Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Measurement and Correlation of the Liquid Density and Viscosity of HFO-1336mzz(Z) (cis-1,1,1,4,4,4-Hexafluoro-2-butene) at High Pressure Yukun Sun,† Xiaojing Li,‡ Xianyang Meng,† and Jiangtao Wu*,† †
J. Chem. Eng. Data Downloaded from pubs.acs.org by KAOHSIUNG MEDICAL UNIV on 10/18/18. For personal use only.
Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China ‡ School of Energy Power and Mechanical Engineering, North China Electric Power University, Baoding, Hebei 071000, China ABSTRACT: This work reported experimental measurements of the density and viscosity of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)) over wide ranges of temperature and pressure. The experimental density measurements of HFO-1336mzz(Z) were carried out by a vibrating-tube densimeter over the temperature range 283−373 K and at pressures up to 100 MPa. The measured viscosity data were obtained by a vibrating-wire viscometer at temperatures from 253 to 353 K and pressures up to 40 MPa. In the density system, the combined expanded uncertainties of the temperature, pressure, and density with a level of confidence of 0.95 (k = 2) were estimated to be Uc(T) = 16 mK, Uc(p) = 0.062 MPa (p ≤ 60 MPa), Uc(p) = 0.192 MPa (60 MPa < p ≤ 140 MPa), and from 0.026 to 0.063% depending on the temperature and pressure ranges. The relative combined expanded uncertainty with a confidence level of 0.95 (k = 2) of the reported viscosity data was 2.0%. The deviations between the experimental density data and the Helmholtz equation of state at temperatures from 283 to 373 K and pressures up to 40 MPa were less than 0.11%. A semiempirical equation has been developed using viscosity experimental data with the hardsphere model, which could reproduce the results well.
1. INTRODUCTION Heat pump and organic Rankine cycle (ORC) have attracted significant attention in recent years due to the requirement of energy saving and the awareness of environmental impacts. However, according to the Paris Agreement and Kigali Agreement, the traditional working fluids with high GWP, such as HFC-245fa (ODP = 0, GWP = 10301), should be phased out gradually. Alternatives that could meet the requirements of both thermodynamic properties and environmental compatibility were still eager to be developed. HFO-1336mzz(Z) (cis-CF3CHCHCF3, ODP = 0, GWP = 2), previously also referred to as DR-2, was recently discussed as a developmental working fluid for various applications, including air conditioning chillers, high temperature heat pumps, and organic Rankine cycles.2 Some studies showed that HFO1336mzz(Z) had equivalent or even superior performance compared to conventional refrigerants.3−6 In addition to excellent thermodynamic performance, it had a CC double bond in the molecule which is the key feature facilitating the low global warming characteristic and low atmospheric lifetime. Even more surprisingly, HFO-1336mzz(Z) remained chemically stable at high temperatures despite its unsaturated chemical nature and had a relatively high critical temperature of 444.50 K, which resulted in relatively low vapor pressure and high cycle energy efficiencies.2 Accurate knowledge of the thermophysical properties of HFO-1336mzz(Z) was necessary to develop an accurate equation © XXXX American Chemical Society
of state, evaluate the performance potential of relevant systems, and design the proper components. However, the present experimentally determined thermophysical data of HFO-1336mzz(Z) were still limited. There was only one literature presenting experimental pρT data by the isochoric method along 26 isochores in the temperature range 323−503 K and at pressures up to 10 MPa.7 The Helmholtz equation of state developed by McLinden and Akasaka8 over a temperature range of 182−500 K and at pressures up to 46 MPa with a maximum density of 1637.3 kg·m−3 could be obtained from the new version of NIST REFPROP.9 Alam et al.10 measured the thermal conductivity of liquid and gaseous HFO-1336mzz(Z) by the transient hot-wire method. Just recently, the viscosity data of HFO-1336mzz(Z) were only reported by a tandem capillary tube method at temperatures from 314 to 434 K for liquid and vapor phases, respectively, in the pressure range from 0.5 to 4.0 MPa.11 There was no literature reported for the liquid phase viscosity of HFO1336mzz(Z) at high pressure. In this work, the compressed liquid densities of HFO1336mzz(Z) were measured by a vibrating-tube densimeter over Special Issue: Proceedings of the 20th Symposium on Thermophysical Properties Received: August 14, 2018 Accepted: September 27, 2018
