Compressed Liquid Viscosity Measurements of HFE-7000, HFE-7100

Article pubs.acs.org/jced

Compressed Liquid Viscosity Measurements of HFE-7000, HFE-71000, HFE-7200, and HFE-7500 at Temperatures from (253 to 373) K and Pressures up to 30 MPa Xiaozhen Hu, Xianyang Meng,* Kaixin Wei, Weihua Li, and Jiangtao Wu Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, Xi’an Jiaotong University, Xi’an, 710049, China ABSTRACT: The compressed liquid viscosities of heptafluoropropyl methyl ether (HFE-7000), methoxy-nonafluorobutane (HFE-7100), ethoxy-nonafluorobutane (HFE7200), and 2-trifluoromethyl-3-ethoxydodecafluorohexane (HFE-7500) were measured using a vibrating- wire viscometer over the temperature range of (253 to 373) K and at pressures from (0.1 to 30) MPa. The combined expanded uncertainty of the reported viscosity is about 2 % with a confidence level of 0.95 (k = 2). The experimental data were correlated with the empirical Andrade−Tait equation which could reproduce the results with average absolute percentage deviations of 0.44 %, 0.38 %, 0.56 %, and 0.56 %, respectively.

1. INTRODUCTION Hydrofluoroethers (HFEs) possess many similar thermophysical and chemical properties to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), perfluorocarbons (PFCs) and hydrofluorocarbons (HFCs), including high volatility, low thermal conductivity, low surface tension, and low or nonflammability.1,2 Meanwhile, they have nearly zero stratospheric ozone depletion protential (ODP), relatively low global warming potential (GWP), and short atmospheric lifetimes, which make them be promising alternatives to CFCs, HCFCs, HFCs, and PFCs.3 With respect to the toxicity of HFEs, there are no significant evidence to support the assumption of carcinogencxicity, mutagenicity, reproductive, and other chronic effects.2 Heptafluoropropyl methyl ether (HFE-7000), methoxy-nonafluorobutane (HFE-7100), ethoxy-nonafluorobutane (HFE-7200), and 2-trifluoromethyl-3-ethoxy-dodecafluorohexane (HFE-7500) are the most widely used HFEs as cleaning solvents in industry to replace HCFC-141b,2 among which, HFE-7000 could also be considered for use as a refrigerant to replace CFC-11 and CFC113.4,5 Thermodynamic and transport properties are essential to the optimum design of energy-conversion systems and the selection of alternative environmental friendly working fluids. In our previous work, compressed liquid density data for HFE7000, HFE-7100, HFE-7200, and HFE-7500 and isobaric heat capacity data for HFE-7200 and HFE-7500 had already been reported in a wide ranges of tempreature and pressure.6−9 With regard to viscosity, to the best of our knowledge, only a few data sets at atmospheric pressure or saturated pressure within a limited temperature range were reported in the literature.1,10−13 For a more comprehensive research of these HFEs, in this work, the compressed liquid viscosities of HFE-7000, HFE-7100, HFE7200, and HFE-7500 were reported at pressures from (0.1 to 30) MPa covering a temperature range from (253 to 373) K. © XXXX American Chemical Society

The empirical Andrade-Tait equation was used to correlate the experimental data.

2. EXPERIMENTAL SECTION 2.1. Chemicals. HFE-7000, HFE-7100, HFE-7200, and HFE-7500 were obtained from the 3 M Company with a stated Table 1. Specification of Samples chemical name HEF-7000 HFE-7100b HFE-7200c HFE-7500

CAS No.

formula

375-03-1 163702-07-6 163702-08-7 163702-05-4 163702-06-5 297730-93-9

C3F7OCH3 CF3CF2CF2CF2OCH3 (CF3)2CFCF2OCH3 CF3CF2CF2CF2OC2H5 (CF3)2CFCF2OC2H5 C7F15OC2H5

initial mass fraction puritya 0.995 0.995 0.995 0.995

a

All of the stated purities of the samples listed above were obtained by the certificates of supplier, and no further purity measurements were made after the purification. bHFE-7100 consists of two inseparable isomers, methyl nonafluorobutyl ether (CAS No. 163702-07-6) and methyl nonafluoroisobutyl ether (CAS No. 163702-08-7), with essentially identical properties, and the mass ratio of the two isomers is 0.452:0.548 calculated by 19F NMR spectrum. cHFE-7200 consists of two inseparable isomers, ethyl nonafluorobutyl ether (CAS No. 163702-05-4) and ethyl nonafluoroisobutyl ether (CAS No. 16370206-5), with essentially identical properties, and the mass ratio of the two isomers is 0.422:0.578 calculated by 19F NMR spectrum. Special Issue: Memorial Issue in Honor of Anthony R. H. Goodwin Received: June 15, 2015 Accepted: October 5, 2015

A

DOI: 10.1021/acs.jced.5b00499 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Figure 1. Schematic diagram of experimental system: (A) Manual piston pump; (B) vacuum pump; (C) sample container; (D) pressure transducer; (E) vibrating wire viscometer; (F) thermostatic bath; (G) wasting recycle; (V1−V5) valves.

