Compressed Liquid Density and Vapor Phase PvT Measurements of

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Compressed Liquid Density and Vapor Phase PvT Measurements of cis-1,2,3,3,3-Pentafluoroprop-1-ene (R1225ye(Z)) Published as part of The Journal of Chemical and Engineering Data special issue “Proceedings of the 19th Symposium on Thermophysical Properties” J. Steven Brown,*,† Laura Fedele,‡ Giovanni Di Nicola,§ Sergio Bobbo,‡ and Gianluca Coccia§ †

Department of Mechanical Engineering, The Catholic University of America, Washington, DC, 20064, United States Construction Technologies Institute, National Research Council, (ITC−CNR) Padova, 35127, Italy § Department of Industrial Engineering and Mathematical Sciences, Marche Polytechnic University, (UnivPM) Ancona, 60121, Italy ‡

ABSTRACT: This paper reports 136 compressed liquid density measurements and 104 vapor phase PvT measurements of cis-1,2,3,3,3-pentafluoroprop-1-ene (R1225ye(Z)). The compressed liquid density data represent eight isotherms evenly spaced approximately from (283 to 353) K for pressures from close to saturation to 35 MPa, and the vapor phase PvT data represent six isochores for temperatures approximately from (263 to 368) K for pressures approximately from (135 to 777) kPa. The paper also presents a saturated liquid density correlation, a Tait correlation for the compressed liquid density data, and a Martin-Hou equation of state for the vapor phase PvT data.

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INTRODUCTION For nearly 10 years, researchers increasingly have focused on low global warming potential (GWP) working fluids (e.g., aerosols, blowing agents, refrigerants, and solvents) for many and varied applications, where governmental regulations and taxes have been, and continue to be, the main drivers behind the interest in low-GWP fluids. While not claiming to be exhaustive, several examples can help illustrate these claims. In 2002, the European Union (EU) approved the Kyoto Protocol,1 and then in 2006 adopted the so-called F-Gas Regulations2 and Mobile Directive.3 The purpose of the former is to contain, prevent, and reduced emissions of fluorinated greenhouse gases (GHG), including hydrofluorocarbons (HFCs), emissions and the latter is to ban from 1 January 2017 the use of GHGs with GWP greater than 150 in mobile applications. More recently, the European Union’s (EU) 2014 F-Gas regulations4 instituted a phase-down schedule for HFCs over the period 2015−2030, with the allowed 2030 amounts being only 21% of the 2009−2012 EU average. In addition, these newer regulations place bans and/or use restrictions on HFCs based on GWP and application in new equipment, and place restrictions on importing, servicing, and labeling requirements for HFCs. Also recently, the United States, Canada, and Mexico proposed regulating HFCs under the Montreal Protocol Framework.5 Regarding taxes, several European countries (Denmark, Norway, Slovenia, and Spain) currently tax HFCs based on the mass of fluid and its corresponding GWP, with several other European countries (France, Poland, and Sweden) having considered adopting HFC taxing schemes. © 2015 American Chemical Society

As a last example, in 2012, Australia adopted a carbon tax on HFCs, but later repealed it in 2014.6 One class of low GWP working fluids receiving considerable focus is halogenated olefins and blends containing them. Four of these fluids have already been investigated by the authors. In particular, they have measured vapor pressures, normal boiling point (NBP) temperatures, liquid densities, and vapor phase PvT of (1) R1234yf 7−10 (2,3,3,3-tetrafluoroprop-1-ene, CF3CFCH2, CAS number 754-12-1), (2) R1234ze(E)11,12 (trans-1,3,3,3-tetrafluoroprop-1-ene, CF3CHCHF, CAS number 1645-83-6), (3) R1243zf13,14 (3,3,3-trifluoroprop-1ene, CF3CHCH2, CAS number 677-21-4), and (4) R1234ze(Z)15,16 (2,3,3,3-tetrafluoroprop-1-ene, CF3CHCHF, CAS number 29118-25-0). In addition, they have measured vapor pressures and the NBP temperature of R1225ye(Z), the fluid being investigated in this paper.17 The current paper presents the following: (1) 136 compressed liquid density (ρ) measurements from a vibrating tube densimeter (Anton Paar DMA 512) for eight evenly spaced isotherms from (283.15 to 353.15) K for pressures (P) up to 35 MPa, with an expanded uncertainty with 0.95 level of confidence in ρ of 0.8 kg·m−3. The measured ρ values were extrapolated to estimate saturated liquid densities (ρs). A Tait correlation and saturated liquid density correlation were developed for ρ and ρs, respectively; (2) 104 vapor phase Received: July 8, 2015 Accepted: September 25, 2015 Published: October 2, 2015 3333