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DOI: 10.1021/acs.jced.8b00713 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
high pressure transducer with a pressure range up to 100 MPa and a precision grade of 0.1%. The pressure transducer signal was measured by a nanovolt meter with 7 1/2 digits resolution. The combined expanded uncertainty of pressure measurements were Uc(p) = 0.12 MPa, with a level of confidence of 0.95 (k = 2). The temperature was controlled and measured with the same devices used by the density measurement. The combined expanded uncertainty of temperature measurements were Uc(T) = 12 mK, with a level of confidence of 0.95 (k = 2). Calibration was carried out to obtain the internal damping Δ0 and the radius of tungsten wire R in a vacuum and toluene, respectively, which was discussed in our previous work.18 The system was washed by solvents such as ethanol, acetone, and testing fluids and was evacuated to avoid the impurities before the experiment. The relative combined expanded uncertainty of viscosity was 2% with a level of confidence of 0.95 (k = 2), taking into account the uncertainties of repeatability of measurement, pressure, temperature, and the density of the fluid calculated from the equation of state.9
the temperature range from 283 to 373 K and at pressures up to 100 MPa to extend the pressure range of density data available. The compressed liquid viscosities of HFO-1336mzz(Z) were reported, measured by a vibrating-wire viscometer over a temperature range of 253−353 K and at pressures up to 40 MPa.
2. EXPERIMENTAL SECTION 2.1. Experimental Material. The sample of HFO1336mzz(Z) was provided by Beijing Yuji Science & Technology Co. Ltd., China, with a nominal mass purity specification higher than 99%. No additional purification was performed. The sample purity was analyzed at least three times by a gas chromatograph combined with a thermal conductivity detector and a capillary column (60 m × 0.32 mm), and the results for HFO1336mzz(Z) were higher than 0.9988. The specification of the sample used in this work was listed in Table 1. Table 1. Sample Information chemical name
CAS no.
formula
initial mass fraction purity
GC area fraction
HFO-1336mzz(Z)
692-49-9
C4H2F6
0.99
0.9988
3. EXPERIMENTAL RESULTS 3.1. Density. The densities of compressed liquid HFO1336mzz(Z) were measured at T = 283.15, 293.15, 303.15, 313.15, 323.15, 333.15, 343.15, 353.15, 363.15, and 373.15 K and at pressures from 0.1 to 100 MPa, as shown in Table 2. The distribution of our measurements and the only one literature data set of Tanaka et al.7 in the pressure−temperature diagram were shown in Figure 1. The relative expanded (k = 2) uncertainty was calculated with a maximum value of 0.063%. 3.2. Viscosity. The viscosities of compressed liquid HFO1336mzz(Z) were measured at temperatures of T = 253.15, 263.15, 273.15, 283.15, 293.15, 303.15, 313.15, 323.15, 333.15, 343.15, and 353.15 K and at pressures from 0.1 to 40 MPa, as shown in Table 3. The distribution of our measurements and the only one literature data set of Alam et al.11 in the pressure− temperature diagram were shown in Figure 2. As the discussion in section 4.1, the small deviations between the experimental density data in this work and the REFPROP were observed at pressures below 40 MPa which would have less effect on viscosity results (0.1% change in density caused less than 0.1% change in viscosity), and the experimental measurements for density and viscosity were not performed at exactly the same temperature and pressure. Therefore, the densities used in viscosity measurement were calculated from REFPROP. The viscosity data as a function of pressure at different temperatures were shown in Figure 3.