HFE-7100, are methyl nonafluorobutyl ether (CAS No. 16370207-6) and methyl nonafluoroisobutyl ether (CAS No. 16370208-7), for HFE-7200, are ethyl nonafluorobutyl ether (CAS No. 163702-05-4) and ethyl nonafluoroisobutyl ether (CAS No. 163702-06-5). A Bruker Avance III HD 400 MHz NMR was used to measure the fluorine-19 NMR spectrum of HFE-7100 and HFE-7200 (solvent: CDCl3). The 19F NMR results show that the mass ratio of methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether in HFE-7100 is 0.452:0.548, and for HFE-7200, the mass ratio of ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether is 0.422:0.578. Table 1 lists the specification of the samples stuied. 2.2. Apparatus. The viscosity measurements were carried out with a steady state vibrating-wire viscometer described in detail previously.14,15 The viscometer was mainly formed with a two ends clamped tungsten wire, supplied by Metal Cutting, with a nominal radius of (50.00 ± 0.32) μm and a nominal length of 58 mm, a pair of samarium−cobalt magnets with a length of about 40 mm, and a custom-made stainless steel vessel with a maximum design pressure of 70 MPa. A sinusoidal voltage, achieved by a function generator (model: 33220A, Agilent), was applied to the wire immersed in a fluid; then the wire subject to a permanent magnetic field was driven in transverse oscillation by the Lorentz force. This oscillation motion induced an electromotive force at the wire ends, which is directly related to the viscosity and density of the fluid. The in-phase and quadrature voltages across the wire were detected by the lock-in amplifier (model: SR830, Stanford Research Systems) over the frequency range. For each fluid temperature and pressure, the measured complex voltages were replicated by adjusting the parameters including the viscosity of the fluid according to the working equations. The calibration and validation of the present apparatus has been given in our previous work,15 and it was used in this work without any change. A diagram of the experimental system is shown in Figure 1. A thermostatic bath was used to maintain the constant temperature of the apparatus. The temperature was measured with a calibrated 100 Ω platinum resistance thermometer connected to a DMM (model: 3458A, Agilent). The combined expanded uncertainty of temperature with level of confidence 0.95 (k = 2) is Uc(T) = 12 mK. A nanovolt meter (model: 34420A, Agilent) with 7 1/2 digits resolution was employed for the transformation of the pressure transducer measurement signal. The combined

Figure 2. Viscosity of HFE-7000, η, as a function of pressure at different temperatures. ■, 253.15 K; □, 263.15 K; ▲, 273.15 K; △, 283.15 K; ●, 293.15 K; ○, 303.15 K; ▼, 313.15 K; ▽, 323.15 K; ⧫, 333.15 K; ◊, 343.15 K; ◀, 353.15 K; ◁, 363.15 K. The solid line corresponds to eq 1.

Figure 3. Viscosity of HFE-7100, η, as a function of pressure at different temperatures. ■, 263.15 K; □, 273.15 K; ▲, 283.15 K; △, 293.15 K; ●, 303.15 K; ○, 313.15 K; ▼, 323.15 K; ▽, 333.15 K; ⧫, 343.15 K; ◊, 353.15 K; ◀, 363.15 K. The solid line corresponds to eq 1.

mass purity higher than 0.995 and used as they were supplied. HFE-7000 (CAS No. 375-03-1) and HFE-7500 (CAS No. 297730-93-9) are pure substances, while HFE-7100 and HFE7200 consist of two inseparable isomers with essentially identical properties, according to the supplier. The isomers, for B



Article

Table 2. Viscosity η of HFE-7000 at Temperature Range of (253 to 363) K from (1 to 30) MPaa T/K

p/MPa

ρb/kg·m−3

η/mPa·s

253.160 253.160 253.160 253.160 253.160 253.160 253.160 263.160 263.160 263.160 263.160 263.160 263.160 263.160 273.150 273.150 273.150 273.150 273.150 273.150 273.150 283.145 283.145 283.145 283.145 283.145 283.145 283.145 293.153 293.153 293.153 293.153 293.153 293.153 293.153 303.153 303.153 303.153 303.153 303.153 303.153 303.153 313.143 313.143 313.143 313.143 313.143 313.143 313.143 323.156 323.156 323.156 323.156 323.156 323.156 323.156 333.150 333.150 333.150

1.00 5.01 10.00 15.01 19.99 25.00 29.99 1.00 5.00 10.00 15.00 20.00 24.98 30.00 1.00 5.00 10.00 15.00 20.00 25.00 30.01 1.01 5.01 10.00 15.01 20.00 25.00 30.00 1.00 5.00 10.00 15.00 20.01 25.00 30.00 1.00 5.01 10.00 14.99 20.00 25.00 29.99 0.99 5.00 10.01 15.00 19.99 25.00 30.00 1.01 5.01 10.00 15.00 20.00 25.00 29.99 1.00 4.98 10.00

