy and Material Sciences, Kyushu University, Fukuoka, 816-8580, Japan ABSTRACT: PVT properties in the vapor phase of cis-1,3,3,3-tetrafluoropropene (R1234ze(Z)) were measured by a multiple expansion method in the temperature range from 353 to 413 K and at pressures up to 2.7 MPa. Thirty data along four isotherms are obtained in the temperatures between 353 and 413 K. The vapor pressures at the temperatures were also measured by adding a sample of R1234ze(Z) to a sample cell at the vapor−liquid equilibrium conditions. The uncertainties in temperature and pressure measurements are estimated to be within 6 mK and 0.3 kPa, respectively. The expanded uncertainty in density measurement is estimated within no greater than 0.12% (k = 2). The obtained PVT properties and vapor pressures are compared with the existing equation of state.
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INTRODUCTION Hydrofluoro-olefins (HFOs) have been attractive as HFC alternatives because of their low global warming potential (GWP). R1234ze(Z) (cis-1,3,3,3-tetrafluoropropene) with a GWP of 1 or less is expected to be an environmentally friendly working fluid for high-temperature heat pump systems and for organic Rankine cycle systems. Although accurate thermodynamic properties of the newly synthesized HFO refrigerants are strongly required as fundamental information in designing the heat pump systems and Rankine cycles, only a few experimental data are available. The currently available experimental PVT property data of R1234ze(Z) are summarized in Table 1. Higashi et al.1 measured PVT properties from 360 to 440 K and
0.08−0.4 0.9−2.9
2012
98 303−375 24 360−432 Liquid Phase 54 310−420
0.5−5.0
up to 6 MPa, saturated properties, and critical parameters of R1234ze(Z). Akasaka et al.2 presented an equation of state (EOS) formulating a Helmholtz free energy function available in the temperature range from 273 to 430 K and at pressures up to 6 MPa based on their measurements. The EOS also refers to the PVT properties of Tanaka et al.3 from 310 to 410 K and up to 5 MPa in the liquid phase, and those of Kayukawa et al.4 from 283 to 420 K and up to 5 MPa including the vapor and liquid phases. The uncertainties in the densities calculated from the EOS are 0.2% in the liquid phase and 0.4% in the vapor phase. After the accomplishment of its EOS, Fedele et al.5 measured PVT properties from 283 to 363 K and up to 34 MPa in the liquid phase and those from 303 to 375 K and up to 0.4 MPa in the vapor phase. For the heat pump systems, PVT properties at higher temperatures are necessary. In addition, a relatively larger discrepancy than the uncertainty in the density calculated from the EOS is observed among the published PVT properties in the vapor phase. In this study, gaseous PVT properties of R1234ze(Z) are measured from 353 to 413 K and up to 2.7 MPa by a multiple expansion method, namely, the Burnett method. The obtained data are compared with the previous PVT property measurements in the vapor phase against the EOS by Akasaka et al.2
2013 2014 2015
41 313 47
0.3−5.0 0.2−34.0 1.8−6.0
Received: March 15, 2017 Accepted: May 19, 2017
Table 1. Currently Available Experimental PVT Property Data of R1234ze(Z) author
year
Kayukawa et al.4 Fedele et al.5 Higashi et al.1
2012
Kayukawa et al.4 Tanaka et al.3 Fedele et al.5 Higashi et al.1
2014 2015
no. of points
temp range T/K
Vapor Phase 55 283−373
310−410 283−363 370−440
pressure range P/MPa 0.07−0.9
© XXXX American Chemical Society
A
DOI: 10.1021/acs.jced.7b00263 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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EXPERIMENTAL SECTION Sample. The sample of R1234ze(Z) was furnished by Central Glass Co., Ltd., Japan. In this study, helium was used for the determination of the cell constant of the multiple expansion method. As for the confirmation of the reliability of the present apparatus, nitrogen and R134a were used. The information on the samples is summarized in Table 2. The sample purities are given by the manufacturers. No further purification of the samples was performed.
