Article pubs.acs.org/jced
Pressure−Volume−Temperature Property Measurements for trans1,1,1,3-Tetrafluoro-2-butene [HFO-1354mzy(E)] Takeru Kimura,*,† Yohei Kayukawa,‡ and Kiyoshi Saito† †
Department of Applied Mechanics and Aerospace Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan ‡ Fluid Property Standards Group, Research Institute of Engineering Measurement, National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, AIST Central 3, 1-1-1, Umezono, Tsukuba 305-8563, Japan ABSTRACT: This study presents experimental measurements of the vapor pressures and pressure−volume−temperature (PVT) properties of trans-1,1,1,3tetrafluoro-2-butene, also known as HFO-1354mzy(E). This substance is expected to be a candidate working fluid for high-temperature heat pumps. The densities were measured by magnetic levitation densimeter (MLD). Vapor pressures were measured over the temperature range from (340 to 410) K, at pressures from (0.5 to 2.5) MPa. Liquid-phase PVT properties were measured at temperatures between (280 and 420) K at pressures up to 20 MPa. Gas-phase PVT properties were measured in the temperature range from (340 to 420) K at pressures from (0.5 to 2.5) MPa. The experimental uncertainties of the present measurements were estimated to be within ±18 mK in temperature, ±2.9 kPa in pressure, and ±0.012 % in density, respectively. The vapor pressure correlation and equations of state (EoS) for the liquid-phase and gas-phase PVT properties were derived. The vapor pressure correlation and the proposed EoS were found to well represent the set of measurements within a deviation of ±0.13 % in vapor pressure, ±0.2 % in liquid phase density, and ±0.3 % in pressure for the gas-phase PVT properties, respectively.
1. INTRODUCTION
2. EXPERIMENT 2.1. Apparatus. In this study, the PVT properties of HFO1354mzy(E) were measured with a single sinker MLD, which is based on Archimedes’ principle. The general construction of a MLD was reported by Wagner and Kleinrahm.3 Our instrument is shown in Figure 1. The adopted components are the same as those described by Kayukawa et al.4 Only a brief description is given here. A schematic diagram of the measurement instrument is shown in Figure 1. The temperature is measured using a standard platinum resistance thermometer inserted into the MLD wall. The resistance of the thermometer is measured using a thermometer bridge and then converted to ITS-90.5 Quartz crystal pressure transducers are employed as pressure gauges. The density is given by
Accurately measured thermodynamic properties are important for the design of thermal systems and their components, such as heat pump systems and heat exchangers. In recent years, the utilization of wasted heat from industry for hot water supply has become required for energy saving. High-temperature heat pump systems are one of the effective solutions. These systems can be heated to 150 °C (423.15 K) or higher via the effective use of wasted heat. However, a suitable working fluid for hightemperature heat pumps has still not been found. Most current working fluids have disadvantages such as high GWP (global warning potential), ozone depletion potential, flammability, or low efficiency. HFO (hydrofluoroorefin) refrigerants have attracted much attention in recent years because it has low GWP and low flammability. This study focuses on HFO1354mzy(E) (trans-1,1,1,3-tetrafluoro-2-butene; CF3CHCFCH3, CAS registry no. 791616-87-0, molecular weight 128.07). The normal boiling point of HFO1354mzy(E) is between (289 and 291) K,1 higher than that of R134a at −247.08 K.2 Thus, HFO-1354mzy(E) is expected to be suitable as a working fluid for heat pump systems. However, there is not enough experimental data to allow a reference equation of state to be formulated. Hence, the purpose of this study is to obtain a data set of the pressure−volume−temperature (PVT) properties of HFO-1354mzy(E) using a magnetic levitation densimeter (MLD). © XXXX American Chemical Society
ρ = ρSi
B − B5 ⎫ ΔM ⎧ B2 − B3 ⎨ ⎬(1 + (1 + aχ ) − 6 MSi ⎩ B2 − B1 B5 − B4 ⎭
{1 + βSi (P − P0)}
∫T
T
αSi dT )−3
0
(1)
where B1 to B6 represent balance readings from the electronic balance, and ΔM is the mass difference of the titanium weight and tantalum weight. These values are used to calibrate the Received: November 23, 2016 Accepted: February 8, 2017
A
DOI: 10.1021/acs.jced.6b00980 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Chemical Industrial Co., Ltd., Ibaraki, Japan) was used for device soundness check in this study. HFO-1354mzy(E) was supplied by SynQuest Laboratories, Inc., Alachua, U.S.A.; its purity was specified by the supplier to be 99 area % from gas chromatography data. The sample was transferred to a stainless steel cylinder and frozen with liquefied nitrogen, after which the head space was evacuated to remove undissolved gas components. 2.2. Uncertainties. The sinker used in this study was made of a silicon single crystal. The mass and volume of the sinker were calibrated with an electronic balance and hydrostatic weighing apparatus at the National Institute of Advanced Industrial Science and Technology, Japan. The calibrated mass and volume were (60.210 629 ± 0.000 024) g and (25.850 78 ± 0.000 17) cm3, respectively. Considering the influence of density uncertainty factors (e.g., the mass and volume of the sinker) according to Kayukawa et al.,4 the density uncertainty of the measurement was estimated to be 0.0008 kg·m−3 + 1.8 × 10−4 ρ (1 − ρ/(2600 kg·m−3)). The temperature uncertainty was estimated to be 18 mK, considering the stability of the thermometer (2 mK), temperature fluctuations (0.6 mK), and temperature gradients (8.7 mK). The pressure uncertainty was estimated to be 2.9 kPa, which includes the uncertainty of the pressure gauge (1.3 kPa) and the pressure fluctuation (0.7 kPa). These uncertainties are expanded uncertainties (k = 2).