DOI: 10.1021/acs.jced.5b00562 J. Chem. Eng. Data 2015, 60, 3333−3340

Journal of Chemical & Engineering Data

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Table 1. R1225ye(Z)a Sample Description chemical name R1225ye(Z)a a

source Mexichem Fluor S.A. de C.V.

initial mass fraction purity > 0.97

purification method

final mass fraction purity

analysis method

> 0.98

GC

several cycles of freezing, evacuation, melting, and ultrasonic agitation

cis-1,2,3,3,3-pentafluoroprop-1-ene.

Table 2. Critical State Property Estimates for R1225ye(Z)17

PvT measurements from an isochoric apparatus along six isochores for T approximately from (263 to 368) K for P approximately from (135 to 777) kPa, with an expanded uncertainty with 0.95 level of confidence in specific volume (v) of 0.005 m3·kg−1. A Martin−Hou (M-H) equation of state (EoS) was developed from the vapor phase PvT measurements. R1225ye(Z) was evaluated during 2006 to 2008 as part of the Society of Automotive Engineer’s (SAE) Cooperative Research Program (CRP150). However, to the best of the authors’ knowledge, it is not currently being actively commercialized because it demonstrated chronic toxicological effects in 28-day rat inhalation tests.18 In particular, it showed effects on the myocardium of rats at concentrations of (10 000, 25 000, and 50 000) ppm. Despite these negative toxicological concerns, the authors’ wish to present thermophysical property data since the fluid has not been characterized yet in the open literature and because it could be used in applications where toxicity concerns are less important than in automotive applications. Note: the fluid is nonflammable.

Tc/K

Pc/kPa

ρc/kg·m3

380.05

3529

517.17

Table 3. Constants for eq 2 from Fedele et al.17 A1

A2

A3

A4

−7.53451

1.61073

−2.58309

−1.63098

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EXPERIMENTAL SECTION Materials. Table 1 describes the Mexichem Fluor S.A. de C.V. supplied R1225ye(Z) (cis-1,2,3,3,3-pentafluoroprop-1-ene, CF3CFCHF, CAS number 5528-43-8) test sample. The purity of the provided material was greater than 0.97 in mass fraction, with the largest impurity being the trans isomer R1225ye(E). Before experimentation, the sample was subjected to several cycles of freezing, evacuation, melting, and ultrasonic agitation to eliminate noncondensable gases. A gas chromatography (GC) analysis showed the purity of the final sample was greater than 0.98 in mass fraction. Experimental Apparatus and Procedure. Compressed Liquid Density. The compressed liquid density measurements were conducted in the Construction Technologies Institute of the National Research Council (ITC−CNR) located in Padova, Italy, using a stainless steel vibrating tube densimeter (Anton Paar DMA 512). The period of oscillation of the vibrating tube is related to the sample density through a calibration equation which is a function of pressure and temperature. The experimental apparatus, procedure, and calibration are described in previous papers19,20 and will only be briefly described here. The densimeter was charged with the sample by means of a circuit of stainless steel tubes connecting the cell and the refrigerant canister. The fluid was pressurized with a syringe pump (Isco Pump 260D). Pressure was measured with a piezoresistive pressure gauge (Druck DPI 145) with an expanded uncertainty with 0.95 level of confidence of 10 kPa, while temperature, controlled with a stability of about ± 0.003 K, is measured by means of a Pt 100 Ω resistance thermometer with an expanded uncertainty with 0.95 level of confidence of 0.05 K. The densimeter was calibrated by measuring the oscillation period of the U-tube under vacuum and filled with a fluid of