(Paroscientific: 42K-101), and the pressure transducer is set inside the constant temperature bath. The pressure transducer is calibrated up to 3 MPa by a lower-range pressure transducer (Paroscientific: 31K-101), which is calibrated by a dead weight pressure gauge. The uncertainty in the pressure measurement is estimated to be 0.3 kPa. The temperature of the bath is measured by a 25 Ω standard platinum resistance thermometer with a precise thermometer bridge (ASL: F700B) according to ITS-90. The uncertainty in the temperature measurement is estimated to be within 6 mK. Determination of the Cell Constant. The cell constant, which is the volume ratio of the sample cell and the expansion cell, is a fundamental parameter in the multiple expansion method. The cell constant, N, is defined by (VA + VB)/VA, where VA and VB are the inner volumes of the sample cell (about 250 cm3) and the expansion cell (about 100 cm3), respectively. Helium was used at temperatures of 353, 373, 393, and 413 K and at pressures up to 1.2 MPa, and the cell constant was determined as 1.39760 ± 0.00005. The temperature dependence of the cell constant was not confirmed. The densities of the helium were also evaluated, and the experimental results are summarized in Table 3. The density deviations between the present data and an EOS by Ortiz-Vega et al.,8 which is cited in REFPROP 9.1,9 are shown in Figure 2. The estimated uncertainty in density, u(ρi ), is derived by
Table 2. Sample Information
a
sample
CASRN
purity
manufacturer
helium nitrogen R134aa R1234ze(Z)b
7440-59-7 7727-37-9 811-97-2 29118-25-0
0.99995c 0.99995c 0.9998d 0.9996d
Japan Helium Center Co., Ltd. Fukuoka Oxygen Co., Ltd. Daikin Industries, Ltd. Central Glass Co., Ltd.
1,1,1,2-Tetrafluoroethane. fraction. dMole fraction.
b
cis-1,3,3,3-Tetrafluoropropene. cVolume
Apparatus. A schematic diagram of the experimental apparatus is shown in Figure 1. The multiple expansion method prepares two vessels, which are a sample cell and an expansion cell. A gaseous sample filled in the sample cell is isothermally expanded to the evacuated expansion cell. The isothermal expansion is repeated, and the density at each expansion step is derived from the equilibrium pressures before and after the expansions. Details of the measurement principle are described in previous publications.6,7 The apparatus was originally developed for the PVT property measurement of hydrogen from 353 to 473 K and up to 100 MPa,7 and a modification in the pressure measurement was performed for refrigerants in this study. A high-pressure range quartz pressure transducer (Paroscientific: 420K-101) available up to 138 MPa was replaced to that for a lower pressure range up to 13.8 MPa
u(ρi ) ρi
2 ⎡⎛ ⎤1/2 u(ρm ) ⎞ ⎛ ⎞2 2 u(N ) ⎥ ⎢ ⎟ + (m − i ) ⎜ = ⎜⎜ ⎟ ⎢⎝ ρ ⎟⎠ ⎝ N ⎠ ⎥⎦ m ⎣
(1)
where u(N) denotes the uncertainty in the cell constant.6 ρi and ρm are the densities after the ith and mth (last) expansions, respectively. The lowest density is determined with an uncertainty of 0.05%, and the uncertainty of the highest density is estimated to be less than 0.12% (k = 2) by eq 1. The
Figure 1. Schematic diagram of the experimental apparatus. B
DOI: 10.1021/acs.jced.7b00263 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 3. Experimental Results of PVT Property Measurements for Helium from 353 to 413 Ka P/MPa
Table 4. Experimental Results of PVT Property Measurements for Nitrogen and R134a at 353 and 413 Ka
