Article pubs.acs.org/jced
pρT Property of HFO-1336mzz(E) (trans-1,1,1,4,4,4-Hexafluoro-2butene) Katsuyuki Tanaka,*,† Junichi Ishikawa,‡ and Konstantinos Kostas Kontomaris§ †
Department of Precision Machinery Engineering, Nihon University, Chiba, 274−8501, Japan Dupont−Mitsui Fluorochemicals Co., Ltd., Tokyo, 101−0064, Japan § The Chemours Company, Delaware, 19805, United States ‡
ABSTRACT: The pρT (pressure−density−temperature) properties of HFO-1336mzz(E) (trans-1,1,1,4,4,4-hexafluoro-2-butene) is measured by the isochoric method. A total of 154 pρT property data points are obtained at temperatures from 323 to 523 K and pressures up to 10 MPa along 19 isochores at densities from 84 kg·m−3 to 1212 kg·m−3. The Benedict−Webb− Rubin−Starling equation of state is used to correlate the present data. Saturated temperatures are analytically determined at 15 state points by extrapolating the isochores to intersect with the vapor pressure curve.
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INTRODUCTION HFO-1336mzz(E) (trans-1,1,1,4,4,4-hexafluoro-2-butene) is a hydro-fluoro-olefin with the chemical formula C4H2F6 and structure trans-CF3CHCHCF3. This fluid is considered an alternative for HFC-245fa, a working fluid used in high temperature heat pumps,1 organic Rankine cycle systems,1 and chillers. However, thermodynamic property information available for HFO-1336mzz(E) in open sources is limited. The vapor pressures and critical parameters for HFO-1336mzz(E) were obtained and its normal boiling point and acentric factor were determined and used to calculate saturated properties such as saturated densities and heat of vaporization.2 In this work, the pρT (pressure−density−temperature) properties of HFO1336mzz(E) were acquired at temperatures from 323 to 523 K and pressures up to 10 MPa to calculate the single-phase (i.e., compressed liquid and superheated vapor, including the supercritical region) properties. The Benedict−Webb−Rubin− Starling (BWRS) equation of state3 was used to correlate the present data. The BWRS equation of state parameters for HFO-1336mzz(E) are provided. In addition, saturated temperatures were analytically determined from the pρT data.
523 K). The density of the sample was obtained from the volume of the sample cell and the mass of sample in the cell. The temperature of the sample was controlled by a thermostatic oil bath. the temperature of which was measured with a temperature sensor (CHINO, R900-F25AD). The pressure of the sample was measured with a pressure sensor (OMEGA, PX1009) connected to the cell. The pρT properties could be obtained along the isochoric line. The experimental uncertainties in the measurements of temperatures, pressures, and densities were estimated to be 0.03 K, 4 kPa, 0.4%, respectively. For densities below 100 kg·m−3, the uncertainty was 0.5%.
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The pρT data were obtained along 19 isochores at 10 K intervals in the temperature range from 323 to 523 K and at pressures up to 10 MPa. The data are presented in Table 2 and represented graphically in Figure 1. Figure 2 shows the data rearranged along isotherms. The Benedict−Webb−Rubin−Starling (BWRS) equation of state was used to correlate the present data. The functional form is given in eq 1.