Figure 1. Compressed liquid density data for R1225ye(Z). Data also provided in Table 4. ●, 283.15 K; ○, 293.15 K; ▼, 303.15 K; △, 313.15 K; ■, 323.15 K; □, 333.15 K; ▲, 343.15 K; ▽, 353.15 K.

known density, that is, water. For each constant temperature value the calibration equation was π 2 = (a1·P 2 + a 2 ·P + a3) ·ρ + B

(1)

where π is the oscillation period in μs, P the pressure in kPa, ρ the density in kg·m−3and a1, a2, a3, and B are regression coefficients. After charging the water in the circuit, at each temperature the period of oscillation was measured at more than 15 different pressures over the range from saturation to 35 MPa. The water density at each calibration temperature and pressure was obtained by the equation proposed by Wagner and Pruss,21 while a1, a2, a3, and B were regressed from the set of periods of oscillations and water densities obtained from the calibration. For the measurements, after purging and evacuating the system, R1225ye(Z) was charged into the vibrating tube and associated measurement circuit. At a given temperature, pressure was set at a fixed level by acting on the syringe pump. After stabilization of temperature and pressure, the period of oscillation was acquired. To average the very minute fluctuations of pressure and temperature also in stable conditions, a sequence of around 20 pressures and corresponding periods of oscillation were taken and the average values were used to calculate the density by inversing eq 1. After this, pressure was changed by acting on the syringe pump and a new measurement 3334

DOI: 10.1021/acs.jced.5b00562 J. Chem. Eng. Data 2015, 60, 3333−3340

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Table 4. Compressed Liquid Density Measurements for R1225ye(Z) for Which the Relative Deviations Are e = 100·Δρ/ ρ = (ρcalc − ρexp)/ρexp of the Values Calculated (ρcalc) Using eq 4 (Tait) from the Experimental Data (ρexp). Expanded Uncertainties with 0.95 Level of Confidence Are U(T) = 0.05 K, U(P) = 1 kPa, and U(ρ) = 0.8 kg·m−3 T/K

P/MPa

ρ/kg·m−3

eTait/%

T/K

P/MPa

ρ/kg·m−3

eTait/%

283.16 283.16 283.16 283.16 283.15 283.15 283.15 283.15 283.15 283.14 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15

35.004 32.498 29.999 27.503 25.000 22.497 20.001 17.501 15.001 12.501 9.998 7.499 5.000 2.500 1.997 1.499 1.003 0.604 0.510

1442.4 1436.2 1430.3 1423.9 1417.0 1409.9 1402.5 1395.0 1387.0 1378.7 1369.8 1360.3 1350.2 1339.1 1336.8 1334.5 1332.0 1330.1 1329.6

−0.081 −0.054 −0.068 −0.059 −0.036 −0.017 0.004 0.003 0.000 −0.004 −0.007 −0.015 −0.022 −0.026 −0.029 −0.036 −0.028 −0.028 −0.030

323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.16 323.16 323.16 323.16 323.15

35.001 32.501 30.001 27.500 25.001 22.500 19.999 17.499 15.000 12.499 10.001 7.500 4.998 2.502 2.000 1.499 1.296

1347.7 1340.0 1331.8 1323.2 1314.1 1304.4 1294.0 1282.9 1270.8 1257.6 1243.3 1226.8 1207.9 1185.5 1180.3 1175.1 1172.9

−0.016 −0.009 −0.004 0.000 0.004 0.008 0.010 0.010 0.010 0.006 −0.018 −0.018 −0.023 −0.019 −0.009 −0.006 −0.005