ρ/mol·dm−3
P/MPa
0.3835 0.2744 0.1964 0.1405 0.1005 0.07193
2.4252 1.7331 1.2391 0.8861 0.6338 0.4534 0.3244 0.2321
T/K = 353.163 1.1312 0.8084 0.5779 0.4132 0.2955 0.2114
Nitrogen T/K = 353.172
T/K = 373.167 1.1437 0.8174 0.5843 0.4179 0.2988 0.2138
0.3671 0.2627 0.1879 0.1345 0.09621 0.06884
T/K = 413.162
0.3647 0.2609 0.1867 0.1336 0.09557 0.06838
0.7372 0.5275 0.3774 0.2701 0.1932 0.1383 0.09893 0.07078 R134a T/K = 353.171
1.7615 1.3597 1.0260 0.7621 0.5599 0.4082 0.2960 0.2138
T/K = 413.134 1.2495 0.8930 0.6385 0.4566 0.3265 0.2336
0.8229 0.5888 0.4213 0.3014 0.2157 0.1543 0.1104 0.07900
2.5536 1.8226 1.3019 0.9304 0.6651 0.4756 0.3402 0.2433
T/K = 393.119 1.1969 0.8554 0.6115 0.4373 0.3127 0.2237
ρ/mol·dm−3
0.3623 0.2592 0.1855 0.1327 0.09496 0.06795
0.7767 0.5557 0.3976 0.2845 0.2036 0.1457 0.1042 0.07457 T/K = 413.165
a
2.6068 1.9688 1.4646 1.0776 0.7867 0.5710 0.4128 0.2975 0.2140
Standard uncertainties u are u(T) = 6 mK, u(P) = 0.3 kPa, and the relative expanded uncertainty Ur is Ur(ρ) = 0.0012 (0.95 level of confidence).
0.9188 0.6574 0.4704 0.3366 0.2408 0.1723 0.1233 0.08822 0.06312
a
Standard uncertainties u are u(T) = 6 mK, u(P) = 0.3 kPa, and the relative expanded uncertainty Ur is Ur(ρ) = 0.0012 (0.95 level of confidence). Figure 2. Density deviations for helium between the present data and an EOS by Ortiz-Vega et al.:8 ○, 353 K; △, 373 K; □, 393 K; ×, 413 K.
present data are in agreement with the EOS by Ortiz-Vega et al.8 within the uncertainty as shown in Figure 2.
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RESULTS AND DISCUSSION PVT Property Measurements of Nitrogen and R134a. PVT properties of nitrogen and R134a in the vapor phase were measured at 353 and 413 K in order to confirm the reliability of the present measurements. Experimental results are summarized in Table 4. Figure 3 shows density deviations from reliable EOSs by Span et al.10 for nitrogen and by Tillner-Roth and Baehr11 for R134a. The present data are in good agreement with their EOSs within 0.1%. Gaseous PVT Property Measurement of R1234ze(Z). The gaseous PVT properties of R1234ze(Z) were measured in
Figure 3. Density deviations between the present data and EOSs by Span et al.10 for nitrogen: ○, 353 K; □, 413 K, and Tillner-Roth and Baehr11 for R134a: ×, 353 K; ▽, 413 K.
the temperature range from 353 to 413 K. The sample is filled in the sample cell at the vapor−liquid equilibrium condition before the multiple expansions, and the vapor pressure at each temperature was measured. The comparisons of the vapor pressure with the EOS by Akasaka et al.2 and the other C
DOI: 10.1021/acs.jced.7b00263 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 5. Experimental Results of PVT Properties in the Vapor Phase and Vapor Pressures (PS) for R1234ze(Z) from 353 to 413 Ka
published vapor pressure data are shown in Figures 4 and 5, which are percent deviations and absolute deviations from the
P/MPa T/K 0.7391 0.5589 0.4162 0.3063 0.2236 0.1623 T/K 0.9663 0.7346 0.5485 0.4044 0.2956 0.2148 T/K 1.8419 1.4810 1.1490 0.8711 0.6492 0.4782 0.3493 0.2536 T/K 2.7340 2.3183 1.8703 1.4581 1.1087 0.8283 0.6112 0.4470 0.3249 0.2351
Figure 4. Percentage deviations of the vapor pressure for R1234ze(Z) between the experimental data and the EOS by Akasaka et al.:2 +, Fedele et al. (ITC−CNR);13 ▽, Fedele et al. (UnivPM);13 ×, Higashi et al.;1 ○, Tanaka;12 ▲, this work.