Figure 1. Cross section of the present PVT property measurement system. MLD: magnetic levitation densimeter cell, VV: variable volume vessel with metallic bellows, EB: electronic balance, AS: airtight shield, PRT: standard platinum resistance thermometer, RS: radiation shield with cooling jacket, AB: aluminum heat-soaking blocks, TB: thermostatic bath, DC: programmable DC power source, H1−H2: electric heaters, CP: charging port, VC: vacuum chamber, V1 and V2: valves, PT: pressure transducer, PP: pipe port, PrP: pressurization port, VP: vacuum port.
sensitivity of the electronic balance. MSi and ρSi denote the mass and density of the silicon sinker, respectively. χ and a are the magnetic susceptibility of the sample fluid and a device-specific proportional constant for correcting the imperfectness of the magnetic coupling, respectively. The device-specific proportional constant a = 4.3 was determined from the force transmission error of magnetic coupling estimated by linear approximation using the finite element method.6 No previous information on the magnetic susceptibility of HFO-1354mzy(E) was available, so we obtained an estimate using Pascal’s additive law.7 To correct for the deformation effect of the silicon sinker at elevated temperature and pressure, the thermal expansion coefficient,6 αSi, and isothermal compressibility,6 βSi, were applied. The chemical sample descriptions are tabulated in Table 1. Isobutane of 99.99 mol % purity (as reported by Takachiho
3. RESULTS AND DISCUSSION Measurements were first carried out on isobutane as a test to confirm the reliability of the measurement procedure. The data set of these measurement results were tabulated in Tables 2. The deviation in relative density between the experimental results and resulted calculated by Buecker8 are illustrated in Figure 2. The deviation in the present measurements was well
Table 1. Chemical Samples Used in This Study chemical name isobutane trans-1,1,1,3tetrafluoro-2butene
source Takachiho Chemical Industrial Co., Ltd. SynQuest Laboratories, Inc.
mole fraction purity
purification method
0.9999
none
0.99a
none
Figure 2. Relative density deviation for the present experimental data for isobutane from an EoS by Buecker.8
represented by the EoS within ±0.2 %. Reasonable agreement between our values and the calculated values was confirmed, indicating that the present measurement method was suitably reliable.
a
The sample purity is 99 area % from gas chromatography data reported by the supplier.
Table 2. PVT Properties Measured in the Present Study for Isobutanea
a
T/K
P/kPa
ρ/(kg·m−3)
u(ρ)/(kg·m−3)
ρcalc/ (kg·m−3)b
100(ρ/ρcalc − 1)
phase
293.152 340.001 370.001
646.8 496.3 550.2
556.91 11.20 11.23
0.08 0.003 0.005
557.54 11.22 11.23
−0.11 −0.10 −0.07
liquid gas gas
Standard uncertainties: u(T) = 18 mK and u(P) = 2.9 kPa. bDensity is calculated from EoS by Buecker8 B
DOI: 10.1021/acs.jced.6b00980 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Using the present MLD system, 14 vapor pressure points, 50 PVT property points in the liquid phase, and 52 PVT property points in the gas phase were measured. The vapor pressures were measured directly with the pressure gauge. The data set of these measurement results is tabulated in Tables 3−5, and all data are illustrated in Figure 3.
