Low GWP halocarbon refrigerants: A review of thermophysical properties

International Journal of Refrigeration 90 (2018) 181–201

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International Journal of Refrigeration journal homepage: www.elsevier.com/locate/ijrefrig

Review

Low GWP halocarbon refrigerants: A review of thermophysical propertiesR Sergio Bobbo a,∗, Giovanni Di Nicola b, Claudio Zilio c, J. Steven Brown d, Laura Fedele a a

Istituto per le Tecnologie della Costruzione, Consiglio Nazionale delle Ricerche, Corso Stati Uniti 4, 35131 Padova, Italy Dipartimento di Ingegneria Industriale e Scienze Matematiche, Università Politecnica delle Marche, Ancona I-60131, Italy c Dipartimento di Tecnica e Gestione dei Sistemi Industriali, Università degli Studi di Padova, Vicenza I-36100, Italy d Department of Mechanical Engineering, The Catholic University of America, Washington, DC 20064, United States b

a r t i c l e

i n f o

Article history: Received 28 September 2017 Revised 28 March 2018 Accepted 29 March 2018 Available online 19 April 2018 Keywords: HCFO HFO Low GWP Refrigerants Thermophysical properties Experimental data

a b s t r a c t In the present work, a large number of compounds described in the publicly available literature have been reviewed with the aim to identify possible substitutes for high-GWP HFCs in HVAC&R and organic Rankine cycle (ORC) applications. Taking into account various criteria (particularly low toxicity, low flammability, low GWP, and high energy efficiency), only a few single-component compounds are suitable for many of the relevant applications. In particular, in addition to natural fluids, studies have shown that there are only a few HFCs and a dozen or so HFOs, i.e. halogenated olefins characterized by the presence of a C=C double bond in the molecule, that are potentially suitable for a number of relevant applications. Here, a review of the present state-of-the-art of experimentally-determined thermophysical properties of a number of HFOs working fluids and their mixtures also with other categories of refrigerants is presented, with particular emphasis placed on saturation and critical properties, vapor phase PVT data, liquid density, specific heat capacity, thermal conductivity, viscosity, and surface tension. © 2018 Elsevier Ltd and IIR. All rights reserved.

Revue des propriétés thermophysiques des frigorigènes halocarbures à faible GWP Mots-clés: HCFO; HFO; Faible GWP; Frigorigènes; Propriétés thermophysiques; Données expérimentales

1. Introduction Following the Montreal Protocol (1987) (see UNEP Ozone Secretariat, 20 0 0), the refrigeration industry has undertaken a process to reduce the negative environmental impact of working fluids. In a first step, chlorinated compounds (CFCs and HCFCs) were substituted by fluorinated hydrocarbons (HFCs) and natural fluids (e.g., ammonia, carbon dioxide, hydrocarbons) to solve the problem of stratospheric ozone depletion. In a second step that followed the Kyoto Protocol (UNFCCC, 1997), a process was begun and is still underway, to limit and control the emissions of HFCs that contribute to global warming and climate change. The process of reducing the R An earlier, less complete version of this paper was presented at the 5th IIR International Conference on Thermophysical Properties and Transfer Processes of Refrigerants, Seoul (Korea), 23–26 April, 2017. ∗ Corresponding author. E-mail address: [email protected] (S. Bobbo).

https://doi.org/10.1016/j.ijrefrig.2018.03.027 0140-7007/© 2018 Elsevier Ltd and IIR. All rights reserved.

emissions of high-GWP refrigerants is increasing as more and more national and international agreements, regulatory actions, and taxing schemes are being negotiated and implemented (see, e.g., EU, 2014). Regardless, the recognition of the importance of the issue of the global warming impact of working fluids promises to become increasingly more widespread in the coming years, making it all the more important to continue to identify, characterize, and develop alternative low-GWP working fluids for a wide-range of HVAC&R and organic Rankine cycle (ORC) applications. Therefore, the goal of this paper is to survey for a number of HFO (hydrofluoroolefin) and HCFO (hydrochlorofluoroolefin) working fluids the publicly available literature reporting experimentally-determined thermophysical property data necessary for building accurate equations of state (EoS) and for being able to accurately evaluate the performance potential of working fluids in refrigeration, heat pumping, and ORC applications.

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Nomenclature AAD% cp cp o cv CP GWP100 MAD% MM SLE

percentage absolute average deviation isobaric specific heat capacity [J mol–1 K–1 ] ideal gas specific heat capacity [J mol–1 K–1 ] isochoric specific heat capacity [J mol–1 K–1 ] critical point Greenhouse Warming Potential (100 years horizon) Maximum Absolute Deviation Molar Mass [kg kmol−1 ] Solid Liquid Equilibria