2.2. Density Measurement. The vibrating-tube densimeter used in this work has been introduced previously including a schematic diagram and detailed description.12−17 Only a brief introduction was given here. The Anton Paar DMA HPM and a model mPDS 2000 V3 evaluation unit were used to measure density. The temperature was controlled by a refrigeration circulator with silicon oil and was measured by a 100 Ω platinum resistance thermometer connected to an Agilent 3458A 8 1/2 digital multimeter. The combined expanded uncertainty Uc (k = 2, level of confidence = 0.95) was Uc(T) = 16 mK. Different pressures were generated by a piston screw pump controlled by a stepping motor and were measured by a Druck model UNIK 5000 (up to 70 MPa with accuracy of 0.04%) less than or equal to 60 MPa and a Viatran model 345 series (up to 140 MPa with an accuracy of 0.1%) over 60 MPa. The combined expanded uncertainties Uc (k = 2, level of confidence = 0.95) were Uc(p) = 0.062 MPa (p ≤ 60 MPa) and Uc(p) = 0.192 MPa (60 MPa < p ≤ 140 MPa), respectively. Before the experiment, this apparatus was calibrated with a vacuum and water measuring over the entire temperature and pressure ranges. 2.3. Viscosity Measurement. The vibrating wire viscometer in a steady-state mode used in this work has been described in our previous publicions.18,19 A tungsten wire with a nominal diameter of 0.1 mm and length of 58 mm was clamped by stainless steel pieces at both ends. The two clamps were separated from each other by a machinable glass ceramic tube. The magnetic field was generated by two parallel samarium−cobalt magnets of 6 mm distance and 40 mm length (Sm2Co17). The cell was mounted inside a custom-made stainless-steel vessel sealed with metal gaskets and flanges. Two wires were drawn from each end of the tungsten wire to connect the measuring circuit and the instrument. About 60 mL of sample was required for the experimental device. A sinusoidal voltage achieved by a function generator drove the wire’s transverse oscillation motion immersed in the testing fluid, and then a lock-in amplifier detected the in-phase and quadrature voltages of the signal across the wire over the frequency range to calculate the viscosity. The pressure was generated by a manual piston pump with a maximum working pressure of 100 MPa and was measured by a
4. DISCUSSION 4.1. Density. To our best knowledge, only one available experimental density source of HFO-1336mzz(Z) was found in the published literature. Tanaka et al.7 measured 344 pρT data points along 26 isochores between 88 and 1295 kg·m−3 in the temperature range from 323 to 503 K and at pressures up to 10 MPa covering single-phase liquid and vapor regions, twophase region, and supercritical region. The experimental uncertainties of temperatures, pressures, densities below 100 kg·m−3, and higher densities were estimated to be 0.028 K, 4 kPa, 0.6%, and 0.4%, respectively. Deviations in liquid density data of Tanaka et al.7 and our experimental data from the calculated data obtained in REFPROP as a function of temperature were shown in Figure 4 except for one point at T = 443.49 K, p = 2.9 MPa with a deviation of 4.0%. The experimental data of Tanaka et al.7 B
DOI: 10.1021/acs.jced.8b00713 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 2. Experimental Values of Density ρ for HFO-1336mzz(Z) at Different Temperatures T and Pressures pa T/K
p/MPa
ρexpb/kg·m−3
Ucc(k = 2)/%
ρcald/kg·m−3
deviatione/%
283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.16 293.16 293.15 293.15 293.15 303.15 303.15 303.16 303.16 303.15 303.15 303.16 303.15 303.15 303.16 303.15 303.15 303.15 303.15 313.15 313.14 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.16 313.16 313.15 313.14 323.15 323.15 323.16 323.14 323.14