τ=1−
a
T/K
P/kPa
T/K
P/kPa
534.7 687.5 775.7 871.6 976.6 1091.4 1215.9
380.000 385.001 390.000 395.000 400.000 405.000 410.000
1349.3 1495.1 1651.3 1822.3 2004.3 2202.8 2416.9
(3)
where Pc and Tc denote the critical pressure and critical temperature, respectively, and Ts represents the saturated temperature. Correlation constants a1 through a4 were obtained by least-squares fitting and are given in Table 6. The critical pressure Pc was 3250 kPa, and the critical temperature Tc was 424.73 K by experimental result.9 The pressure deviation of the measured data from those calculated by eq 2 is shown in Figure 4. The present measurements were well represented by the vapor pressure correlation, to within (−0.06 to +0.13) % except the single datum at 410 K (−0.26 %), and the average absolute deviation (AAD) was calculated to be 0.06 % in pressure. The liquid phase EoS for HFO-1354mzy(E) is given by
Table 3. Experimental Vapor Pressure Data in the Present Study for HFO-1354mzy(E)a 340.000 350.000 355.000 360.000 365.000 370.000 375.000
Ts Tc
ρr =
Standard uncertainties: u(T) = 18 mK and u(P) = 2.9 kPa.
(Pr + A(Tr))C(Tr) D(Tr)
(4)
2
A(Tr) =
To check the consistency of the present measurements, a vapor pressure correlation and EoS for the liquid phase and gas phase for HFO-1354mzy(E) were developed on the basis of the experimental data. Only the data from the present study were used to develop the equations. In this study, the functional form of the vapor pressure correlation originally proposed by Wagner3 was employed. Using this function, vapor pressure Ps is given by P T ln s = c Pc Ts
∑ aiTrk
(5)
k=0 2
C(Tr) =
∑ ciTrk
(6)
k=0 2
D(Tr) =
∑ diTrk
(7)
k=0
4
∑ aiτ
bi
The functional form of the EoS proposed by Sato10 was applied. Tr, Pr, and ρr are reduced parameters represented as Tr
(2)
i=1
Table 4. Liquid-Phase PVT Properties Measured in the Present Study for HFO-1354mzy(E)a
a
T/K
P/kPa
ρ/ (kg·m−3)
u(ρ)/(kg·m−3)
T/K
P/kPa
ρ/(kg·m−3)
u(ρ)/ (kg·m−3)
280.080 280.010 279.999 280.000 279.996 279.998 280.005 300.014 299.992 300.004 300.020 300.008 300.026 300.033 300.019 299.998 319.993 319.982 319.970 320.016 320.026 320.002 319.998 339.995 340.001
20045.0 15043.5 10196.2 7731.4 5338.9 2639.6 1115.2 20014.3 15115.4 15060.1 15014.8 10014.4 10045.1 5037.4 2520.0 1030.6 19400.8 19307.4 14999.8 10000.0 5001.8 2500.7 1143.6 19999.3 18406.0
1225.72 1216.21 1206.16 1200.74 1195.28 1188.70 1184.83 1189.09 1178.53 1178.07 1177.80 1165.87 1165.54 1151.58 1143.28 1139.17 1150.55 1149.67 1138.17 1123.05 1105.84 1096.22 1090.52 1112.93 1110.33
0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.11 0.11 0.12 0.12
340.028 340.013 340.014 340.009 340.004 360.044 360.011 359.990 360.027 360.007 360.002 379.999 380.036 380.014 379.998 380.026 400.010 400.004 400.005 400.030 400.010 420.025 420.005 420.001 420.001
14999.004 10000.2 5001.3 2501.2 1000.8 20000.3 15002.0 10000.8 5206.4 2507.6 1007.8 20000.0 15000.8 9999.8 4973.3 2524.0 20003.4 15000.2 9999.9 5000.8 2513.2 20000.6 15003.8 10000.4 5001.1
1096.95 1078.72 1056.90 1044.09 1035.51 1073.40 1054.40 1031.66 1004.33 985.19 972.55 1032.89 1009.69 980.98 941.74 914.60 992.88 964.84 928.14 871.99 821.92 948.99 914.45 866.15 774.99
0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.10 0.11 0.11 0.10 0.10
Standard uncertainties: u(T) = 18 mK and u(P) = 2.9 kPa. C
DOI: 10.1021/acs.jced.6b00980 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 5. Gas-Phase PVT Properties Measured in the Present Study for HFO-1354mzy(E)a
a
T/K
P/kPa
ρ/(kg·m−3)
u(ρ)/(kg·m−3)
T/K
P/kPa
ρ/(kg·m−3)