1528.63 1537.94 1548.79 1558.98 1568.50 1577.55 1586.08 1501.08 1511.22 1523.01 1533.97 1544.22 1553.81 1562.93 1474.04 1485.18 1498.02 1509.87 1520.88 1531.17 1540.86 1447.20 1459.49 1473.51 1486.39 1498.22 1509.24 1519.55 1420.13 1433.79 1449.23 1463.21 1476.04 1487.84 1498.84 1392.68 1407.98 1424.98 1440.22 1454.10 1466.80 1478.53 1364.47 1381.69 1400.62 1417.28 1432.26 1445.95 1458.50 1335.31 1354.78 1375.76 1394.07 1410.36 1425.06 1438.45 1304.75 1326.88 1350.47

0.8457 0.8894 0.9548 1.0126 1.0774 1.1438 1.2196 0.7157 0.7588 0.8121 0.8626 0.9205 0.9822 1.0345 0.6197 0.6565 0.7036 0.7523 0.7972 0.8468 0.8987 0.5330 0.5656 0.6121 0.6499 0.6926 0.7350 0.7802 0.4642 0.4955 0.5372 0.5703 0.6063 0.6491 0.6902 0.4084 0.4366 0.4751 0.5072 0.5416 0.5751 0.6115 0.3594 0.3827 0.4163 0.4503 0.4835 0.5154 0.5480 0.3163 0.3424 0.3725 0.4042 0.4343 0.4659 0.4955 0.2820 0.3076 0.3356

Table 2. continued T/K

p/MPa

ρb/kg·m−3

η/mPa·s

333.150 333.150 333.150 333.150 343.152 343.152 343.152 343.152 343.152 343.152 343.152 353.148 353.148 353.148 353.148 353.148 353.148 353.148 363.160 363.160 363.160 363.160 363.160 363.160 363.160

15.00 20.00 25.01 30.00 1.00 5.00 10.01 14.99 20.00 25.00 29.99 1.00 5.00 10.00 15.00 20.00 25.00 30.00 1.01 5.00 10.01 15.00 19.99 25.00 30.00

1370.59 1388.27 1404.12 1418.42 1272.63 1298.21 1324.59 1346.64 1365.87 1382.87 1398.14 1238.69 1268.36 1297.95 1322.28 1343.09 1361.34 1377.64 1202.75 1237.29 1270.64 1297.31 1319.78 1339.36 1356.69

0.3613 0.3946 0.4217 0.4478 0.2509 0.2717 0.3008 0.3292 0.3574 0.3824 0.4089 0.2226 0.2450 0.2718 0.2993 0.3252 0.3517 0.3769 0.1969 0.2204 0.2485 0.2724 0.2975 0.3220 0.3468

a The combined expanded uncertainty Uc(k = 2) are Uc(T) = 12 mK, Uc(p) = 0.12 MPa, and Uc(η) = 2 % with confidence level of 0.95. b Density ρ listed above was calculated from Qi et al.6

expanded uncertainty of pressure Uc(p) = 0.12 MPa (k = 2). In consideration of the uncertainties of temperature, pressure, repeatability of measurement, regression procedure, and the density of fluid, the combined expanded uncertainty of viscosity with level of confidence 0.95 (k = 2) is better than 2 %.

3. RESULTS AND DISCUSSION Qi et al. and Fang et al.6−8 measured the compressed liquid densities for HFE-7000, HFE-7100, HFE-7200, and HFE-7500 between (283 to 363) K and at pressures up to 100 MPa. The maximum expanded uncertainty with level of confidence 0.95 (k = 2) are 0.04 %, 0.03 %, 0.04 %, and 0.03 %, respectively. The density values of the samples, prerequisite to obtaining the viscosity from the working equations here, were calculated from the modified Tait equation of Qi et al. and Fang et al.6−8 The viscosities of compressed liquid HFE-7000 and HFE-7100 were measured at pressures from (1 to 30) MPa, along 12 isotherms from (253 to 363) K for HFE-7000 and 11 isotherms from (263 to 363) K for HFE-7100, listed in Table 2 and Table 3 and shown in Figure 2 and Figure 3. With regard to HFE-7200 and HFE-7500, the viscosity measurements were both performed along 14 isotherms over the temperature range of (253 to 373) K and at pressures from (0.1 to 30) MPa, which were listed in Table 4 and Table 5 and shown in Figure 4 and Figure 5. The experimental data of viscosity were correlated with the following empirical Andrade-Tait equation, proposed by Baylaucq et al.16 ⎛ p + E (T ) ⎞ D ⎛ B ⎞ ⎟ ⎟⎟ exp⎜ η(p , T ) = A⎜⎜ ⎝T − C ⎠ ⎝ pref + E(T ) ⎠ C

(1)



Article

Table 3. Viscosity η of HFE-7100 at Temperature Range of (263 to 363) K from (1 to 30) MPa.a T/K

p/MPa

ρb/kg·m−3

η/mPa·s

263.165 263.165 263.165 263.165 263.165 263.165 263.165 273.151 273.151 273.151 273.151 273.151 273.151 273.151 283.145 283.145 283.145 283.145 283.145 283.145 283.145 293.153 293.153 293.153 293.153 293.153 293.153 293.153 303.157 303.157 303.157 303.157 303.157 303.157 303.157 313.145 313.145 313.145 313.145 313.145 313.145 313.145 323.162 323.162 323.162 323.162 323.162 323.162 323.162 333.157 333.157 333.157 333.157 333.157 333.157 333.157 343.157 343.157 343.157