0.10 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.00 100.00 0.10 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.01 99.99 0.10 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.00 100.01 0.50 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.01 100.01 0.50 1.00 2.00 5.00 10.00
1402.57 1405.16 1408.09 1416.40 1429.39 1441.21 1452.25 1462.46 1472.00 1489.73 1505.53 1520.01 1545.15 1566.76 1377.12 1380.09 1383.27 1392.34 1406.41 1419.13 1430.86 1441.76 1451.97 1470.38 1486.98 1501.97 1528.17 1550.16 1351.47 1354.72 1358.24 1368.33 1383.63 1397.49 1410.02 1421.76 1432.55 1452.02 1469.43 1485.09 1512.19 1535.09 1325.41 1327.46 1331.40 1342.64 1359.50 1374.49 1388.16 1400.64 1412.04 1432.78 1451.06 1467.37 1495.94 1519.55 1297.83 1300.12 1304.59 1317.21 1335.83
0.029 0.029 0.029 0.029 0.028 0.028 0.028 0.028 0.027 0.027 0.027 0.026 0.029 0.028 0.030 0.030 0.030 0.029 0.029 0.028 0.028 0.028 0.027 0.027 0.027 0.026 0.030 0.029 0.031 0.031 0.031 0.030 0.029 0.029 0.028 0.028 0.028 0.027 0.027 0.026 0.030 0.029 0.033 0.033 0.032 0.031 0.030 0.029 0.029 0.028 0.028 0.027 0.027 0.027 0.031 0.029 0.035 0.034 0.034 0.033 0.031
1403.20 1405.79 1408.61 1416.77 1429.41 1441.02 1451.82 1461.91 1471.41 1488.92 1504.80 1519.38f 1545.48 1568.50 1377.73 1380.65 1383.78 1392.79 1406.62 1419.26 1430.90 1441.74 1451.88 1470.44 1487.19 1502.52 1529.81 1553.70 1351.60 1354.84 1358.33 1368.33 1383.55 1397.29 1409.85 1421.49 1432.32 1452.03 1469.72 1485.81 1514.29 1539.12 1326.28 1328.33 1332.26 1343.40 1360.16 1375.12 1388.72 1401.20 1412.77 1433.70 1452.34 1469.20 1498.96 1524.72 1298.58 1300.86 1305.30 1317.83 1336.36
−0.045 −0.045 −0.037 −0.026 −0.001 0.013 0.030 0.037 0.040 0.054 0.048 0.042 −0.021 −0.111 −0.044 −0.041 −0.037 −0.032 −0.015 −0.009 −0.003 0.001 0.006 −0.004 −0.014 −0.036 −0.107 −0.228 −0.010 −0.009 −0.006 0.000 0.006 0.014 0.012 0.019 0.016 −0.001 −0.020 −0.049 −0.139 −0.263 −0.066 −0.065 −0.064 −0.057 −0.048 −0.046 −0.040 −0.040 −0.052 −0.064 −0.088 −0.125 −0.202 −0.340 −0.058 −0.057 −0.054 −0.047 −0.039
C
DOI: 10.1021/acs.jced.8b00713 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 2. continued T/K
p/MPa
ρexpb/kg·m−3
Ucc(k = 2)/%
ρcald/kg·m−3
deviatione/%
323.15 323.15 323.15 323.15 323.15 323.15 323.16 323.15 323.15 333.16 333.15 333.16 333.15 333.16 333.16 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 343.16 343.16 343.15 343.16 343.16 343.15 343.16 343.16 343.16 343.15 343.15 343.15 343.15 343.15 353.15 353.15 353.16 353.16 353.15 353.16 353.15 353.15 353.15 353.15 353.15 353.15 353.15 363.15 363.16 363.16 363.15 363.16 363.16 363.15 363.15 363.16 363.16 363.15
15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.01 100.01 0.50 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.00 100.00 0.50 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.00 100.00 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00 80.01 100.00 1.00 2.00 5.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 60.00
1352.25 1366.96 1380.35 1392.69 1414.60 1433.91 1451.12 1480.77 1505.41 1269.32 1271.96 1277.07 1291.31 1312.03 1330.02 1346.00 1360.41 1373.57 1396.93 1417.34 1435.25 1466.47 1492.09 1239.61 1242.66 1248.57 1264.73 1287.86 1307.63 1324.98 1340.52 1354.59 1379.44 1400.93 1419.91 1452.33 1478.79 1211.33 1218.18 1236.75 1262.64 1284.42 1303.28 1320.02 1335.13 1361.50 1384.21 1404.05 1438.01 1465.73 1177.46 1185.52 1207.05 1236.32 1260.38 1280.92 1298.98 1315.14 1343.17 1367.09 1387.96