Greek symbols λ thermal conductivity [W m−1 K−1 ] μ dynamic viscosity [kg m−1 s−1 ] ρ density [kg m−3 ] Superscripts cl compressed liquid l liquid ncp near critical point Subscripts b normal boiling point crit critical exp experimental max maximum NBP Normal Boiling Point temperature P pressure [kPa] R molar gas constant [8.314 4598 J mol–1 K–1 ] (Mohr et al., 2016) T temperature [K] V molar volume [mol L–1 ] VLE Vapor Liquid Equilibria x mass fraction w speed of sound [m s−1 ] σ surface tension [N m−1 ] ω acentric factor [dimensionless] ν kinematic viscosity [m2 s−1 ] scr supercritical sv superheated vapor v vapor r reduced Ref Refprop (or Reference EoS) sat saturation 2. Selection of HFOs and HCFOs as potential refrigerants The selection of the most suitable working fluids for refrigeration, heat pumping, and ORC applications are based on a number of criteria, including environmental considerations (low GWP, zero or near-zero ODP), safety (low toxicity, low flammability), and performance (high efficiency, appropriate capacity). Note that there are many other important criteria which often must be considered, e.g., cost, material compatibility, lubricant solubility/miscibility, inter alia; however, they are not included herein as they fall outside the scope of the present paper. The most systematic and complete analyses conducted to date of working fluids capable of satisfying the above-mentioned criteria for a few applications have been undertaken by McLinden et al. (2014, 2015). For low- and medium-temperature HVAC&R applications, they limited their focus to a group of sixty-two potentially attractive working fluids, with the largest number of them being HFOs. In fact, the working fluids considered herein are those identified by the analyses of McLinden and co-workers plus a few additional fluids more suitable for ORC applications [R1336mzz(E),

R1336mzz(Z), R1354mzy(E), R1354myf(E)]. Table 1 lists the HFOs and HCFOs considered in this paper, together with some of their fundamental properties. 3. Experimental data available in the publicly available literature While not claiming that the analysis provided in this paper is exhaustive, a thorough and wide-ranging search of the publicly available literature was conducted. The analysis placed special emphasis on papers published in peer-reviewed journals catalogued by the International Scientific Indexing (ISI) server, with the aim to determine and evaluate the experimentally-determined data for a number of important thermodynamic and transport properties of several HFO and HCFO working fluids. Table 2 lists the actual number of papers for each refrigerant which report experimental data and which were identified using the above described methodology (it should be emphasized that a single paper often presents data sets for more than one thermophysical property). It is evident that the most investigated fluids are R1234yf and R1234ze(E), followed by R1234ze(Z) and R1233zd(E). Many fewer references are available for R1123, R1243zf, R1225ye(Z), R1336mzz(E), R1336mzz(Z), R1354mzy(E), and R1354myf(E), while no references were found for the remaining fluids. In the following paragraphs, the available literature references are considered in more detail. It is worth noting once again that the present authors do not claim the overview presented herein is exhaustive or complete. Probably, some papers were not included, particularly if they are published in conference proceedings not accessible to the authors. Regardless, the present authors believe they have captured much of the publicly available, peer-reviewed, and experimentallydetermined data for the selected refrigerants. 4. Thermodynamic and transport properties of single-component working fluids 4.1. Thermodynamic properties Accurate knowledge of the thermodynamic properties of working fluids is essential for developing accurate EoS, as well as for being able to accurately evaluate the performance potential (energy efficiency and capacity) of working fluids in refrigeration, heat pumping, and organic Rankine cycle applications. For these purposes, the main thermodynamic properties needed are those along the boundaries of the thermodynamic space (i.e., critical point, vapor pressure, saturation densities) and PVT properties in the single-phase regions. Less essential, but still very helpful in developing accurate fundamental EoS and for verifying the thermodynamic consistency of experimental data, are specific heat capacity and speed of sound. The following sections provide the references which report experimental data for the above-mentioned thermodynamic properties for the working fluids of Table 1, with special mention given of the number of experimental data and the temperature and pressure ranges for the various data sets. Herein, we provide more detailed analyses for the four fluids, i.e., R1234yf, R1234ze(E), R1234ze(Z), and R1233zd(E), for which a significant number of data sets are available in the literature. Diagrams showing the distributions of the available data on the P−T plane and relative deviations of the data from reference values are presented to allow the reader to better identify the most studied thermodynamic regions and, secondly, to show relative comparisons between the various data sets. It must be highlighted that reference values for the thermodynamic properties (vapor pressure, PvT properties, specific heat capacity and speed of sound) are calculated through the database REFPROP 9.1 (Lemmon et al., 2013), REFPROP from now on, which

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183

Table 1 ASHRAE Designation, IUPAC Name, and select properties of several working fluids (The data are taken from Lemmon et al., 2013, unless noted otherwise.). ASHRAE designation (ISO standard 817)

IUPAC name

MM (kg/kmol)

Tb (K)

Tcrit (K)

Pcrit (kPa)

ω

GWP100

R1141a R1123 R1132(E)a R1234yf R1243zf R1225zcb R1234ye(E)a R1234ze (E) R1225ye(Z)a R1132(Z)a R1225ye(E)a R1234ze(Z) R1336mzz(E)c R1354mzy(E) R1233zd(E) R1354myf(E) R1336mzz(Z)d