1.01 4.99 9.99 15.00 20.01 24.99 30.00 1.00 5.01 10.00 15.00 20.00 24.99 30.00 1.00 5.00 10.00 15.00 19.99 25.01 30.00 0.99 5.00 10.01 15.00 20.00 25.00 30.00 0.99 5.00 10.01 15.01 19.99 25.00 30.00 1.00 5.01 10.01 15.00 20.00 25.01 30.00 1.00 5.00 10.00 15.00 20.01 25.00 30.00 1.00 5.01 10.00 15.00 20.01 25.00 30.00 1.00 5.00 10.01

1609.75 1618.90 1629.68 1639.81 1649.34 1658.29 1666.84 1583.44 1593.47 1605.11 1615.98 1626.15 1635.71 1644.77 1557.52 1568.46 1581.13 1592.84 1603.73 1613.97 1623.58 1531.69 1543.74 1557.56 1570.21 1581.93 1592.83 1603.06 1505.80 1519.11 1534.22 1547.97 1560.53 1572.23 1583.12 1479.67 1494.43 1511.00 1525.91 1539.51 1552.03 1563.63 1452.89 1469.36 1487.59 1503.86 1518.55 1531.96 1544.32 1425.40 1443.89 1464.05 1481.79 1497.65 1512.01 1525.19 1396.90 1417.75 1440.15

1.2571 1.3401 1.4472 1.5712 1.6888 1.8111 1.9430 1.0450 1.1140 1.2040 1.3014 1.4009 1.5077 1.6132 0.8758 0.9349 1.0147 1.0955 1.1803 1.2647 1.3529 0.7437 0.7963 0.8659 0.9364 1.0077 1.0806 1.1543 0.6412 0.6892 0.7466 0.8119 0.8722 0.9328 0.9987 0.5566 0.5979 0.6520 0.7067 0.7626 0.8155 0.8762 0.4863 0.5226 0.5709 0.6189 0.6700 0.7193 0.7700 0.4273 0.4620 0.5048 0.5483 0.5964 0.6404 0.6877 0.3780 0.4084 0.4489


p/MPa

ρb/kg·m−3

η/mPa·s

343.157 343.157 343.157 343.157 353.156 353.156 353.156 353.156 353.156 353.156 353.156 363.161 363.161 363.161 363.161 363.161 363.161 363.161

15.01 20.00 25.00 30.00 1.00 5.01 10.00 15.00 20.01 25.01 30.00 0.99 5.00 10.00 15.00 20.01 25.00 29.99

1459.48 1476.61 1492.02 1506.05 1367.18 1390.90 1415.69 1436.83 1455.34 1471.84 1486.74 1336.05 1363.04 1390.64 1413.70 1433.66 1451.27 1467.08

0.4942 0.5360 0.5738 0.6162 0.3373 0.3638 0.3998 0.4375 0.4821 0.5204 0.5550 0.2964 0.3247 0.3637 0.4004 0.4354 0.4706 0.5044

a The combined expanded uncertainty Uc(k = 2) are Uc(T) = 12 mK, Uc(p) = 0.12 MPa, and Uc(η) = 2 % with confidence level of 0.95. b Density ρ listed above was calculated from Qi et al.6

where η is the viscosity in mPa·s, T is the temperature in K, p is the pressure in MPa, pref = 0.1 MPa is the reference pressure, E(T) = E0 + E1T + E2T2 and A, B, C, D, E0, E1, and E2 are the coefficients. To assess the performances of the correlations, the average absolute percentage deviation, AAD, the maximum absolute percentage deviation, MAD, the average percentage deviation, Bias, and the relative standard deviation, RSD, are defined as follows: AAD/% =

100 N

i=N

∑

ηi ,cal − ηi ,exp ηi ,exp

i=1

(2)

⎛ ηi ,cal − ηi ,exp MAD/% = max⎜⎜100· ηi ,exp ⎝ Bias/% =

100 N

i=N

⎛η

i=1

⎝

∑ ⎜⎜

⎞ ⎟ ⎟ ⎠

(3)

− ηi ,exp ⎞ ⎟ ⎟ ηi ,exp ⎠

(4)

⎛ η − η ⎞2 i ,cal i ,exp ⎟ ∑ ⎜⎜ ⎟ η ⎠ i ,exp i=1 ⎝

(5)

i ,cal

1 RSD/% = 100· N−1

i=N

The obtained coefficients and the statistical values are summarized in Table 6. The solid lines in Figures 2 to 5 are the correlation of eq 1. The relative deviations of the values calculated from eq 1 from experimental data are shown in Figures 6 to 9 as a function of density for HFE-7000, HFE-7100, HFE-7200, and HFE-7500, respectively. Most of the deviations in this work are less than ± 2 %, except two data points of HFE-7000 at 253.16 K, 30 MPa and 363.16 K, 1 MPa. The AADs for HFE-7000, HFE-7100, HFE-7200, and HFE-7500 are 0.44 %, 0.38 %, 0.56 %, and 0.56 %, and the MADs are 2.21 %, 1.53 %, 1.77 %, and 1.91 %. To the authors’ knowledge, only five sets of viscosity data at atmospheric pressure were found in the published papers for D