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EXPERIMENTAL APPARATUS AND METHOD The sample was supplied by The Chemours Company. The sample information is listed in Table 1. HFO-1336mzz(E) pρT properties were measured by the isochoric method. The apparatus and experimental procedures have been described in our previous work.4 A sample of known mass was introduced to a constant-volume cell (10.48 cm3 at 323 K and 10.69 cm3 at
⎛ C D E ⎞ p = ρRT + ⎜B0 RT − A 0 − 02 + 30 + 04 ⎟ρ2 ⎝ T ⎠ T T ⎛ ⎛ d⎞ d⎞ + ⎜bRT − a − ⎟ρ3 + α⎜a + ⎟ρ6 ⎝ ⎠ ⎝ T T⎠ +
Table 1. Sample Information
a
RESULTS AND DISCUSSION
sample
CASRN
purity
manufacture
HFO-1336mzz(E)a
66711-86-2
99.99%
The Chemours Company
(1)
Received: April 23, 2017 Accepted: July 12, 2017 Published: July 25, 2017
trans-1,1,1,4,4,4-Hexafluoro-2-butene. © 2017 American Chemical Society
cρ3 (1 + γρ2 ) exp(−γρ2 ) T2
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DOI: 10.1021/acs.jced.7b00381 J. Chem. Eng. Data 2017, 62, 2450−2453
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Table 2. Experimental Data of the Pressure p, Temperature T, and Density ρ for HFO-1336mzz(E)a T
p
K
kPa
373.43 383.44 393.44 403.44 413.44 423.43 433.43 443.42 453.43 463.42 473.44 483.45 493.45 503.45 513.44 523.45 383.41 393.42 403.43 413.42 423.42 433.42 443.43 453.42 463.44 473.46 483.46 493.43 503.44 513.42 523.41 403.44 413.44 423.45 433.45 443.45 453.45 463.46 473.45 483.46 493.47
1203.4 1263.0 1320.8 1377.2 1432.9 1487.5 1541.9 1595.5 1648.3 1700.0 1751.3 1803.6 1854.7 1906.1 1956.7 2008.3 1661.4 1764.3 1863.4 1959.4 2053.6 2146.1 2237.3 2327.6 2415.5 2503.4 2590.8 2677.3 2763.1 2848.4 2933.2 2465.8 2664.9 2857.2 3045.2 3230.1 3412.1 3590.1 3766.0 3941.1 4117.6
ρ kg·m
T −3
83.9 83.9 83.8 83.7 83.6 83.5 83.4 83.4 83.3 83.2 83.1 83.0 83.0 82.9 82.8 82.7 129.2 129.1 128.9 128.8 128.7 128.6 128.4 128.3 128.2 128.1 128.0 127.8 127.7 127.6 127.5 220.8 220.6 220.3 220.1 219.9 219.7 219.5 219.3 219.1 218.9
p
K
kPa
503.47 513.46 523.46 403.45 413.45 423.45 433.44 443.45 453.44 463.46 473.45 483.45 493.46 503.47 513.47 523.44 403.44 413.44 423.45 433.45 443.44 453.46 463.45 473.45 483.44 493.46 503.46 513.46 523.45 403.44 413.44 423.43 433.43 433.43 443.43 453.44 463.46 473.45 483.44 493.46 503.45
4290.5 4460.3 4629.7 2727.9 3064.7 3387.7 3703.4 4013.8 4319.3 4621.8 4919.9 5216.5 5509.7 5802.6 6092.7 6379.8 2774.7 3213.6 3637.3 4055.4 4469.0 4880.1 5285.9 5690.2 6093.0 6493.6 6891.7 7287.8 7680.8 2774.4 3284.4 3786.7 4286.7 4284.4 4783.2 5280.1 5775.9 6269.7 6761.7 7253.0 7742.3
ρ kg·m
T −3
218.7 218.4 218.2 325.0 324.7 324.4 324.1 323.8 323.4 323.1 322.8 322.5 322.2 321.9 321.6 321.3 402.7 402.3 402.0 401.6 401.2 400.8 400.4 400.0 399.6 399.3 398.9 398.5 398.1 460.7 460.2 459.8 459.3 459.3 458.9 458.5 458.0 457.6 457.1 456.7 456.3
p
K
kPa
513.42 523.41 403.44 413.43 423.42 433.42 443.42 453.42 463.44 473.43 483.43 493.42 503.44 513.43 523.44 403.43 413.42 423.42 433.42 443.42 453.42 463.42 473.43 483.44 493.44 503.45 403.45 413.46 423.46 433.45 443.45 453.46 463.47 473.46 403.45 413.45 423.45 433.45 443.44 453.46 463.45