Fluoroethene (vinylfluoride) 1,1,2-trifluoroethene trans-1,2-difluorethene 2,3,3,3-tetrafluoropropene 3,3,3-trifluoroprop-1-ene 1,1,3,3,3-pentafluoroprop-1-ene trans-1,2,3,3-tetrafluoroprop-1-ene trans-1,3,3,3-tetrafluoropropene cis-1,2,3,3,3-pentafluoroprop-1-ene cis-1,2-difluorethene trans-1,2,3,3,3-pentafluoroprop-1-ene (TRANS) 1,3,3,3-tetrafluoroprop-1-ene trans-1,1,1,4,4,4-hexafluoro-2-butene trans-1,1,1,3-tetrafluoro-2-butene trans-1-chloro-3,3,3-trifluoro-1-propene trans-2,4,4,4-tetrafluoro-2-butene cis-1,1,1,4,4,4-hexafluoro-2-butene

46.04 82.03 64.03 114.04 96.05 132.03 114.04 114.04 132.03 64.03 164.03 114.04 164.05 128.07 130.50 128.07 164.05

209.71 215.07 237.49 243.70 247.70 251.35 252.39 254.18 255.44 259.80 259.89 282.90 280.58 289–291 291.41 N.A. 306.60

327.20 331.70 370.51 367.85 376.93 376.6 382.66 382.51 383.97 405.77 390.83 423.27 403.37 N.A. 439.60 N.A. 444.50

5162.2 4546.0 5089.3 3382.2 3517.1 3312 3731.0 3634.9 3407.1 5221.4 3423.3 3533.0 2766.4 N.A. 3623.7 N.A. 2895

0.1675 0.1900 0.2091 0.2760 0.2606 0.303 0.2819 0.3130 0.2730 0.2170 0.2747 0.3274 0.4053 N.A. 0.3025 N.A. 0.3867

<1e 3e 1e <1 e 0.8f n.a. 2.3f 6f 2.9f 1e 2.9f 1.4f N.A. N.A. 7g N.A. 2h

N.B.: values in italics are estimated and taken from the reference cited in the first column. a Brown et al. (2015). b Brown et al. (2010). c Tanaka et al. (2017a). d Tanaka et al. (2017b). e McLinden et al. (2015). f McLinden et al. (2014). g Orkin et al. (2014). h Myhre et al. (2013).

Table 2 Number of peer-reviewed literature references reporting experimental data/estimations for important thermophysical properties of several HFO and HCFO refrigerants. ASHRAE designation

R1123 R1141 R1132(E) R1234yf R1243zf R1234ye(E) R1234ze(E) R1225ye(Z) R1132(Z) R1225ye(E) R1234ze(Z) R1233zd(E) R1336mzz(E) R1336mzz(Z) R1354mzy(E) R1354myf(E)

Thermodynamic properties

Transport properties

cp

w

λ

μ/ν

σ

10 1

5

4

1

7

2 1

13 1

14 1

6

4

2

4

3

8 4 1 4 1

7 5 1 1 3 1

1 2

1

1

2 1

1 2

CP

Psat

PVT

2

2

2

2 1

11 2

2

1 1 1 1 1

1

N.B.: the same paper can report sets of data for different properties.

applies for each fluid specific reference EoS. For all fluids, they are fundamental equations of state (FES) explicit in the Helmholtz energy. For simplicity, REFPROP will be cited as reference for the calculations, but it must be understood that the calculations are actually performed for each fluid with the specific EoS presented in the references reported in Table 3. 4.1.1. Critical point Experimental data of the critical properties or the region around the critical point are available for nine of the selected refrigerants, namely R1123, R1234yf, R1243zf, R1234ze(E), R1234ze(Z), R1233zd(E), R1336mzz(E), R1336mzz(Z) and R1354mzy(E). The references are provided in Table 4. In some cases (e.g. Fukushima et al., 2015 and Tanaka and Higashi, 2010a), critical density and critical temperature were determined on the basis of measurements of the density-temperature relationship

along the vapor-liquid coexistence curve, while critical pressure was extrapolated from vapor pressure measurements. Critical temperature was directly measured for all fluids, while pressure was generally extrapolated or determined as an adjustable parameter during vapor pressure curve regression. Fig. 1 shows the distributions of the available critical point experimental data for the various fluids on P−T and ρ −T planes. 4.1.2. Vapor pressure Vapor pressure measurements are available for ten of the selected refrigerants, i.e. the nine for which critical point measurements are available, plus R1225ye(Z). Table 5 lists the available data sets. The most investigated refrigerants are R1234yf, R1234ze(E), R1234ze(Z) and R1233zd(E). Here below, we perform more detailed analyses of the available data for these fluids based on the deviations of the experimental data from the reference values calculated with the EoSs implemented in REFPROP and reported in Table 3. The results are provided in Fig. 2(a)–(d). R1234yf: 11 data sets consisting of a total of 162 data points have been identified in the literature. It is worth noting that several papers reporting VLE data for binary or ternary mixtures with R1234yf as one of the components report data on the vapor pressure of the pure compound. In particular, 6 of such papers have been published by the Department of Thermal Science and Energy Engineering, University of Science and Technology of China, Hefei. However, 4 of them (Hu et al., 2013, 2014a, 2014b, 2014c) report the same data, measured with a relatively low accuracy in pressure (±3.5 kPa). More recently, the same group measured the vapor pressure with higher accuracy (±0.5 kPa) and published the same data in two different papers (Chen et al., 2015a, 2015b; Hu et al., 2016). Moreover, all the six papers report vapor pressure data at the same 5 temperatures. For all these reasons, only the paper of Chen et al. (2015a, 2015b), where the most accurate data were published for the first time, has been considered in this review. This paper reports 5 data in the range Tr = 0.80–0.88 with AAD% = 0.05% and MAD% = 0.08%). The data of Di Nicola, G. et al. (2010b) have an AAD% of 0.14% with a maximum deviation of 1.3% and are distributed over a wide range of temperatures (Tr = 0.61–0.995); the data are more scat-