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Table 4. Viscosity η of HFE-7200 at Temperature Range of (253 to 373) K from (0.1 to 30) MPa.a T/K

p/MPa

ρb/kg·m−3

η/mPa·s

253.190 253.197 253.229 253.235 253.228 253.236 263.369 263.367 263.320 263.356 263.305 263.321 273.172 273.163 273.160 273.132 273.148 273.144 283.276 283.285 283.296 283.294 283.298 283.297 293.245 293.222 293.203 293.222 293.217 293.216 298.158 298.159 298.157 298.160 298.165 298.168 303.176 303.178 303.176 303.180 303.182 303.183 313.136 313.138 313.138 313.139 313.142 313.140 322.973 322.990 323.166 323.188 323.195 323.200 333.262 333.269 333.287 333.305 333.197

0.10 1.02 4.99 10.00 20.00 29.97 0.11 1.02 5.03 9.98 19.92 29.98 0.10 1.00 5.00 9.99 20.02 30.02 0.11 1.10 5.01 10.08 20.05 30.01 0.11 1.07 5.02 10.03 20.04 30.00 0.10 1.00 5.00 10.02 20.03 30.01 0.10 1.05 5.03 10.01 20.12 30.00 0.11 1.02 5.14 10.03 19.99 29.85 0.15 1.00 5.01 10.00 20.00 30.00 0.13 1.04 5.00 10.09 20.06

1534.08 1535.96 1543.83 1553.28 1570.62 1586.17 1507.86 1509.89 1518.68 1528.66 1547.15 1563.72 1483.50 1485.71 1495.08 1506.06 1525.79 1543.26 1459.18 1461.79 1471.74 1483.71 1504.75 1523.21 1435.65 1438.53 1449.56 1462.32 1485.01 1504.63 1424.14 1426.92 1438.57 1451.96 1475.46 1495.69 1412.47 1415.50 1427.67 1441.52 1466.14 1486.79 1389.27 1392.55 1406.37 1421.21 1447.31 1469.31 1366.32 1369.68 1384.22 1400.75 1429.05 1452.76 1341.63 1345.73 1362.07 1380.60 1411.24

1.3429 1.3697 1.4575 1.5708 1.8163 2.1122 1.1093 1.1218 1.1933 1.2994 1.5182 1.7533 0.9458 0.9566 1.0178 1.1140 1.3009 1.4865 0.8005 0.8157 0.8655 0.9409 1.0892 1.2495 0.6885 0.7004 0.7510 0.8125 0.9427 1.0875 0.6423 0.6527 0.6986 0.7598 0.8836 1.0150 0.5987 0.6091 0.6539 0.7110 0.8285 0.9512 0.5241 0.5339 0.5732 0.6242 0.7277 0.8423 0.4649 0.4744 0.5089 0.5555 0.6495 0.7461 0.4103 0.4181 0.4512 0.4956 0.5779


p/MPa

ρb/kg·m−3

η/mPa·s

333.199 343.247 343.238 343.242 343.260 343.316 343.333 354.042 354.063 354.083 354.063 354.080 354.142 363.168 363.165 363.155 363.170 363.183 363.177 373.262 373.231 373.265 373.265 373.258 373.255

30.03 0.14 1.00 5.01 10.00 20.00 29.88 0.15 1.01 4.99 9.96 19.97 30.02 0.18 1.01 5.01 10.00 19.98 30.05 0.23 1.00 5.01 10.01 19.99 30.02

1436.37 1317.13 1321.52 1340.06 1360.00 1392.92 1419.47 1289.70 1294.58 1315.34 1337.45 1373.31 1402.02 1265.57 1270.99 1294.19 1318.29 1356.51 1386.90 1237.81 1243.63 1269.65 1296.12 1337.20 1369.15

0.6638 0.3630 0.3710 0.4029 0.4432 0.5226 0.6020 0.3214 0.3278 0.3577 0.3963 0.4687 0.5423 0.2903 0.2954 0.3257 0.3604 0.4285 0.4974 0.2600 0.2650 0.2943 0.3273 0.3919 0.4554

a The combined expanded uncertainty Uc(k = 2) are Uc(T) = 12 mK, Uc(p) = 0.12 MPa, and Uc(η) = 2 % with confidence level of 0.95. b Density ρ listed above was calculated from Fang et al.7,8

Table 5. Viscosity η of HFE-7500 at Temperature Range of (253 to 373) K from (0.1 to 30) MPa.a

E

T/K

p/MPa

ρb/kg·m−3

η/mPa·s

253.133 253.124 253.101 253.086 253.082 253.097 263.196 263.182 263.187 263.191 263.194 263.197 273.163 273.156 273.164 273.156 273.156 273.155 283.151 283.154 283.169 283.167 283.170 283.184 293.190 293.195 293.196

0.10 1.07 4.99 9.95 19.90 29.90 0.10 1.01 5.02 10.03 20.02 30.03 0.10 1.01 5.08 10.06 20.02 30.02 0.10 1.02 5.01 10.02 20.05 30.06 0.10 1.05 5.05