293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15

34.999 32.500 30.000 27.499 25.000 22.500 20.000 17.500 14.999 12.500 10.001 7.500 5.000 2.500 2.000 1.500 1.000 0.598 0.470

1418.5 1412.0 1405.4 1398.5 1391.4 1383.9 1376.0 1367.8 1359.0 1349.7 1339.8 1329.0 1317.4 1304.6 1301.9 1299.1 1296.2 1293.9 1293.2

−0.005 0.014 0.025 0.029 0.035 0.037 0.040 0.037 0.036 0.034 0.031 0.024 0.014 0.009 0.006 0.007 0.008 0.008 0.008

333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15

35.000 32.500 29.999 27.500 25.003 22.500 20.000 17.500 15.000 12.500 10.000 7.500 5.000 2.500 1.999 1.502

1326.3 1317.8 1308.2 1298.8 1288.8 1278.1 1266.6 1255.0 1240.4 1225.4 1208.6 1189.4 1166.8 1138.6 1132.0 1124.9

−0.173 −0.158 −0.098 −0.088 −0.076 −0.067 −0.059 −0.123 −0.035 −0.035 −0.041 −0.057 −0.081 −0.099 −0.097 −0.093

303.16 303.16 303.16 303.15 303.15 303.15 303.15 303.16 303.16 303.15 303.15 303.15 303.16 303.16 303.15 303.15 303.15 303.15

35.000 32.500 30.000 27.500 24.999 22.501 20.000 17.500 14.996 12.500 9.999 7.500 5.000 2.499 2.000 1.500 1.000 0.700

1395.6 1388.8 1381.8 1374.4 1366.0 1357.8 1349.2 1340.2 1330.5 1320.1 1308.8 1296.6 1283.2 1267.8 1264.3 1260.9 1257.4 1255.3

−0.043 −0.035 −0.029 −0.023 0.032 0.038 0.042 0.031 0.031 0.030 0.026 0.021 0.004 0.024 0.042 0.045 0.050 0.054

343.15 343.15 343.15 343.15 343.16 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15

35.000 32.500 30.000 27.500 25.000 22.500 20.000 17.500 15.000 12.500 10.001 7.500 5.001 2.500 2.000 1.800

1302.5 1293.3 1283.5 1273.2 1262.3 1250.3 1237.6 1223.8 1208.5 1191.5 1172.0 1149.2 1121.1 1083.8 1074.1 1070.0

−0.106 −0.087 −0.069 −0.052 −0.039 −0.008 0.005 0.015 0.021 0.020 0.011 −0.005 −0.033 −0.044 −0.011 0.006

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Table 4. continued T/K

P/MPa

ρ/kg·m−3

eTait/%

T/K

P/MPa

ρ/kg·m−3

313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.14 313.14 313.15 313.16 313.15 313.15 313.15

35.000 32.500 30.001 27.500 25.000 22.500 20.000 17.497 15.000 12.501 10.000 7.500 5.000 2.501 2.008 1.500 1.000

1371.0 1363.7 1356.1 1348.1 1339.7 1330.8 1321.4 1311.3 1300.5 1288.9 1276.1 1262.1 1246.4 1228.3 1224.6 1220.4 1216.2

0.022 0.033 0.041 0.049 0.056 0.060 0.062 0.063 0.061 0.055 0.052 0.041 0.027 0.014 −0.006 −0.005 −0.004

353.16 353.15 353.15 353.15 353.15 353.15 353.14 353.15 353.15 353.15 353.15 353.15 353.15 353.16

35.001 32.502 30.000 27.500 25.000 22.500 20.000 17.500 15.000 12.500 10.000 7.500 5.000 2.500

1279.2 1269.4 1259.0 1247.9 1235.9 1223.0 1209.0 1193.5 1176.3 1156.8 1134.0 1106.5 1070.7 1016.9

eTait/% 0.070 0.081 0.090 0.099 0.113 0.118 0.133 0.138 0.141 0.138 0.130 0.116 0.097 0.162

