Measurement of pρT Properties of 1, 1, 1, 2, 2, 4, 5, 5, 5-Nonafluoro-4

Nov 1, 2016 - for use in next generation organic Rankine cycle systems because its GWP (global warming potential) is 1. However, there is insufficient...
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Measurement of pρT Properties of 1,1,1,2,2,4,5,5,5-Nonafluoro-4(trifluoromethyl)-3-pentanone in the Near-Critical and Supercritical Regions Katsuyuki Tanaka* Department of Precision Machinery Engineering, Nihon University, Chiba 274−8501, Japan ABSTRACT: In this work, measurements of pρT (pressure−density−temperature) properties of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone in the near-critical and supercritical regions were carried out. This novel fluid has potential for use in next generation organic Rankine cycle systems because its GWP (global warming potential) is 1. However, there is insufficient data available especially near the critical point. In this work, 155 pρT data points of 1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3-pentanone along 21 isochores were obtained for densities between 107 and 1526 kg·m−3, for temperatures ranging from 333.5 to 523.5 K, and at pressures up to 10 MPa. The experimental uncertainties in the measurements of temperatures, pressures, and densities were estimated to be 0.028 K, 4 kPa, and 0.5%, respectively. For densities above 200 kg·m−3, the uncertainty is 0.4%.

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INTRODUCTION 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone is expected to be a next generation working fluid because it has no ozone depletion potential (ODP) and low global warming potential (GWP). This novel fluid is already synthesized and traded as Novec649 by 3M. Thermodynamic properties of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone can be calculated with REFPROP, but experimental data are limited. McLinden et al.1 presented the equation of state for 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, including experimental data of vapor pressure, pρT properties, and the speed of sound.1 Their equation of state can be used with the NIST REFPROP database.3 Almost all of their experimental data for pρT properties are distributed in the liquid phase. In this work, measurements of pρT (pressure− density−temperature) properties of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone were carried out at temperatures ranging from 333.5 to 523.5 K and pressures up to 10 MPa in the density range from 107 to 1526 kg·m−3 including near the critical density3 of 606 kg·m−3.

(OMEGA, PX1009). The pρT properties can be obtained along the isochoric line. The sample was of commercial grade and was obtained from 3M. The sample information is listed in Table 1. The Table 1. Sample information

a

CAS Reg. No.

purity, %

manufacture

756−13−8

99.5

3M

1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone.

experimental uncertainties in the measurements of temperatures, pressures, and densities were estimated to be 0.028 K, 4 kPa, and 0.5%, respectively. For densities above 200 kg·m−3, the uncertainty is 0.4%.

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RESULTS AND DISCUSSION The data of pρT properties were obtained in the temperature range from 333 to 523 K and at pressures up to 10 MPa along 21 isochores. The data are presented in Table 2 and graphically shown in Figure 1. The data by McLinden et al.1 were taken at temperatures ranging from 225 to 470 K and for densities ranging from 35 to 1821 kg·m−3, but almost all of the densities were above 1000 kg·m−3. The present data were taken for densities ranging from 107 to 1526 kg·m−3; almost all of the present data were taken at densities ranging from 100 to 1000 kg·m−3 and near a critical density1 of 606 kg·m−3. Density deviations of the experimental data from the calculations with the equation of state by McLinden et al.1 are shown against density in Figure 2, temperature in Figure 3,

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EXPERIMENTAL APPARATUS AND METHOD The measurements were carried out with the isochoric method previously employed to measure the pρT properties of fluids.2 The apparatus and experimental procedures are described in detail elsewhere.2 A sample of known mass is filled in a constant volume cell (about 10 cm3). The density of the sample is obtained from the volume of the sample cell and the mass of the sample in the cell. The temperature of the sample is controlled by a thermostatic oil bath that can operate in the temperature range 323−523 K. The temperature of the oil bath is measured with a temperature sensor (CHINO, R900-F25AD). The pressure of the sample is measured with a pressure sensor © 2016 American Chemical Society

sample Novec649a

Received: September 1, 2016 Accepted: October 24, 2016 Published: November 1, 2016 3958

DOI: 10.1021/acs.jced.6b00772 J. Chem. Eng. Data 2016, 61, 3958−3961

Journal of Chemical & Engineering Data

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Table 2. Experimental Values of the Pressure p, Temperature T, and Density ρ for 1,1,1,2,2,4,5,5,5-Nonafluoro-4(trifluoromethyl)-3-pentanonea T/K

p/kPa

ρ/(kg·m−3)