1711.65 1713.43 1720.43 1728.82 1744.34 1758.50 1692.01 1693.82 1701.44 1710.47 1727.02 1742.01 1672.20 1674.13 1682.47 1692.10 1709.65 1725.48 1652.02 1654.13 1662.91 1673.31 1692.16 1708.87 1631.41 1633.77 1643.32

3.3345 3.4065 3.7217 4.1678 5.1349 6.2779 2.5624 2.6120 2.8393 3.1538 3.8467 4.6655 2.0427 2.0880 2.2531 2.4898 3.0011 3.6206 1.6442 1.6764 1.8166 1.9993 2.4096 2.8908 1.3696 1.3948 1.5075



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p/MPa

ρb/kg·m−3

η/mPa·s

293.198 293.201 293.195 298.159 298.161 298.163 298.162 298.158 298.161 303.135 303.137 303.140 303.148 303.156 303.166 313.163 313.164 313.168 313.167 313.167 313.167 323.169 323.169 323.167 323.168 323.167 323.167 333.139 333.142 333.148 333.148 333.152 333.158 343.172 343.178 343.180 343.180 343.185 343.182 353.191 353.199 353.206 353.208 353.217 353.221 363.217 363.223 363.226 363.228 363.224 363.225 373.164 373.165 373.167 373.169 373.167 373.167

10.04 20.07 30.03 0.10 0.98 5.04 10.03 20.02 30.00 0.10 0.96 5.02 10.05 20.05 30.08 0.10 1.07 5.04 10.02 20.02 29.97 0.10 1.01 5.01 10.01 20.01 30.00 0.11 1.02 5.01 10.00 20.00 30.00 0.10 1.00 5.01 10.01 20.00 30.00 0.10 0.99 5.01 10.00 19.99 29.99 0.10 1.01 5.01 10.01 19.99 30.02 0.12 1.02 5.01 10.00 20.01 30.02

1654.44 1674.55 1692.20 1621.08 1623.35 1633.48 1645.02 1665.73 1683.92 1610.66 1612.98 1623.54 1635.59 1657.01 1675.79 1589.45 1592.31 1603.53 1616.44 1639.36 1659.12 1567.98 1570.93 1583.27 1597.29 1621.83 1642.86 1546.31 1549.55 1563.00 1578.19 1604.46 1626.72 1524.19 1527.72 1542.56 1559.03 1587.17 1610.75 1501.85 1505.73 1522.02 1539.93 1570.02 1594.95 1479.23 1483.62 1501.52 1520.95 1553.15 1579.55 1456.63 1461.50 1481.09 1502.16 1536.58 1564.35

1.6566 1.9842 2.3517 1.2545 1.2809 1.3843 1.5168 1.8113 2.1379 1.1522 1.1786 1.2664 1.3910 1.6588 1.9582 0.9835 1.0016 1.0834 1.1882 1.4102 1.6537 0.8476 0.8674 0.9339 1.0249 1.2179 1.4247 0.7382 0.7534 0.8153 0.8973 1.0639 1.2437 0.6476 0.6636 0.7162 0.7902 0.9367 1.0955 0.5732 0.5848 0.6367 0.7012 0.8348 0.9738 0.5094 0.5206 0.5675 0.6273 0.7463 0.8702 0.4554 0.4659 0.5077 0.5627 0.6719 0.7862

Figure 4. Viscosity of HFE-7200, η, as a function of pressure at different temperatures. ■, 253.15 K; □, 263.15 K; ▲, 273.15 K; △, 283.15 K; ●, 293.15 K; ○, 298.15 K; ▼, 303.15 K; ▽, 313.15 K; ⧫, 323.15 K; ◊, 333.15 K; ◀, 343.15 K; ◁, 353.15 K; ▶, 363.15 K; ▷, 373.15 K. The solid line corresponds to eq 1.

Figure 5. Viscosity of HFE-7500, η, as a function of pressure at different temperatures. ■, 253.15 K; □, 263.15 K; ▲, 273.15 K; △, 283.15 K; ●, 293.15 K; ○, 298.15 K; ▼, 303.15 K; ▽, 313.15 K; ⧫, 323.15 K; ◊, 333.15 K; ◀, 343.15 K; ◁, 353.15 K; ▶, 363.15 K; ▷, 373.15 K. The solid line corresponds to eq 1.

HFE-7000, HFE-7100, and HFE-7200. Sekiya and Misaki1 reported the viscosity of HFE-7000 at 296.15 K. Nakazawa et al.10 measured the viscosity of HFE-7000 from (278 to 303) K with a torsional vibrating viscometer with a claimed uncertainty of 3 %. Kho et al.11 measured the viscosity of HFE-7100 and HFE-7200 from (298 to 328) K with an in-line electromagnetic viscometer. Warrier and Teja12 measured the viscosity of HFE-7200 at 297.8 K and 298.2 K with a factory calibrated size 25 Cannon-Fenske viscometer. Zhao13 measured the saturated liquid viscosity of HFE-7000, HFE-7100, and HFE-7200 from (293 to 393) K with the surface light scattering method, which could obtained the liquid kinematic viscosity and surface tension simultaneously.17 No published measurements for viscosity of HFE-7500 were found. To compare the literature data with this work, the viscosity at atmospheric pressure or saturated pressures was obtained by slightly extrapolating eq 1 where the minimum pressure for viscosity measurements is 0.1 MPa for HFE-7200 or 1 MPa for HFE-7000 and HFE-7200 in this work. The comparison was limited to within the temperature range of this work because there is no evidence that eq 1 can be used safely outside the temperature range of experimental data. The relative deviations of literature data and the results of this work at 0.1 or 1 MPa from

a The combined expanded uncertainty Uc(k = 2) are Uc(T) = 12 mK, Uc(p) = 0.12 MPa, and Uc(η) = 2 % with confidence level of 0.95. b Density ρ listed above was calculated from Fang et al.7,8