Figure 5. Absolute deviations of the vapor pressure for R1234ze(Z) between the experimental data and the EOS by Akasaka et al.:2 +, Fedele et al. (ITC−CNR);13 ▽, Fedele et al. (UnivPM);13 ×, Higashi et al.;1 ○, Tanaka;12 ▲, this work.
EOS, respectively. The EOS is in good agreement with the present data within 0.1%, and represents most of the data by Higashi et al.1 and by Tanaka12 within 0.2% in Figure 4. The present data are consistent with the experimental data by Tanaka. The EOS shows relatively larger percentage deviations from the data by Fedele et al.13 in Figure 4 at low temperatures below 330 K because the vapor pressure becomes small. In the absolute pressure deviation by Figure 5, the EOS is in good agreement with the data by Fedele et al. almost within 2 kPa. After the vapor pressure measurements, some of the sample was released to become the single vapor-phase, and the isothermal expansions were performed. The measured PVT property data of R1234ze(Z) are tabulated in Table 5 including the measured vapor pressures. The density deviations between the present data and the EOS are shown in Figure 6. The comparisons of the data by Fedele et al.5 from 350 to 375 K and those by Higashi et al. from 360 to 415 K in the vapor phase are also given in Figure 6. In the vapor phase, the available PVT property data are very limited. The present data supplement the region where experimental data are insufficient between the data by Fedele et al. and by Higashi et al. The EOS agrees with the present data within 0.3% except for close to the saturated vapor density at 413 K in Figure 6. The EOS deviates from the present data slightly larger than the measurement uncertainty at some data points, so the uncertainty of the EOS will be improved by fitting the present data.
ρ/mol·dm−3 = 353.165 (PS/MPa = 0.8583) 0.3052 0.2184 0.1563 0.1118 0.07999 0.05724 = 373.145 (PS/MPa = 1.3475) 0.3833 0.2742 0.1962 0.1404 0.1005 0.07188 = 393.125 (PS/MPa = 2.0237) 0.8383 0.5998 0.4292 0.3071 0.2197 0.1572 0.1125 0.08048 = 413.144 (PS/MPa = 2.9404) 1.432 1.024 0.7330 0.5244 0.3752 0.2685 0.1921 0.1375 0.09835 0.07037
a Standard uncertainties u are u(T) = 6 mK, u(P) = 0.3 kPa, and the relative expanded uncertainty Ur is Ur(ρ) = 0.0012 (0.95 level of confidence).
Figure 6. Density deviations of the PVT property for R1234ze(Z) in the vapor phase between the experimental data and the EOS by Akasaka et al.:2 +, Fedele et al.5 from 350 to 375 K; ×, Higashi et al.1 from 360 to 415 K; This work: ○, 353 K; △, 373 K; □, 393 K; ▽, 413 K.
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CONCLUSION The PVT properties in the vapor phase of R1234ze(Z) were measured from 353 to 413 K by the multiple expansion method. Thirty points of PVT property data at four isotherms are presented. The vapor pressure at each temperature was also
measured. The existing EOS represents the present vapor pressure and PVT property data within 0.1% and within 0.3% except for close to the saturated vapor density, respectively. D
DOI: 10.1021/acs.jced.7b00263 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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(13) Fedele, L.; Di Nicola, G.; Brown, J. S.; Bobbo, S.; Zilio, C. Measurements and correlations of cis-1,3,3,3,-tetrafluoroprop-1-ene (R1234ze(Z)) saturation pressure. Int. J. Thermophys. 2014, 35, 1−12.