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Table 3 Reference EoS used in REFPROP to calculate the reference values for the thermodynamic properties for the four selected fluids. ASHRAE

Type of Eos

EoS uncertainties

Designation

(Reference)

Vapor pressure

PvT properties

Specific heat capacity

Speed of sound

R1234yf

15-term Helmholtz FES (Richter et al. 2011)

0.1%

T 240 K–320 K P up to 10 MPa 0.1% Outside of this region and Even higher in the critical T 200 K–380 K P up to 40 MPa 0.1% Outside of this region and Even higher in the critical Vapor phase 0.4% Liquid phase 0.2% 0.020%

5%

Gas phase 0.1% Liquid phase 0.5%

5%

Gas phase 0.05% Liquid phase 0.2%

N.D.

Gas phase 0.05%

N.D.

0.131%

R1234ze(E)

16-term Helmholtz FES (Thol and Lemmon, 2016)

R1234ze(Z) R1233zd(E) a

a

17-term Helmholtz FES (Akasaka et al., 2014) 15-term Helmholtz FES (Mondejar et al., 2015)

0.1%

0.15% 0.223%

in the vapor phase up to 0.5% region

in the vapor phase up to 0.5% region

It is worth to note that the EoS developed by Mondejar et al. (2015) is based on their own data only.

Fig. 1. Critical parameters obtained from experimental measurements. (a) Critical pressure as a function of critical temperature; (b) Critical density as a function of critical temperature. It is worth noting that in almost all cases Pcrit was determined by extrapolating vapor pressure measurements to the critical temperature.

Table 4 Available experimental data for the critical parameters of several HFO and HCFO refrigerants. ASHRAE designation

References

R1123

Fukushima et al. (2015) Higashi and Akasaka (2016) Tanaka and Higashi (2010a) Hulse et al. (2009) Daubert et al. (1987) Higashi et al. (2010) Grebenkov et al. (2009) Higashi et al. (2015) Hulse et al. (2012) Tanaka et al. (2017a) Tanaka et al. (2017b) Kimura et al. (2017a)

R1234yf R1243zf R1234ze(E) R1234ze(Z) R1233zd(E) R1336mzz(E) R1336mzz(Z) R1354mzy(E) a b

ρ crit

Tcrit (K)

Pcrit (MPa)

(kg m−3 )

331.8 331.73 367.85 367.95 378.55 382.51 382.75 423.27 438.75 403.37 444.50 424.73

4.545a 4.546a 3.382a 3.260a 3.609 3.632a 3.681a 3.533b 3.7721a 2.7664 2.895 3.250

510 504 478 – – 486 – 470 – 515.3 507 424.0

Extrapolated to Tcrit . Treated as an adjustable parameter during vapor pressure curve regression.

tered and possess higher deviations at the lower temperatures. The data of Fedele et al. (2011) are distributed over a medium range of temperatures (Tr = 0.67–0.93) and possess an AAD% = 0.07%

and a maximum deviation of 2.4% (but only four points possess deviations higher than 0.2%); also for this data set, scattering and deviations are higher at the lower temperatures. Hulse et al. (2009) report 12 data distributed in the range Tr = 0.65–0.96. They show systematic and quite large negative deviations from REFPROP, (AAD% = 1.36%, MAD% = 2.81%), and demonstrate a tendency to increase with increasing temperature. Hu et al. (2017b) report data in a limited range of temperatures (Tr = 0.77–0.88). The deviations are low (AAD% = 0.09%, MAD% = 0.21%), but systematically negative. The data of Kamiaka et al. (2013) are distributed in the range Tr = 0.74–0.91, with AAD%= 0.17% and MAD% = 0.24%. They show a constant trend to decrease from positive to negative values at increasing temperatures. Kochenburger et al. (2017) data are distributed in a quite wide range of temperatures (Tr = 0.65– 0.96). The data are a bit scattered from negative to positive values, with AAD% = 0.24% and MAD% = 0.34%. In a similar range of temperatures (Tr = 0.69–0.95) Madani et al. (2016) report data with AAD% = 0.15% and MAD% = 0.39% and fluctuations between positive and negative deviations. The data of Richter et al. (2011), distributed over a wide range of temperatures (Tr = 0.67–0.93) show very good agreement with REFPROP (AAD% = 0.05% with a maximum deviation of 0.49%), but again with the higher devia-

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Table 5 Available experimental data for the vapor pressure of selected HFO and HCFO refrigerants. ASHRAE designation

Reference

No. data

T range (K)