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Table 6. Coefficients and Deviations of eq 1 for HFE-7000, HFE-7100, HFE-7200, and HFE-7500 parameters

HFE-7000

HFE-7100

HFE-7200

HFE-7500

A B C D E0 E1 E2 AAD/% MAD/% Bias/% RSD/%

4.82989·10−4 3415.99 −205.365 0.917886 97.4060 −6.97495·10−2 −2.86316·10−4 0.44 2.21 0.002 0.59

3.75404·10−3 1769.53 −42.3413 1.27680 −1.80017 0.591121 −1.19077·10−3 0.38 1.53 0.001 0.47

3.26005·10−3 1959.43 −72.7263 1.19547 6.24312 0.485426 −9.85134·10−4 0.56 1.77 0.002 0.71

1.98166·10−2 986.704 60.2401 2.21856 −266.348 2.28110 −3.42669·10−3 0.56 1.91 0.003 0.70

Figure 6. Relative deviations of the calculated results of eq 1, ηcal, from the experimental data, ηexp, for HFE-7000 as a function of density at different pressures. □, 1 MPa; ▲, 5 MPa; ▽, 10 MPa; ●, 15 MPa; ◁, 20 MPa; ▶, 25 MPa; ◊, 30 MPa.

Figure 8. Relative deviations of the calculated results of eq 1, ηcal, from the experimental data, ηexp, for HFE-7200 as a function of density at different pressures. □, 0.1 MPa; ▲, 1 MPa; ▽, 5 MPa; ●, 10 MPa; ◁, 20 MPa; ▶, 30 MPa.

Figure 7. Relative deviations of the calculated results of eq 1, ηcal, from the experimental data, ηexp, for HFE-7100 as a function of density at different pressures. □, 1 MPa; ▲, 5 MPa; ▽, 10 MPa; ●, 15 MPa; ◁, 20 MPa; ▶, 25 MPa; ◊, 30 MPa.

Figure 9. Relative deviations of the calculated results of eq 1, ηcal, from the experimental data, ηexp, for HFE-7500 as a function of density at different pressures. □, 0.1 MPa; ▲, 1 MPa; ▽, 5 MPa; ●, 10 MPa; ◁, 20 MPa; ▶, 30 MPa.

eq 1 are plotted in Figures 10 to 12 as a function of temperature for HFE-7000, HFE-7100, and HFE-7200, respectively. HFE-7000. As shown in Figure 10, the data of Zhao13 exhibit scattered deviations around the baseline (the correlation of eq 1) within ± 2.3 %, while the deviations of the data from Nakazawa et al.10 lie above the baseline with a maximum deviation of 2.7 % at 303.15 K. The only one datum reported by Sekiya and Misaki1 at 296.15 K deviates from this work by 7.4 %. HFE-7100. As we can see from Figure 11, the deviations of the data from Zhao13 also show good agreement with our data within ± 2.5 %; however, the deviations of the data from Kho et al.11 show a temperature dependence, which reach to −14.9 % at 328.6 K. HFE-7200. Though most of the viscosities from Zhao13 are lower than this work, the deviations do not exceed −2.8 %.

The results reported by Kho et al.11 agree very well with this work at (298.2 and 308.5) K, but the deviations approach to −10.1 % and −8.9 % at (318.3 and 329.0) K, respectively. The data from Warrier and Teja12 show a large deviation of about −6 % from this work.

4. CONCLUSION In present work, the new viscosity measurements for HFE-7000, HFE-7100, HFE-7200, and HFE-7500 were reported, which were performed with a vibrating-wire viscometer. The measurements were carried out at pressures up to 30 MPa, and along 12 isotherms from (253 to 363) K for HFE-7000, 11 isotherms from (263 to 363) K for HFE-7100, and 14 isotherms from (253 to 373) K for HFE-7200 and HFE-7500. The combined G



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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: +86-29-82663737. Funding