Table 5. Constants for eq 3 B1

B2

B3

B4

3.0710

−5.5898

11.8457

−7.1235

Table 6. Constants for eqs 4 and 5 C

a

b

d

e

0.0825

−9.344

72.323

−180.323

185.114

Figure 3. PvT data in the vapor phase for R1225ye(Z). Data also provided in Table 7. ●, v = 0.116 m3·kg−1; ○, v = 0.079 m3·kg−1; ▼, v = 0.054 m3·kg−1; △, v = 0.040 m3·kg−1; ■, v = 0.032 m3·kg−1; □, v = 0.027 m3·kg−1.

(UnivPM) located in Ancona, Italy, using a constant volume apparatus consisting of a stainless steel sphere. The total volume of the spherical test cell, tubing, and pressure transducer cavity were estimated to be 273.5 ± 0.3 cm3 at 298 K. The experimental apparatus, procedure, and calibration are described in previous papers22,23 and will only be briefly described here. The test cell and pressure transducer were submerged in one of two constant temperature baths operating over temperature ranges from (210 to 290) K and from (290 to 360) K. A pressure transducer and controller (Ruska 7000) measured the pressure with an expanded uncertainty with 0.95 level of confidence of 0.2 kPa. However, when including the uncertainty associated with fluctuations in the bath temperature, the expanded uncertainty with 0.95 level of confidence for the pressure measurements is 1 kPa. A Pt 25 Ω resistance thermometer (Hart Scientific 5680) measured the temperature with an expanded uncertainty with 0.95 level of confidence of 0.03 K. The expanded uncertainty with 0.95 level of confidence for the specific volume measurements is estimated to be 0.005 m3·kg−1.

Figure 2. Deviations (Δρ/ρ = (ρcalc − ρexp)/ρexp) between values calculated using eq 4 (ρcalc) and the experimental data (ρexp) of Figure 1 and Table 4. ●, 283.15 K; ○, 293.15 K; ▼, 303.15 K; △, 313.15 K; ■, 323.15 K; □, 333.15 K; ▲, 343.15 K; ▽, 353.15 K.

was taken repeating the same procedure. Steps of pressure of around 0.5 MPa from saturation to 2.5 MPa and of around 2.5 MPa from 2.5 MPa and 35.0 MPa were applied. The expanded uncertainty with 0.95 level of confidence for the density measurements is estimated to be approximately 0.8 kg·m−3. Recently, the apparatus has been used to measure compressed liquid densities of four HFOs: R1234yf,8,10 R1234ze(E),11 R1243zf,13 and R1234ye(Z).15 Vapor Phase PvT. The vapor phase PvT measurements were conducted in the Department of Industrial Engineering and Mathematical Sciences of Marche Polytechnic University 3336

DOI: 10.1021/acs.jced.5b00562 J. Chem. Eng. Data 2015, 60, 3333−3340

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Table 7. PvT Measurements in the Vapor Phase for R1225ye(Z) for Which the Relative Deviations Are e = 100·ΔP /P = (Pcalc−Pexp)/Pexp of the Values Calculated (Pcalc) from eq 6 (M-H) from the Experimental Values (Pexp). Expanded Uncertainties with 0.95 Level of Confidence Are U(T) = 0.03 K, U(P) = 1 kPa, and U(v) = 0.005 m3·kg−1 T/K

P/kPa

v/(m3·kg−1)

eM‑H/%

T/K

P/kPa

v/(m3·kg−1)

eM‑H/%

263.15 268.15 273.14 278.15 283.16 288.15 293.15 298.15 303.15 308.14 313.15 318.15 323.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.16 368.15

135.2 138.3 141.3 144.3 147.3 150.2 152.7 155.7 158.7 161.7 164.2 166.8 169.7 169.7 172.6 174.9 177.9 181.0 183.8 186.6 189.5 192.3 194.3