AAD%

R1123

Fukushima et al. (2015) Higashi and Akasaka (2016) Chen et al. (2015a, 2015b) Di Nicola, G. et al. (2010b) Fedele et al. (2011) Hu et al. (2017b) Hulse et al. (2009) Kamiaka et al. (2013) Kochenburger et al. (2017) Madani et al. (2016) Richter et al. (2011) Tanaka and Higashi (2010a) Yang et al. (2016a) Brown et al. (2013) Daubert et al. (1987) Di Nicola et al. (2012a) (CNR-ITC) Di Nicola et al. (2012a) (UnivPM) Dong et al. (2011) Dong et al. (2012) Dong et al. (2013) Gong et al. (2016a) Grebenkov et al. (2009) Hu et al. (2017c) Kayukawa and Fuji (2009) McLinden et al. (2010) Tanaka (2016a) Tanaka et al. (2010a) Yin et al. (2018) Fedele et al. (2016) (2 labs) Fedele et al. (2014a) (CNR-ITC) Fedele et al. (2014a) (UnivPM) Gong et al. (2016b) Higashi et al. (2015) Kayukawa et al. (2012) Sakoda et al. (2017) Tanaka (2016a) Zhuo et al. (2017) Di Nicola et al. (2017) (CNR-ITC) Di Nicola et al. (2017) (UnivPM) Hulse et al. (2012) Mondejar et al. (2015) Tanaka et al. (2017a) Henne and Finnegan (1949) Haszeldine (1953) Kontomaris (2014) Tanaka et al. (2016) Kimura et al. (2017b)

16 13 5 34 40 9 12 7 5 7 28 11 4 83 39 49 29 4 4 4 10 49 9 32 28 18 8 15 96 36 28 5 19 49 4 22 63 32 49 16 23 17 1 1 1 13 14

313 ÷ 331 300 ÷ 331 293 ÷ 323 224 ÷ 366 246 ÷ 343 283 ÷ 323 241 ÷ 353 273 ÷ 333 193 ÷ 273 254 ÷ 348 250 ÷ 320 310 ÷ 360 283 ÷ 313 234 ÷ 373 256 ÷ 379 259 ÷ 343 223 ÷ 348 258 − 283 258 − 288 258 − 288 253 ÷ 293 237 ÷ 379 283 − 323 258 − 330 261 ÷ 280 300 ÷ 380 310 ÷ 380 303 − 373 233 ÷ 366 283 ÷ 353 238 ÷ 373 253 ÷ 293 310 ÷ 420 273 ÷ 373 353 ÷ 413 300 ÷ 400 273 ÷ 373 293 ÷ 353 234 ÷ 375 263 ÷ 353 280 ÷ 438 323 ÷ 403 306.35 (NBP) 306.65 (NBP) 306.55 (NBP) 324 ÷ 443 340 ÷ 410

–

R1234yf

R1243zf R1234ze(E)

R1225ye(Z) R1234ze(Z)

R1233zd(E)

R1336mzz(E) R1336mzz(Z)

R1354mzy(E)

tions at the lower temperatures. The data of Tanaka and Higashi (2010a) cover a limited range of temperatures (reduced temperature Tr between 0.84 and 0.98). Their data have an AAD% of 0.12% relative to REFPROP, with a maximum deviation of 0.26%. Finally, Yang et al. (2016a) measured their data in the range Tr = 0.77– 0.85, with very limited deviations from REFPROP (AAD% = 0.03%, MAD% = 0.05). It is worth noting here that, in addition to the Chen et al. (2015a, 2015b) data, also those of Hu et al. (2017b), Kamiaka et al. (2013), Kochenburger et al. (2017), Madani et al. (2016) and Yang et al. (2016a) are included in papers dedicated to VLE measurements for mixtures. R1234ze(E): 13 data sets consisting of a total of 259 data points have been identified in the literature. Di Nicola et al. (2012a) present data sets from two different laboratories (CNR-ITC and UnivPM). The data of CNR-ITC have an AAD% = 0.10% with a maximum deviation of 0.3% in the range Tr = 0.67–0.90. The data of UnivPM cover a much wider range of temperatures (Tr = 0.58– 0.923), with several points below atmospheric pressure. The AAD% is 0.22%, with a maximum deviation of 1.19%, and the data are quite scattered with higher deviations at low temperatures, due to the increasing importance of the absolute errors of the measur-

0.05 0.14 0.07 0.11 1.36 0.17 0.24 0.15 0.05 0.12 0.03 – 0.10 0.22 0.56 0.52 0.06 0.33 1.94 0.11 0.71 0.03 0.04 0.03 0.05 – 0.42 0.60 0.22 0.11 n.a. 0.10 0.32 0.51 0.33 0.59 1.93 0.09 – –