This work was supported by the National Natural Science Foundation of China (No. 51476130 and 51176154) and the Fundamental Research Funds for the Central Universities. Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Sekiya, A.; Misaki, S. The potential of hydrofluoroethers to replace CFCs, HCFCs and PFCs. J. Fluorine Chem. 2000, 101, 215−221. (2) Tsai, W. Environmental risk assessment of hydrofluoroethers (HFEs). J. Hazard. Mater. 2005, 119, 69−78. (3) Tsai, W. Environmental risks of new-generation fluorocarbons in replacement of potent greenhouse gases. Int. J. Global Warm. 2013, 5, 84−95. (4) Widiatmo, J. V.; Uchimura, A.; Tsuge, T.; Watanabe, K. Measurements of vapor pressures and PVT properties of heptafluoropropyl methyl ether. J. Chem. Eng. Data 2001, 46, 1448−1451. (5) Klomfar, J.; Součková, M.; Pátek, J. Surface Tension and p-ρ-T Data for 1,1,1,3,3-Pentafluorobutane (HFC-365mfc) and 1,1,1,2,2,3,3Heptafluoro-3- methoxy-propane (HFE-347mcc). J. Chem. Eng. Data 2013, 58, 2316−2325. (6) Qi, H.; Fang, D.; Meng, X.; Wu, J. Liquid density of HFE-7000 and HFE-7100 from T = (283 to 363) K at pressures up to 100 MPa. J. Chem. Thermodyn. 2014, 77, 131−136. (7) Fang, D.; Li, Y.; Meng, X.; Wu, J. Liquid density of HFE-7200 and HFE-7500 from T = (283 to 363) K at pressures up to 100 MPa. J. Chem. Thermodyn. 2014, 69, 36−42. (8) Fang, D.; Li, Y.; Meng, X.; Wu, J. Corrigendum to “Liquid density of HFE-7200 and HFE-7500 from 283 to 363K at pressures up to 100MPa” [J. Chem. Thermodyn. 69 (2014) 36−42]. J. Chem. Thermodyn. 2015, 83, 123−125. (9) Zheng, Y.; Gao, H.; Chen, Q.; Meng, X.; Wu, J. Isobaric heat capacity measurements of liquid HFE-7200 and HFE-7500 from 245 to 353K at pressures up to 15 MPa. Fluid Phase Equilib. 2014, 372, 56−62. (10) Nakazawa, N.; Kawamura, M.; Sekiya, A.; Ootake, K.; Tamai, R.; Kurokawa, Y.; Murata, J. Liquid viscosities of fluorinated dialkylethers. Nippon Reito Kyokai Ronbunshu 2002, 19, 33−41. (11) Kho, Y. W.; Conrad, D. C.; Knutson, B. L. Phase equilibria and thermophysical properties of carbon dioxide-expanded fluorinated solvents. Fluid Phase Equilib. 2003, 206, 179−193. (12) Warrier, P.; Teja, A. S. Density, viscosity, and thermal conductivity of mixtures of 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane (HFE 7200) with methanol and 1-ethoxybutane. J. Chem. Eng. Data 2011, 56, 4291−4294. (13) Zhao, G. Development of surface laser light scattering apparatus for liquid viscosity and surface tension measurement and its applications. Ph.D. Dissertation, Xi’an Jiaotong University, Xi’an, 2013. (14) Meng, X.; Zhang, J.; Wu, J. Compressed liquid viscosity of 1,1,1,3,3-pentafluoropropane (R245fa) and 1,1,1,3,3,3-hexafluoropropane (R236fa). J. Chem. Eng. Data 2011, 56, 4956−4964. (15) Meng, X.; Qiu, G.; Wu, J.; Abdulagatov, I. M. Viscosity measurements for 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) and trans1,3,3,3-tetrafluoropropene (R1234ze(E)). J. Chem. Thermodyn. 2013, 63, 24−30. (16) Baylaucq, A.; Comuñas, M. J. P.; Boned, C.; Allal, A.; Fernández, J. High pressure viscosity and density modeling of two polyethers and two dialkyl carbonates. Fluid Phase Equilib. 2002, 199, 249−263. (17) Zhao, G.; Bi, S.; Fröba, A. P.; Wu, J. Liquid viscosity and surface tension of R1234yf and R1234ze under saturation conditions by surface light scattering. J. Chem. Eng. Data 2014, 59, 1366−1371.

Figure 10. Relative deviations of the experimental data, ηexp, from the calculated results of eq 1, ηcal, for HFE-7000 as a function of temperature at atmospheric pressure. ●, This work at 1 MPa; ▼, Sekiya and Misaki;1 ☆, Nakazawa et al.;10 △, Zhao13 at saturated pressure.

Figure 11. Relative deviations of the experimental data, ηexp, from the calculated results of eq 1, ηcal, for HFE-7100 as a function of temperature at atmospheric pressure. ●, This work at 1 MPa; ◊, Kho et al.;11 △, Zhao13 at saturated pressure.

Figure 12. Relative deviations of the experimental data, ηexp, from the calculated results of eq 1, ηcal, for HFE-7200 as a function of temperature at atmospheric pressure. □, This work at 0.1 MPa; ●, this work at 1 MPa; ◊, Kho et al.;11 ★, Warrier and Teja;12 △, Zhao13 at saturated pressure.

expanded uncertainty of the results with a level of confidence of 0.95 (k = 2) was estimated to be about 2 %. The experimental data were successfully correlated with the empirical Andrade-Tait equation. The AADs for HFE-7000, HFE-7100, HFE-7200, and HFE-7500 are 0.44 %, 0.38 %, 0.56 %, and 0.56 %, respectively. H


Compressed Liquid Viscosity Measurements of HFE-7000, HFE-7100

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