u(ρ)/ (kg·m−3)
420.001 419.999 419.999 420.000 420.000 420.000 420.001 410.000 410.000 410.000 410.000 410.000 410.000 400.000 400.000 400.000 400.000 400.000 400.000 390.001 389.999 389.999 390.000 390.000 390.000 390.000
2465.4 2052.0 1531.2 987.2 898.4 792.4 716.2 1480.4 982.8 901.7 799.1 707.0 697.6 1487.2 1445.0 1400.1 1299.4 1200.0 991.5 1300.2 1194.5 1099.2 1031.5 1019.4 900.7 800.9
149.28 107.15 70.25 41.24 37.05 32.15 28.75 70.85 42.61 38.56 33.61 29.30 28.88 75.64 72.66 69.57 62.94 56.86 44.84 66.85 59.60 53.49 49.35 48.64 41.78 36.40
0.03 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
390.000 390.000 380.000 380.000 380.000 380.000 380.000 380.000 380.000 380.000 380.000 370.000 370.000 370.000 370.000 370.000 370.000 360.000 360.000 360.000 350.000 350.000 350.000 340.000 340.000 340.000
699.7 666.3 1276.3 1199.6 1100.5 1000.2 966.0 915.0 891.6 799.4 651.2 995.5 931.1 872.2 784.5 712.9 662.8 801.7 699.2 632.2 689.2 612.8 543.3 537.3 503.7 482.2
31.19 29.52 69.84 63.79 56.70 49.99 47.84 44.62 43.26 37.92 29.87 52.67 48.17 44.34 38.85 34.57 31.74 42.05 35.48 31.43 36.70 31.77 27.50 28.49 26.41 25.04
0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Standard uncertainties: u(T) = 18 mK and u(P) = 2.9 kPa.
Figure 4. Pressure differences of the vapor pressure correlation for HFO-1354mzy(E).
Figure 3. PVT data distribution for HFO-1354mzy(E); ―, saturation line from eq 2; ○, liquid phase PVT properties; △, vapor pressures; ▽, gas-phase PVT properties; ×, critical point.9
Table 7. Correlation Constants of the Present EoS for HFO1354mzy(E)
Table 6. Correlation Constants of the Present Vapor Pressure Correlation for HFO-1354mzy(E) i
ai
bi
1 2 3 4
−9.7456 9.1703 −2.0968 × 10 1.7506 × 102
1 1.5 2.5 5
i
ai
ci
di
0 1 2
4.79780 × 10 −7.94347 × 10 3.05929 × 10
5.890 × 10−2 −5.570 × 10−2 1.100 × 10−1
3.39491 × 10−1 −4.64134 × 10−2 2.51762 × 10−1
The relative deviation in relative density between the experimental results and calculated results is illustrated in Figure 5. The deviation in the present measurements are well represented by the EoS within (−0.1 to +0.2) %, and the AAD was calculated to be 0.05 % in density. A truncated virial EoS was employed for the gas-phase PVT properties of HFO-1354mzy(E). Second, third, and fourth virial coefficients were obtained in this study. The formulation of the EoS is represented by eq 8.
= T/Tc, Pr = P/Pc, and ρr = ρ/ρc, respectively. Tc, Pc, and ρc denote the critical temperature, pressure, and density, respectively. The values of Tc and Pc are same as those used in the vapor pressure correlation above. The critical density was 424.0 kg·m−3.9 The correlation constants of the EoS were obtained by a nonlinear least-squares fitting that minimized the density deviations. These correlation constants are shown in Table 7. D
DOI: 10.1021/acs.jced.6b00980 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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pressure correlation and EoS were developed to check the consistency of the measurements. These equations well represented the experimental results within a deviation of ±0.13 % in vapor pressure, ±0.2 % in liquid density, and ±0.3 % in pressure for the gas-phase PVT properties. Further experimental reports on the critical parameters and caloric properties are expected to assist the development of the reference EoS for HFO-1354mzy(E).
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected].
Figure 5. Relative deviation in density of experimental data of HFO1354mzy(E) about the liquid-phase PVT properties from eqs 4−7.