–

ing devices at very low pressures. Dong et al. (2011) report 4 data in the range Tr = 0.66–0.77, with AAD% = 0.30 and MAD% = 1.09%. Dong et al. (2012, 2013) report 4 data each in the same range of temperatures (Tr = 0.67–0.75), but with different absolute deviations (AAD% = 0.52% and 0.06% respectively) and maximum deviations (MAD% = 0.65% and MAD% = 0.10%, respectively). These last three data sets belong to papers dedicated to VLE measurements for mixtures. A small amount of data are presented also by Gong et al. (2016a) for a limited range of temperatures (Tr = 0.66–0.77). The data are relatively scattered, with AAD% = 0.33% with a maximum deviation of 1.09%. Grebenkov et al. (2009) reported 49 data measured with two different methods in a wide range of temperatures (Tr = 0.62–0.993). The data are very scattered and the overall deviations from RFEPROP are quite high, being AAD%= 1.94%, with a maximum deviation of 7.53% (not all the deviations are shown in Fig. 2(b)). Hu et al. (2017c) data are distributed in the range Tr = 0.74–0.85, with AAD% = 0.11% and MAD% = 0.15% and systematic positive deviations from REFPROP. The data of McLinden et al. (2010) cover a wider range of temperatures (Tr = 0.68–0.993) and the agreement with REFPROP is excellent (AAD% = 0.03% with a maximum deviation of 0.05%). The data of Tanaka (2016a) show

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Fig. 2. Deviations of the experimental vapor pressure data for (a) R1234yf, (b) R1234ze(E), (c) R1234ze(Z) and (d) R1233zd(E) from the values calculated using REFPROP.

good agreement with REFPROP (AAD% = 0.04% with a maximum deviation of 0.08%) for a range of temperatures closer to the critical point (Tr = 0.78–0.993). The data of Tanaka et al. (2010a) show good agreement with REFPROP (AAD% = 0.03% with a maximum deviation of 0.07%), although the temperature range was limited (Tr = 0.81–0.993). Finally, Yin et al. (2018) reported data in the range Tr = 0.79–0.98 and limited deviations, systematically positive, from REFPROP (AAD% = 0.05%, MAD% = 0.06%). The paper of Kayukawa and Fuji (2009) is not available to the authors, even if the range of temperatures (Tr = 0.74–0.85) and the deviations from REFPROP (AAD% = 0.71%) are known. Then, the deviations from REFPROP are not displayed in Fig. 2(b). R1234ze(Z): 8 data sets consisting of a total of 226 data points have been identified in the literature. Fedele et al. (2014a) present

data from two different laboratories (CNR-ITC and UnivPM). The data of CNR-ITC, measured in the range Tr = 0.67–0.834 have an AAD% = 0.42% with the same bias, showing systematic positive deviations relative to the calculations of REFPROP, with a maximum deviation of 0.3%. The data of UnivPM cover a much wider range of temperatures (Tr = 0.56–0.88), with 9 points falling below atmospheric pressure. The AAD% is 0.58%, with a maximum deviation of 0.75%. The deviations increase at lower temperatures; however, below 277 K the data fall out of the range of validity of the EoS. Gong et al. (2016b) measured the vapor pressure in the range of temperatures Tr = 0.60–0.69, with AAD% = 0.22 and MAD% = 0.22%. However, the two points at the lowest temperatures are excluded because out of the validity of the reference EoS. The data of Higashi et al. (2015) fall in the range of

S. Bobbo et al. / International Journal of Refrigeration 90 (2018) 181–201

Tr = 0.73–0.992. The absolute deviations are unbiased and are generally less than 0.2% with AAD% = 0.41% with a maximum deviation of 0.20%. Sakoda et al. (2017) report 4 data in the range Tr = 0.83–0.976, with AAD% = 0.10% and MAD = 0.10%. The data of Tanaka et al. (2016) fall in the range Tr = 0.71–0.945. The deviations from REFPROP are small for temperatures greater than 320 K, but tend to continuously increase for decreasing temperatures. The AAD% is 0.32% with a maximum deviation of 1.64%. Finally, Zhuo et al. (2017) report data in the range of reduced temperatures between 0.57 and 0.88 with quite scattered and almost all positive deviations from REFPROP (AAD% = 0.51%, MAD% = 1.07%). The paper of Kayukawa et al. (2012), reporting 49 data, is not accessible to the authors and thus a direct comparison of their data with REFPROP is not possible. Tanaka et al. (2013) do not provide their actual experimental data, but instead provide only a correlation of their data. Thus, a direct comparison of their data with REFPROP is not possible. R1233zd(E): 4 data sets consisting of a total of 120 data points have been identified in the literature. Di Nicola et al. (2017) present data from two different laboratories (CNR-ITC and UnivPM). The data of CNR-ITC, measured over the temperature range Tr = 0.67–0.805, show an AAD% = 0.37% with the same bias, showing systematic positive deviations from the calculations of REFPROP, with a maximum deviation of 1.2%. The data of UnivPM cover a much wider temperature range (Tr = 0.53–0.86), with 19 points taken below atmospheric pressure. The AAD% is 0.59% with a maximum deviation of 18.41% at the lowest temperature (234 K). The percentage deviations are clearly increasing at the lower temperatures due to the very low pressures in relation to the absolute deviations from the calculation (constant at around 1 kPa over the entire temperature range). The data of Hulse et al. (2012) are quite scattered and show relatively high negative deviations over the entire range of temperature (Tr = 0.60–0.804). The AAD% deviation is 1.93% with a maximum deviation of 6.67%. The data of Mondejar et al. (2015), on the other hand, exhibit small deviations at temperatures higher than 310 K but demonstrate increasing deviations (up to a maximum of 0.92% at 280 K) at temperatures below 310 K. Across the entire temperature range (Tr = 0.64–0.998) the AAD% is 0.09%. 4.1.3. PVT properties Table 6 reports the publicly available experimental PVT data identified in the peer-reviewed literature for eleven working fluids, namely the same ones of Table 5, with the addition of R1354myf(E). The PVT measurements can be grouped into single phase PVT measurements and saturated density measurements. In some cases (e.g. Fukushima et al., 2015 or Richter et al., 2011) data in both the superheated vapor phase and in the compressed liquid phase are reported. In other cases, only compressed liquid data (e.g. Fedele et al., 2012) or superheated vapor data (e.g. Di Nicola et al., 2010a) are reported. In a few cases, saturated liquid density data were directly measured. Three data sets (Fukushima et al., 2015 for R1123; Tanaka and Higashi, 2010a for R1234yf; and Higashi et al., 2010 for R1234ze(E)) report saturation data near the critical point. The most investigated fluids are R1234yf (12 data sets totalling almost 950 data points) and R1234ze(E) (20 data sets totalling more than 1300 data points). For these two fluids, together with R1234ze(Z) and R1233zd(E), two other fluids with a considerable amount of data and at least three sets, just as we did for vapor pressure, we conduct a more detailed analysis with the aim to evaluate the property distributions and their deviations from values calculated with the reference EoS implemented in REFPROP (Table 3). Fig. 3 (a)–(d) shows the distribution on the P−T plane of the available data for these fluids. It is worth noting that for better readability, the pressure is represented in logarithmic scale. For almost all the other fluids,