T/K

p/kPa

ρ/(kg·m−3)

T/K

p/kPa

ρ/(kg·m−3)

403.46 413.48 423.49 433.49 443.49 453.49 463.50 473.50 483.51 493.51 503.51 513.50 523.50 433.46 443.48 453.50 463.48 473.50 483.49 493.49 503.50 513.49 523.50 443.47 453.50 463.49 473.49 483.49 493.49 503.50 513.49 523.49 443.48 453.49 463.50 473.50 483.49 493.49 503.51 513.51 523.50 443.49 453.53 463.51 473.51 483.52 493.54 503.52 513.53 523.52 443.48 453.49

831.5 873.1 913.6 953.3 991.3 1028.2 1065.3 1102.0 1138.4 1174.7 1210.7 1245.5 1281.4 1423.0 1517.2 1608.6 1697.6 1785.0 1870.9 1955.0 2038.9 2121.4 2203.4 1703.9 1836.0 1963.3 2087.5 2209.8 2329.9 2448.7 2565.8 2682.3 1862.8 2074.0 2277.3 2476.2 2672.1 2865.0 3055.8 3244.9 3433.0 1905.5 2192.7 2470.7 2746.7 3020.8 3292.9 3562.4 3830.9 4099.2 1909.2 2237.3

107.8 107.8 107.7 107.7 107.6 107.6 107.5 107.5 107.4 107.4 107.3 107.3 107.2 209.1 209.0 208.9 208.8 208.7 208.6 208.5 208.4 208.3 208.2 270.5 270.4 270.2 270.1 270.0 269.9 269.7 269.6 269.5 384.5 384.3 384.1 383.9 383.8 383.6 383.4 383.2 383.0 490.7 490.4 490.2 490.0 489.7 489.5 489.3 489.0 488.8 553.6 553.3

463.50 473.50 483.51 493.52 503.53 513.52 523.54 443.50 453.50 463.50 473.50 483.50 493.50 503.51 513.50 523.49 443.49 453.49 463.50 473.49 483.50 493.50 503.52 513.50 523.52 443.50 453.52 463.51 473.53 483.52 493.52 503.53 513.54 523.53 443.50 453.50 463.51 473.52 483.52 493.51 503.53 513.52 523.53 443.50 453.52 463.52 473.52 483.52 493.52 503.53 513.52 523.54

2561.8 2884.8 3208.9 3532.9 3855.8 4177.8 4499.9 1925.1 2302.1 2685.7 3074.2 3464.6 3858.2 4251.2 4646.1 5040.8 1950.5 2415.6 2908.5 3412.0 3924.7 4442.7 4964.5 5488.2 6015.2 1983.4 2543.8 3127.9 3727.6 4336.7 4954.4 5577.4 6204.5 6832.9 2050.5 2679.9 3336.1 4008.9 4691.3 5382.6 6079.9 6780.4 7485.5 2089.1 2753.3 3442.0 4147.0 4863.8 5589.2 6319.5 7055.0 7793.7

553.0 552.8 552.5 552.2 552.0 551.7 551.5 626.4 626.1 625.8 625.5 625.2 624.9 624.7 624.4 624.1 733.6 733.2 732.9 732.5 732.2 731.8 731.5 731.1 730.8 797.9 797.5 797.1 796.7 796.4 796.0 795.6 795.2 794.9 844.7 844.3 843.9 843.5 843.1 842.7 842.3 841.9 841.5 861.9 861.5 861.1 860.7 860.3 859.9 859.5 859.1 858.7

443.48 453.48 463.50 473.49 483.48 493.50 503.49 513.50 523.49 433.49 443.50 453.51 463.52 473.51 483.52 493.53 503.53 513.53 433.48 443.50 453.51 463.49 473.51 483.50 493.50 413.46 423.47 433.47 443.48 453.49 463.50 403.48 413.48 423.49 433.49 443.50 453.52 393.50 403.50 413.50 423.49 373.46 383.46 393.47 403.46 353.46 363.45 373.46 343.46 353.46 333.47

2368.4 3187.2 4032.8 4891.4 5762.4 6642.5 7526.9 8416.4 9308.2 1785.7 2696.6 3642.6 4610.0 5591.7 6584.0 7585.3 8592.1 9599.7 2354.6 3478.7 4628.3 5794.1 6974.8 8161.0 9354.4 1666.3 3219.0 4799.8 6401.8 8016.6 9636.7 1044.1 2784.0 4554.9 6349.0 8156.2 9972.1 1730.8 3917.8 6126.2 8348.4 849.3 3567.3 6308.0 9056.2 597.1 4019.0 7450.4 3695.1 7818.2 4628.4