ORCID
Takeru Kimura: 0000-0002-6733-0974
P = Z = 1 + B(T )ρ + C(T )ρ2 + D(T )ρ3 ρRT
Funding
(8)
This research was partially supported by the Thermal Management Materials and Technology Research Association (TherMAT) program, New Energy and Industrial Technology Development Organization (NEDO), and Waseda Research Institute for Science and Engineering, Japan.
where Z is a compressibility factor. The second, third, and fourth virial coefficients are given by B(T ) = b1 + b2Tr−1 + b3exp(Tr−1)
(9)
C(T ) = c1 + c 2Tr−5 + c3Tr−12
D(T ) =
Notes
(10)
d1Tr−3
The authors declare no competing financial interest.
■
(11) −1
−1
In eq 8, the gas constant, R = 64.921 213 J·kg ·K was used. Tr is the reduced temperature and had the same definition as in eq 4. The correlation constants of the virial EoS are shown in Table 8. The pressure deviations are illustrated in Figure 6. The present measurements were well represented by the virial EoS within ±0.3 %, and the AAD was 0.08 % in pressure. Table 8. Correlation Constants of the Present Virial EoS for HFO-1354mzy(E) i 1 2 3
bi/(m3 kg−1) −3
4.8037 × 10 0 −2.8594 × 10−3
ci/(m6 kg−2) −6
1.6771 × 10 4.9552 × 10−6 −9.8904 × 10−7
REFERENCES
(1) SynQuest Laboratories, Material Safety Data Sheet, Product No. 1300-3-46, (E)-1,1,1,3-tetrafluoro-2-butene, 2015. Available at the following: http://www.synquestlabs.com. (2) Lemmon, E. W.; Huber, M. L.; McLinden, M. O. NIST Reference Fluid Thermodynamic and Transport PropertiesREFPROP, NIST Standard Reference Database 23, Version 9.1; National Institute of Standards and Technology (NIST): Gaithersburg, MD, 2013. (3) Wagner, W.; Brachthauser, K.; Kleinrahm, R.; Losch, H. W. A new, accurate single-sinker densitometer for temperatures from 233 to 523 K at pressures up to 30 MPa. Int. J. Thermophys. 1995, 16, 399− 411. (4) Kayukawa, Y.; Kimura, T.; Kano, Y.; Fujiata, Y.; Saito, K. Thermodynamic property measurements for hydrofluorobutenes by a magnetic levitation densimeter. Proceedings of the International Congress of Refrigeration, Yokohama, Japan, August 16−22, 2015. (5) Preston Thomas, H. The International Temperature Scale of 1990 (ITS-90). Metrologia 1990, 27, 3−10. (6) Kano, Y.; Kayukawa, Y.; Fujii, K.; Sato, H. A new method for correcting a force transmission error due to magnetic effects in a magnetic levitation densimeter. Meas. Sci. Technol. 2007, 18, 659−666. (7) Bain, G. A.; Berry, J. F. Diamagnetic Corrections and Pascal’s Constants. J. Chem. Educ. 2008, 85, 532−536. (8) Buecker, D.; Wagner, W. Reference Equations of State for the Thermodynamic Properties of Fluid Phase n-Butane and Isobutane. J. Phys. Chem. Ref. Data 2006, 35 (2), 929−1019. (9) Widiatmo, J. V.; Saito, I.; Yamazawa, K. Critical parameters of trans-1,1,1,3-tetrafluoro-2-buten[HFO-1354mzy(E)] Int. J. Thermophys. 2017, 38, DOI: 10.1007/s10765-016-2172-8 (10) Morimura, M.; Okabe, T.; Sato, H. Development of thermodynamic equations of state for liquid hydrofluorocarbons. Proceedings of the 24th Japan Symposium on Thermophysical Properties, Okayama, Japan, October 6−8, 2003 (in Japanese).
di/(m9 kg−3) 2.2540 × 10−9
Figure 6. Deviation in relative pressure of experimental gas-phase PVT property data for HFO-1354mzy(E) from eqs 8−11.
5. CONCLUSIONS In this study, a set of measurement results for the vapor pressure and PVT properties of HFO-1354mzy(E) was presented. The measurements were conducted using a MLD for a temperature range of 280 to 420 K, pressure range of up to 20 MPa, and the density range of 25 kg·m−3 to 1225 kg·m−3. The experimental uncertainties of the measurements were estimated to be within ±18 mK in temperature, ±2.9 kPa in pressure, and ±0.012 % in density, respectively. A vapor E
DOI: 10.1021/acs.jced.6b00980 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