187

only 1 or 2 sets of data are available, even if in several cases with a considerable amount of data (R1234zf: 1 reference, 403 data; R1225ye(Z): 1 reference, 240 data; R1336mzz(E): 1 reference, 169 data; R1336mzz(Z): 1 reference, 359 data; R1354mzy(E); 3 references, 173 data, R1354myf(E): 1 reference, 47 data). Fig. 4 (a)–(d) shows the percentage deviations of the experimental data for the four most studied fluids from the values calculated with REFPROP at the same temperatures and pressures as a function of temperature. It is worth noting here that in the diagram for R1234ze(E) (Fig. 3(b)), the maximum pressure has been limited to 8 MPa for better readability, even if the data of Yamaya et al. (2011a) have deviations up to 34% and thus are not all shown in the diagram. R1234yf: 10 papers identified in the literature report experimental PVT data for R1234yf: 6 of them report data for compressed liquid density, 3 for superheated vapor density, 1 for supercritical density, 1 for saturated liquid and 1 for saturated liquid and vapor densities near the critical point. Compressed liquid: Fedele et al. (2012) report 280 data in the range Tr = 0.77–0.96 and a much wider range of pressures (Pr = 0.20–10.35, Pmax = 35 MPa), with an AAD% = 0.09% and a maximum deviation of 0.47% and slightly higher percentage deviations at the highest temperatures and for pressures approaching saturation. Klomfar et al. (2012a) measured 89 data for a wide range of temperatures (Tr = 0.77–0.96) and pressures (Pr = 0.28– 11.85) with small deviations (AAD% = 0.05% with a maximum deviation = 0.17%) for the entire range, with slightly higher deviations at high and low pressures. 128 data are reported by Qiu et al. (2013) with Tr = 0.77–0.96 and a wide range of pressures (Pr = 0.30–29.57, Pmax = 100 MPa). The deviations (AAD% = 0.16%, with a maximum deviation = 1.59%) are slightly higher than those of other sets of compressed liquid data, especially at the highest temperatures. It should be noted that the pressures over 60 MPa are not included, as they fall outside the range of validity of the EoS implemented in REFPROP. Richter et al. (2011) report 41 data with Tr = 0.63–1.03 and Pr = 0.30–2.83; in this region the AAD% is only 0.02% with a maximum deviation of 0.08%. The 23 data of Tanaka et al. (2010b) cover a relatively limited region of the P−T plane, with reduced temperature Tr = 0.84–0.98 and reduced pressures Pr = 0.30–1.48. The AAD% is 0.11%, with a maximum deviation of 0.82%. Yoshitake et al. (2009) measured density in the range Tr = 0.74–0.88, but they report only an equation correlating the experimental data. Superheated vapor: Di Nicola, C. et al. (2010a) report 136 data in the range Tr = 0.66–1.014 for pressures Pr = 0.085–3.716. The deviations are relatively higher than those of the compressed liquid set of data, with an AAD% = 0.45% with a maximum deviation of 3.09%, excluding one anomalous point with a deviation of −34.9%. The deviations show more bias in the lower temperature region. Hu et al. (2017a) report 83 density data, with Tr = 0.69–0.940 and Pr = 0.021–0.565. The deviations from REFPROP are AAD% = 0.19 and MAD% = 0.72%. Finally, Richter et al. (2011) report 51 density data in a smaller region (Tr = 0.87–1.087, Pr = 0.164–1.034), with AAD% = 0.32 and MAD% = 0.76% without any bias. Supercritical region: Richter et al. (2011) report 16 data with Tr = 1.01–1.03 and Pr = 1.02–1.95 in the near critical region. The scattering is quite evident, with an AAD% of 0.38% and a maximum deviation of 1.57%. Saturation: Hulse et al. (2009) report 9 liquid density data in the range Tr = 0.72–0.994, with AAD% = 0.17% from REFPROP and increasing deviations with temperature (maximum deviation of 0.43% at Tr = 0.994). Tanaka and Higashi (2010a) report 12 data for the liquid density and 10 data for the vapor. All of these data were measured in the region close to the critical point (Tr = 0.95– 1.00) in order to determine the critical density. The AAD% is 1.17%, with a maximum deviation of 3.03%.