932.0 931.6 931.2 930.7 930.3 929.8 929.4 928.9 928.5 980.1 979.6 979.1 978.7 978.2 977.8 977.3 976.8 976.4 1044.1 1043.6 1043.2 1042.7 1042.2 1041.7 1041.2 1157.5 1156.9 1156.4 1155.8 1155.3 1154.7 1195.8 1195.2 1194.6 1194.1 1193.5 1192.9 1273.5 1272.9 1272.3 1271.7 1348.0 1347.4 1346.8 1346.1 1425.9 1425.2 1424.5 1489.0 1488.3 1526.2

Standard uncertainties u are u(T) = 0.028 K and u(p) = 4 kPa. The relative expanded uncertainty Ur(ρ) is 0.005 for densities below 200 kg·m−3 and 0.004 for densities above 200 kg·m−3 (0.95 level of confidence). a

and pressure in Figure 4. The data of McLinden et al.1 are in good agreement with the calculations because the equation of state was developed by them. The present data excluding those at the near-critical point are in good agreement with the

calculations within 1%. However, the data near the critical point have large deviations. Especially, the deviations in the vicinity of the critical temperature1 of 448.81 K and critical density1 of 606 kg·m−3 are larger, with deviations of 9.5%, 20.0%, and 11.1% at 3959

DOI: 10.1021/acs.jced.6b00772 J. Chem. Eng. Data 2016, 61, 3958−3961

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Figure 4. Deviations against the pressure in the data from the equation of state by McLinden et al.:1 ×, this work; ○, McLinden et al.1

Figure 1. Distribution of the pρT property data for 1,1,1,2,2,4,5,5,5nonafluoro-4-(trifluoromethyl)-3-pentanone in a temperature−density diagram: ×, this work; ○, McLinden et al.;1 −, calculation of the phase boundary by McLinden et al.1

T = 443.49 K, p = 1905.5 kPa, and ρ = 490.7 kg·m−3; at T = 443.48 K, p = 1909.2 kPa, and ρ = 553.6 kg·m−3; and at T = 443.50 K, p = 1925.1 kPa, and ρ = 626.4 kg·m−3, respectively. It can be assumed that the equation of state was developed with insufficient data near the critical density. The present data can compensate for the lack of data near the critical point and can be used in the development of the next equation of state.

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CONCLUSION Measurements of the pρT properties of 1,1,1,2,2,4,5,5,5nonafluoro-4-(trifluoromethyl)-3-pentanone near the critical region were performed with the isochoric method. A set of 155 data points was obtained along 21 isotherms. The present data can compensate for the lack of existing data for pρT properties of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone.

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AUTHOR INFORMATION

Corresponding Author

Figure 2. Deviations against density in the data from the equation of state by McLinden et al.:1 ×, this work; ○, McLinden et al.1

*E-mail: [email protected]. Tel.: +81−47−469−8396. Fax: +81−47−467−9504. Funding

This work was supported by the Japan Science and Technology Agency (JST) under the Strategic International Collaborative Research Program (SICORP). Notes

The author declares no competing financial interest.

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REFERENCES

(1) McLinden, M. O.; Perkins, R. A.; Lemmon, E. W.; Fortin, T. J. Thermodynamic Properties of 1, 1, 1, 2, 2, 4, 5, 5, 5-Nonafluoro-4(trifluoromethyl)-3-pentanone: Vapor pressure, (p, ρ, T) Behavior, and Speed of Sound Measurements, and an Equation of State. J. Chem. Eng. Data 2015, 60, 3646−3659. (2) Tanaka, K.; Akasaka, R.; Sakaue, E.; Ishikawa, J.; Kontomaris, K. K. Thermodynamic properties of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)): 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. (3) Lemmon, E. W.; Huber, M. L.; McLinden, M. O. NIST Reference Fluid Thermodynamic and Transport Properties−REFPROP, version 9.1; NIST Standard Reference Database 23; Standard Reference Data

Figure 3. Deviations against temperature in the data from the equation of state by McLinden et al.:1 ×, this work; ○, McLinden et al.1

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DOI: 10.1021/acs.jced.6b00772 J. Chem. Eng. Data 2016, 61, 3958−3961

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Program, National Institute of Standards and Technology: Gaithersburg, MD, USA, 2013.

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DOI: 10.1021/acs.jced.6b00772 J. Chem. Eng. Data 2016, 61, 3958−3961