0.115 0.115 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116 0.116

0.100 0.030 0.005 −0.027 −0.054 −0.053 0.196 0.141 0.058 −0.023 0.181 0.319 0.263 0.269 0.225 0.528 0.407 0.248 0.233 0.219 0.174 0.144 0.518

297.14 303.15 308.15 313.15 318.15 323.16 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.16 368.15

418.9 430.0 439.0 447.9 457.0 466.1 475.1 483.9 492.8 501.5 510.2 518.9 527.6 536.1 544.7

0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040

−0.263 −0.190 −0.119 −0.028 −0.025 −0.022 −0.016 0.014 0.028 0.054 0.071 0.088 0.096 0.113 0.117

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 312.86 318.15 323.15 328.15 333.15 338.15 343.15 348.15 353.15 358.15 363.14 368.16

202.4 207.0 211.5 215.6 220.0 224.3 228.2 232.8 236.9 241.3 245.6 249.7 253.9 257.7 262.4 266.6 270.7 274.5 278.7 282.9

0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079 0.079

−0.508 −0.532 −0.541 −0.388 −0.401 −0.382 −0.202 −0.319 −0.341 −0.296 −0.303 −0.228 −0.247 −0.093 −0.289 −0.284 −0.273 −0.121 −0.162 −0.195

298.15 303.14 308.12 313.13 318.23 323.14 328.07 333.10 338.08 343.08 348.06 353.11 358.17 363.14 368.16

498.5 510.2 522.1 533.4 544.9 555.9 566.8 578.2 589.4 600.4 611.4 622.8 633.7 644.4 655.3

0.032 0.032 0.032 0.032 0.033 0.033 0.033 0.033 0.033 0.033 0.033 0.033 0.033 0.033 0.033

−0.097 −0.062 −0.083 −0.024 0.024 0.069 0.127 0.105 0.092 0.090 0.093 0.035 0.042 0.044 0.037

282.83 287.91 292.78 298.47 303.14 308.15 313.16 318.14 323.14 328.11 333.10 338.14 343.09 348.07

301.1 307.5 314.1 320.7 327.0 333.9 340.4 346.9 353.4 360.1 365.4 371.5 377.8 383.7

0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054 0.054

−0.495 −0.337 −0.333 0.008 −0.013 −0.101 −0.075 −0.075 −0.078 −0.152 0.141 0.248 0.230 0.322

308.14 313.14 318.14 323.14 328.14 333.13 338.08 343.13 348.14 353.13 358.15 363.13 368.10

612.3 627.0 641.3 655.2 669.2 682.7 696.3 710.0 723.7 737.3 750.7 764.0 777.4

0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027

0.020 0.013 0.032 0.092 0.113 0.177 0.188 0.219 0.207 0.201 0.208 0.217 0.189

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Table 7. continued T/K

P/kPa

v/(m3·kg−1)

353.05 358.11 363.29 368.03

390.1 397.3 404.0 409.8

0.054 0.054 0.054 0.054

eM‑H/%

T/K

v/(m3·kg−1)

P/kPa

eM‑H/%

0.284 0.073 0.017 0.034

Table 8. Constants for eq 6 Tc

R −1

b −1

kJ·kg ·K

K 380.05

m ·kg 3

A2 −1

2.805746 × 10

0.0629740 A3

kJ·m ·kg 3

−4

kJ·m6·kg−3K−1 −4

1.882216 × 10

−2.933015 × 10

1.011902 × 10

−2.026764 B5

A4

kJ·m6·kg−3 −7

kJ·m3·kg−2

−4

−9.506725 × 10 C3

C2 −2 −1

kJ·m ·kg K 3

−2

B3

kJ·m6·kg−3

B2 −2

kJ·m9·kg−4 −3

2.882312 × 10

kJ·m12·kg−5·K−1 −8

−6.082792 × 10

4.402463 × 10−14

Recently, the apparatus has been used to measure vapor phase PvT data of four HFOs: R1234yf,8,10 R1234ze(E),11 R1243zf,13 and R1234ye(Z).15