8228.0 8713.2 2776.5 3371.4 3980.8 4598.0 5218.7 5843.1 6468.5 7093.2 7718.7 8344.4 8968.2 9591.2 10213.2 2784.5 3461.5 4173.8 4900.8 5638.1 6380.9 7127.1 7877.0 8628.9 9378.9 10129.7 2855.7 3739.9 4672.9 5628.3 6600.4 7584.8 8574.6 9568.9 3069.1 4177.9 5329.0 6506.9 7698.7 8905.0 10114.8
ρ kg·m
−3
455.8 455.4 535.5 535.0 534.4 533.9 533.4 532.9 532.4 531.9 531.4 530.8 530.3 529.8 529.3 594.5 594.0 593.4 592.8 592.3 591.7 591.1 590.5 590.0 589.4 588.8 688.4 687.7 687.0 686.4 685.7 685.0 684.4 683.7 755.5 754.8 754.0 753.3 752.6 751.8 751.1
T
p
ρ
K
kPa
kg·m−3
403.43 413.43 423.43 433.44 443.44 453.44 393.45 403.44 413.43 423.44 433.43 383.43 393.45 403.45 413.44 373.43 383.44 393.44 403.44 363.45 373.46 383.46 353.44 363.44 373.44 353.44 363.43 333.46 343.45 353.46 323.43 333.44 343.44
3331.6 4600.2 5906.9 7237.5 8584.0 9941.5 2531.0 4004.8 5530.3 7088.7 8666.9 2410.5 4410.6 6453.8 8521.8 1779.9 4128.8 6524.0 8946.0 2343.0 5302.7 8290.7 1232.2 4495.7 7789.6 4087.2 7766.9 1305.2 5602.3 9911.4 579.7 5332.4 10088.0
794.2 793.4 792.7 791.9 791.1 790.4 848.7 847.9 847.1 846.2 845.4 940.3 939.4 938.5 937.6 991.3 990.3 989.3 988.4 1061.2 1060.2 1059.2 1093.7 1092.6 1091.5 1128.3 1127.2 1180.7 1179.6 1178.4 1212.1 1210.9 1209.8
Standard uncertainties u are u(T) = 0.03 K and u(p) = 4 kPa. The relative expanded uncertainty Ur(ρ) is 0.005 for densities below 100 kg·m−3 and 0.004 for densities above 100 kg·m−3 (0.95 level of confidence). a
polynomial correlations based on the present data. Fifteen data points of saturated temperatures were obtained. They are presented in Table 4 and are graphically presented in Figure 4. The uncertainties of the saturated temperatures UTs were estimated from the following equation.
The parameters for the BWRS equation of state were determined from the present data at state points with densities below 1000 kg·m−3 because the BWRS equation is considered less suitable at higher densities. The regressed parameters are listed in Table 3. The deviations of the present data from the equation are shown in Figure 3. The relative standard and maximum deviations of the present data from the BWRS equation at densities below 1000 kg·m−3 were within 0.5% and 1.4%, respectively. The deviations at densities above 1000 kg·m−3 were within ±4% for most data points and higher than 4% for five data points. The saturated temperatures were determined from the intersections of the vapor pressure curve and isochores. The vapor pressure curve was used for the correlation developed in our previous work.2 The isochores were represented as
⎛ ∂T ⎞2 UTs = 2 (ups 2 + upi 2)⎜ ⎟ + uT 2 ⎝ ∂p ⎠
(2)
where ups is the uncertainty of the vapor pressure, upi is the uncertainty of the pressure by the isochore, uT is the uncertainty of the temperature, and (∂T∂p) can be calculated from the vapor pressure correlation. The present data were in good agreement with the calculations presented in our previous work.2 2451
DOI: 10.1021/acs.jced.7b00381 J. Chem. Eng. Data 2017, 62, 2450−2453
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Figure 1. Distribution of the pρT property data for HFO-1336mzz(E) in a pressure−temperature diagram. Broken line denotes the calculation of the phase boundary by our previous work.2
Figure 3. Deviations against density in the data from the equation of state.