0.030 0.029 0.029 0.028 0.028 0.027 0.027 0.031 0.030 0.037 0.037 0.036 0.034 0.032 0.031 0.030 0.029 0.029 0.028 0.027 0.027 0.032 0.030 0.041 0.041 0.039 0.037 0.034 0.032 0.031 0.030 0.029 0.028 0.028 0.027 0.032 0.030 0.046 0.044 0.040 0.036 0.033 0.032 0.031 0.030 0.029 0.028 0.027 0.033 0.031 0.053 0.050 0.044 0.038 0.035 0.033 0.031 0.030 0.029 0.028 0.028
1352.71 1367.42 1380.83 1393.19 1415.41 1435.06 1452.74 1483.76 1510.47 1269.72 1272.35 1277.42 1291.53 1312.11 1330.01 1345.96 1360.39 1373.59 1397.17 1417.89 1436.42 1468.72 1496.42 1239.53 1242.56 1248.42 1264.44 1287.39 1307.05 1324.34 1339.85 1353.96 1378.98 1400.79 1420.21 1453.85 1482.53 1211.19 1218.01 1236.40 1262.14 1283.77 1302.55 1319.25 1334.34 1360.86 1383.81 1404.13 1439.14 1468.82 1177.84 1185.90 1207.26 1236.30 1260.13 1280.55 1298.55 1314.67 1342.78 1366.92 1388.19
−0.034 −0.034 −0.035 −0.036 −0.057 −0.080 −0.112 −0.202 −0.336 −0.032 −0.030 −0.027 −0.017 −0.006 0.001 0.003 0.001 −0.001 −0.017 −0.038 −0.082 −0.153 −0.290 0.006 0.008 0.012 0.023 0.037 0.044 0.048 0.050 0.047 0.034 0.010 −0.021 −0.105 −0.253 0.012 0.014 0.028 0.040 0.051 0.056 0.058 0.059 0.047 0.029 −0.006 −0.078 −0.211 −0.032 −0.032 −0.018 0.002 0.020 0.029 0.033 0.036 0.029 0.013 −0.017
D
DOI: 10.1021/acs.jced.8b00713 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 2. continued T/K
p/MPa
ρexpb/kg·m−3
Ucc(k = 2)/%
ρcald/kg·m−3
deviatione/%
363.15 363.16 373.15 373.16 373.15 373.15 373.15 373.16 373.15 373.15 373.16 373.15 373.15 373.15 373.15
79.99 100.00 1.00 2.00 5.00 10.02 15.00 20.02 25.00 30.00 40.00 50.00 60.00 80.01 100.01
1423.19 1451.81 1140.74 1150.47 1175.78 1209.06 1235.47 1257.86 1277.24 1294.44 1324.14 1349.23 1370.99 1407.73 1437.36
0.034 0.031 0.063 0.058 0.049 0.041 0.037 0.034 0.032 0.031 0.029 0.029 0.028 0.034 0.032
1424.58 1455.27 1141.97 1151.70 1176.80 1209.89 1236.16 1258.44 1277.74 1294.98 1324.77 1350.15 1372.38 1410.22 1441.94
−0.098 −0.238 −0.108 −0.107 −0.087 −0.069 −0.056 −0.046 −0.039 −0.041 −0.048 −0.068 −0.102 −0.177 −0.319
a The combined expanded uncertainties Uc(k = 2) were Uc(T) = 16 mK, Uc(p) = 0.062 MPa (p ≤ 60 MPa), and Uc(p) = 0.192 MPa (60 MPa < p ≤ 140 MPa) with a confidence level of 0.95. bρexp was the experimental density of HFO-1336mzz(Z). cRelative expanded uncertainties Uc(k = 2) for density were calculated with the method in Qiu et al.12 dρcal was the density value calculated from NIST REFPROP.9 eRelative deviation/% = 100(ρexp − ρcal)/ρexp. fThose data points in italics were beyond the range of the EOS from NIST REFPROP.
where η* was the characteristic viscosity, η was the experimental viscosity in Pa·s, M was the molar mass (0.16406 kg·mol−1 for HFO-1336mzz), T was the absolute temperature in K, R = 8.314472 J·mol−1·K−1 was the universal gas constant, and V was the molar volume in m3·mol−1. The characteristic viscosity η* was proven to depend only on V/V0. The relationship could be expressed as iV y log(η*/R η) = ∑ aijjj 0 zzz V{ i=0 k
i
7
where α0 = 1.0945, α1 = −9.26324, α2 = 71.0385, α3 = −301.9012, α4 = 797.6900, α5 = −1221.9770, α6 = 987.5574, and α7 = −319.4636.21 The proportionality factor, Rη, reflecting the degree of coupling between translational and rotational motions of the molecules was independent of temperature and pressure. V0 was the characteristic molar volume in m3·mol−1, which depended on temperature, given by
Figure 1. Distribution of the density data for HFO-1336mzz(Z). Blue △, this work; red ○, Tanaka et al.;7 olive ◇, Tanaka et al.7 (near the critical point); , vapor−liquid saturation boundary.
below 444 K were in good agreement (deviation