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RESULTS AND DISCUSSION

Estimated Critical State Properties. For the correlations presented in eqs 2 to 6, the critical state properties of R1225ye(Z) are used to reduce the data. The employed values, summarized in Table 2, are ones the authors have previously17 estimated for the critical temperature (Tc), critical pressure (Pc), and critical density (ρc) to be 380.05 K, 3529 kPa, and 517.17 kg·m3, respectively. Vapor Pressure Correlation. Before presenting the saturated liquid density correlation (eq 3), the compressed liquid density correlation (eqs 4 and 5), and the PvT correlation for the vapor phase (eq 6), we present in eq 2 a Wagner vapor pressure correlation (required for eqs 3 to 5) that has been previously17 developed by the authors, which fitted their vapor pressure data with a mean absolute deviation (|100·ΔP/ P|) of 0.084, with the deviations defined as ΔP/P = (Pcalc− Pexp)/Pexp where Pcalc are the values calculated using eq 2 and Pexp are the experimental data. Tr ln(Pr) = A1τ + A 2 τ1.5 + A3τ 2.5 + A4 τ 5

Figure 4. Deviations (ΔP/P = (Pcalc − Pexp)/Pexp) between values calculated using eq 6 (Pcalc) and the experimental data (ρexp) of Figure 3 and Table 7. ●, v = 0.116 m3·kg−1; ○, v = 0.079 m3·kg−1; ▼, v = 0.054 m3·kg−1; △, v = 0.040 m3·kg−1; ■, v = 0.032 m3·kg−1; □, v = 0.027 m3·kg−1.

using the 136 compressed liquid density data of Figure 1 and Table 4.

(2)

where the constants are provided in Table 3. The variables Tr (= T/Tc) and Pr (= P/Pc) are the reduced temperature and reduced pressure, respectively, and τ = 1 − Tr. Compressed Liquid Density Data. Figure 1 and Table 4 present the 136 compressed liquid density measurements for R1225ye(Z) for eight isotherms evenly spaced approximately from (283 to 353) K for pressures from close to saturation to 35 MPa. Saturated Liquid Density Correlation. The 136 compressed liquid density data were used to develop a saturated liquid density (ρs) correlation (eq 3) first by fitting a polynomial for each isotherm for pressures less than 5 MPa and then coupling these with the vapor pressure correlation given in eq 2. ρs = ρc (1 + B1τ1/3 + B2 τ 2/3 + B3τ + B4 τ 4/3)

⎡ ⎛ β + P ⎞⎤ ρ−1 = ρs−1⎢1 − C ln⎜ ⎟⎥ ⎢⎣ ⎝ β + Ps ⎠⎥⎦

(4)

β = Pc( −1 + aτ1/3 + bτ 2/3 + dτ + eτ 4/3)

(5)

where ρs is provided in eq 3, the coefficient β is provided in eq 5, and the constants for both equations are provided in Table 6. The deviations (Δρ/ρ = (ρcalc − ρexp)/ρexp) between values calculated using eq 4 (ρcalc) and the experimental data (ρexp) of Figure 1 and Table 4 are shown in Figure 2. The numerical values for Δρ/ρ = (−0.173 to 0.162) % with a mean absolute deviation (|100·Δρ/ρ|) of 0.044. Vapor Phase PvT Data. Figure 3 and Table 7 present the 104 vapor phase PvT data for six isochores (0.116, 0.079, 0.054, 0.040, 0.032, 0.027) m3·kg−1 for temperatures approximately from (263 to 368) K for pressures approximately from (135 to 777) kPa. Martin-Hou Equation of State for Vapor Phase PvT Data. The Martin-Hou (M-H) Equation of State (EoS)

(3)

with the constants provided in Table 5. Tait Correlation for Compressed Liquid Density. The Tait correlation described in eqs 4 and 5 was developed 3338

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described in eq 6 was developed from the 104 vapor phase PvT data of Figure 3 and Table 7. P=