Table 4. Saturated Densities and Temperature of HFO1336mzz(E)
Figure 2. Distribution of the pρT property data for HFO-1336mzz(E) on pressure−density diagram: (◎) critical point;2 (---) calculations of the phase boundary by our previous work;2 () calculation by eq 1 with the parameters determined in this work.
ρs/kg·m−3
T/K
84.0 129.3 221.0 325.1 688.5 755.8 794.8 848.9 940.6 991.4 1061.7 1093.7 1129.3 1180.9 1212.2
360.52 ± 0.21 376.04 ± 0.19 393.49 ± 0.17 401.93 ± 0.22 401.57 ± 0.43 398.61 ± 0.34 396.05 ± 0.23 390.98 ± 0.23 380.00 ± 0.18 372.08 ± 0.22 359.20 ± 0.19 352.53 ± 0.21 344.38 ± 0.24 331.70 ± 0.31 323.12 ± 0.37
Table 3. Parameters for the BWRS Equation of State for HFO1336mzz(E) A0 B0 C0 D0 E0 a b c d α γ R p T ρ
3.90515 × 10−2 1.07566 × 10−3 6.28766 × 103 2.57639 × 105 4.72705 × 106 1.75060 × 10−4 4.21016 × 10−6 6.79941 × 100 −3.76919 × 10−2 2.86504 × 10−8 2.35793 × 10−6 5.06828 × 10−2 kPa K kg·m−3
Figure 4. Saturated densities of HFO-1336mzz(E): (◎) critical point;2 (×) this work; (---) calculations of the phase boundary by our previous work.2
densities below 1000 kg·m−3 with relative standard and maximum deviations within 0.5% and 1.4%, respectively. In addition, 15 data points of saturated temperatures were obtained. The present data will be useful in estimating the thermodynamic performance of heat pump cycles and organic Rankine cycles with HFO-1336mzz(E) as the working fluid.
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CONCLUSION The pρT properties of HFO-1336mzz(E) were measured by the isochoric method. A total of 154 pρT data points were obtained. The measured data were correlated with the BWRS equation of state. The BWRS equation represents the present data at
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Tel.: +81−47−469−8396. Fax: +81−47−467−9504. 2452
DOI: 10.1021/acs.jced.7b00381 J. Chem. Eng. Data 2017, 62, 2450−2453
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ORCID
Katsuyuki Tanaka: 0000-0003-1042-3755 Notes
The authors declare no competing financial interest.
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REFERENCES
(1) Kontomaris, K. K.; Simoni, L. D. A low GWP working fluid for heating and power generation from low temperature heat: HFO1336mzz(E). Proceedings of the JRAIA International Symposium, December 1, 2016, Kobe, Japan. (2) Tanaka, K.; Ishikawa, J.; Kontomaris, K. K. Thermodynamic properties of HFO−1336mzz(E) (trans−1,1,1,4,4,4−hexafluoro−2− butane) at saturation conditions. Int. J. Refrig. 2017, doi.org/10.1016/j. ijrefrig.2017.06.012. (3) Starling, K. E.; Han, M. S. Thermo data refined for LPG [liquefied petroleum gas]. 14. Mixtures. Hydrocarbon Process 1972, 51, 129−132. (4) Tanaka, K.; Akasaka, R.; Sakaue, E.; Ishikawa, J.; Kontomaris, K. K. Thermodynamic properties of cis−1,1,1,4,4,4−hexafluoro−2−butene: Measurements of the pρT Property and Determinations of Vapor Pressures, Saturated Liquid and Vapor Densities, and Critical Parameters. J. Chem. Eng. Data 2016, 61, 2467−2473.
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DOI: 10.1021/acs.jced.7b00381 J. Chem. Eng. Data 2017, 62, 2450−2453