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Naoya Sakoda: 0000-0003-4899-879X Funding
This research has been conducted as part of the research project by Thermal Management Materials and Technology Research Association (TherMAT), Japan, funded by the New Energy and Industrial Technology Development Organization (NEDO). Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The authors greatly thank Central Glass Co., Ltd., Japan, for providing the sample of R1234ze(Z).
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REFERENCES
(1) Higashi, Y.; Hayasaka, S.; Shirai, C.; Akasaka, R. Measurements of PρT properties, vapor pressures, saturated densities, and critical parameters for R 1234ze(Z) and R 245fa. Int. J. Refrig. 2015, 52, 100− 108. (2) Akasaka, R.; Higashi, Y.; Miyara, A.; Koyama, S. A fundamental equation of state for cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)). Int. J. Refrig. 2014, 44, 168−176. (3) Tanaka, K.; Maruko, K.; Fujimoto, Y.; Tanaka, M. PVT properties of R1234ze(Z). Proceedings of Fourth Conference on Thermophysical Properties and Transfer Processes of Refrigerants (Paper No. TP-072), Delft, The Netherlands, 2013. (4) Kayukawa, Y.; Tanaka, K.; Kano, Y.; Fujita, Y.; Akasaka, R.; Higashi, Y. Experimental evaluation of the fundamental properties of low-GWP refrigerant R-1234ze(Z). Proceedings of the International Symposium on New Refrigerants and Environmental Technology 2012, Kobe, Japan. 2012. (5) Fedele, L.; Brown, J. S.; Di Nicola, G.; Bobbo, S.; Scattolini, M. Measurements and correlations of cis-1,3,3,3,-tetrafluoroprop-1-ene (R1234ze(Z)) subcooled liquid density and vapor-phase PvT. Int. J. Thermophys. 2014, 35, 1415−1434. (6) Sakoda, N.; Shindo, K.; Motomura, K.; Shinzato, K.; Kohno, M.; Takata, Y.; Fujii, M. Burnett method with absolute pressure transducer and measurements for PVT properties of nitrogen and hydrogen up to 473 K and 100 MPa. Int. J. Thermophys. 2012, 33, 6−21. (7) Sakoda, N.; Shindo, K.; Motomura, K.; Shinzato, K.; Kohno, M.; Takata, Y.; Fujii, M. Burnett PVT measurements of hydrogen and the development of a virial equation of state at pressures up to 100 MPa. Int. J. Thermophys. 2012, 33, 381−395. (8) Ortiz-Vega, D. O.; Hall, K. R.; Holste, J. C.; Arp, V. D.; Lemmon, E. W. cited in ref 9. (9) Lemmon, E. W.; Huber, M. L.; McLinden, M. O. NIST Standard Reference Database 23, NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP), version 9.1; Standard Reference Data; National Institute of Standards and Technology: Gaithersburg, MD., 2013. (10) Span, R.; Lemmon, E. W.; Jacobsen, R. T; Wagner, W.; Yokozeki, A. A reference equation of state for the thermodynamic properties of nitrogen for temperatures from 63.151 to 1000 K and pressures to 2200 MPa. J. Phys. Chem. Ref. Data 2000, 29, 1361−1433. (11) Tillner-Roth, R.; Baehr, H. D. An international standard formulation for the thermodynamic properties of 1,1,1,2-tetrafluoroethane (HFC-134a) for temperatures from 170 K to 455 K and pressures up to 70 MPa. J. Phys. Chem. Ref. Data 1994, 23, 657−729. (12) Tanaka, K. Measurements of vapor pressure and saturated liquid density for HFO-1234ze(E) and HFO-1234ze(Z). J. Chem. Eng. Data 2016, 61, 1645−1648. E
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