R1234ze(E), and R1234ze(Z). In particular, Figures 5 and 6 show comparisons between measured compressed liquid density data and measured vapor phase PvT data, respectively, of R1225ye(Z) and modeled24 (using high-accuracy EoS) values of R1234yf, R1234ze(E), and R1234ze(Z). Figure 5 shows that for an isotherm of 283.15 K and a given pressure, the compressed liquid density of R1225ye(Z) is greater by approximately 15%, 10%, and (6 to 7) % than it is for R1234yf, R1234ze(E), and R1234ze(Z), respectively. Figure 6 shows that for an isochore of 0.054 m3·kg−1 and a given temperature, the pressure of R1225ye(Z) is approximately (13 to 14) % lower than it is for R1234yf and R1234ze(E) and is approximately (8 to 10) % lower than it is for R1234ze(Z).

A + B2 T + C2e−5.475T / Tc RT + 2 v−b (v − b)2 +

A3 + B3T + C3e−5.475T / Tc (v − b)3

+

A4 (v − b)4

+

B5T (v − b)5 (6)

where the constants are provided in Table 8, and P is in kPa, v is in m3·kg−1, and T is in K. The deviations (ΔP/P = (Pcalc − Pexp)/Pexp) between values calculated using eq 6 (Pcalc) and the experimental data (Pexp) of Figure 3 and Table 7 are shown in Figure 4. The numerical values are ΔP/P = (−0.541 to 0.528) % with a mean absolute deviation (|100·ΔP/P|) of 0.170. Comparisons with Other Hydrofluoroolefins (HFOs). Figures 5 and 6 show comparisons between R1225ye(Z) and

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CONCLUSIONS Herein, compressed liquid density (ρ) measurements are presented for eight evenly spaced isotherms from (283.15 to 353.15) K for pressures (P) up to 35 MPa, with an expanded uncertainty with 0.95 level of confidence in ρ of 0.8 kg·m−3. The measured ρ values were extrapolated to estimate saturated liquid densities (ρs). A Tait correlation and saturated liquid density correlation were developed for ρ and ρs, respectively. The deviations (Δρ/ρ = (ρcalc − ρexp)/ ρexp) between values calculated using eq 4 (ρcalc) and the experimental data (ρexp) are Δρ/ρ = (−0.173 to 0.162) % with a mean absolute deviation (|100·Δρ/ρ|) of 0.044. In addition, vapor phase PvT measurements are presented along six isochores for T approximately from (363 to 368) K for P approximately from (135 to 777) kPa, with an expanded uncertainty with 0.95 level of confidence in specific volume (v) of 0.005 m3·kg−1. A Martin-Hou EoS was developed from the vapor phase PvT measurements. The deviations (ΔP/P = (Pcalc − Pexp)/Pexp) between values calculated using eq 5 (Pcalc) and the experimental data (Pexp) are ΔP/P = (−0.541 to 0.528) % with a mean absolute deviation (|100·ΔP/P|) of 0.170.

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Figure 5. Comparison of compressed liquid densities between measured data for R1225ye(Z) and modeled24 values for R1234yf, R1234ze(E), and R1234ze(Z) for an isotherm of 283.15 K. ●, R1225ye(Z); , R1234yf; ---, R1234ze(E); bold , R1234ze(Z).

AUTHOR INFORMATION

Corresponding Author

*Tel. +001 202 3194738. Fax +001 202 3194499. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank Antonella Barizza, Laura Colla, and Mauro Scattolini for their assistance and Mexichem Fluor S.A. de C.V. for donating the sample.

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REFERENCES

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Figure 6. Comparison of vapor phase PvT between measured data for R1225ye(Z) and modeled24 values for R1234yf, R1234ze(E), and R1234ze(Z) for an isochore of 0.054 m3·kg−1. ▼, R1225ye(Z); , R1234yf; ---, R1234ze(E); bold , R1234ze(Z).

three other well-described (implies high-accuracy EoS are available) hydrofluoroolefins (HFOs), namely, R1234yf, 3339

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