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Table 6 Available experimental data for the PVT properties of several HFO and HCFO refrigerants. ASHRAE designation

R1123 R1234yf

R1243zf R1234ze(E)

R1225ye(Z) R1234ze(Z)

R1233zd(E)

R1336mzz(E) R1336mzz(Z) R1354mzy(E)

R1354myf(E) a

References

Fukushima et al. (2015) Higashi and Akasaka (2016) Compressed liquid (cl) Fedele et al. (2012) Klomfar et al. (2012a) Qiu et al. (2013) Richter et al. (2011) Tanaka et al. (2010b) Yoshitake et al. (2009)a Superheated vapor (sv) Di Nicola, C. et al. (2010a) Hu et al. (2017a) Richter et al. (2011) Supercritical region (scr) Richter et al. (2011) Saturation Hulse et al. (2009) Tanaka and Higashi (2010a) Di Nicola et al. (2013a) Compressed liquid (cl) Brown et al. (2012) (CNR-ITC) Grebenkov et al. (2009) Klomfar et al. (2012b) McLinden et al. (2010) Qiu et al. (2013) Tanaka et al. (2010a) Yamaya et al. (2011a) Superheated vapor (sv) Brown et al. (2012) (UnivPM) Grebenkov et al. (2009) McLinden et al. (2010) Tanaka and Higashi (2010b) Yin et al. (2018) Zhang et al. (2016a) Supercritical region (scr) McLinden et al. (2010) Yamaya et al. (2011a) Saturation Gong et al. (2016a) Grebenkov et al. (2009) Higashi et al. (2010) Tanaka (2016a) Tanaka et al. (2010a) Brown et al. (2015) Compressed liquid (cl) Fedele et al. (2014b) (CNR-ITC) Higashi et al. (2015) Romeo et al. (2017) Tanaka et al. (2013)a Superheated vapor (sv) Fedele et al. (2014b) (UnivPM) Higashi et al. (2015) Sakoda et al. (2017) Tanaka et al. (2013)a Saturation Higashi et al. (2015) Kayukawa et al. (2012)a Tanaka (2016a) Compressed liquid (cl) Fedele et al. (2018) (CNR-ITC) Mondejar et al. (2015) Romeo et al. (2017) Tanaka (2016b) Superheated vapor (sv) Fedele et al. (2018) (UnivPM) Mondejar et al. (2015) Tanaka (2016b) Supercritical region (scr) Mondejar et al. (2015) Tanaka (2016b) Saturation (sat) Hulse et al. (2012) Tanaka et al. (2017c) Tanaka et al. (2016) Kayukawa et al. (2015)a Kimura et al. (2017a) Kimura et al. (2017b) Kayukawa et al. (2015)a

No. data

T range (K)

P range (MPa)

AAD%

263 ÷ 473 300 ÷ 430

1.385 ÷ 9.782 2.252 ÷ 6.675

–

280 89 128 39 23 73

283 ÷ 353 217 ÷ 353 284 ÷ 363 232 ÷ 365 310 ÷ 360 273 ÷ 323

0.684 ÷ 35.017 0.963 ÷ 40.033 1.0 0 0 ÷ 10 0.0 0 0 1.001 ÷ 9.586 1.0 0 0 ÷ 5.0 0 0 0.800 ÷ 16.000

0.09 0.05 0.16 0.02 0.11 n.a.

136 83 51

243 ÷ 373 253 ÷ 346 320 ÷ 400

0.085 ÷ 3.716 0.070 ÷ 1.910 0.554 ÷ 3.252

0.45 0.19 0.32

370 ÷ 380

1.021 ÷ 1.947

0.32

265 ÷ 365 348 ÷ 368 278 ÷ 368

0.238 ÷ 3.227 2.270 ÷ 3.382 0.260 ÷ 35.0 0 0

0.17 1.17 –

270 20 101 42 131 26 25

283 ÷ 353 283 ÷ 371 205 ÷ 353 240 ÷ 380 283 ÷ 363 310 ÷ 370 270 ÷ 380

0.170 ÷ 9.371 0.644 ÷ 9.472 1.015 ÷ 40.411 0.921 ÷ 15.337 1.0 0 0 ÷ 100.010 2.0 0 0 ÷ 5.0 0 0 2.684 ÷ 16.163

0.07 0.55 0.04 0.02 0.07 0.08 2.96

159 40 40 204 101 26

243 ÷ 373 316 ÷ 390 340 ÷ 420 310 ÷ 360 313 ÷ 373 263 ÷ 293

0.057 ÷ 1.024 0.570 ÷ 3.649 1.096 ÷ 3.609 0.657 ÷ 2.300 0.117 ÷ 2.831 0.102 ÷ 0.409

0.63 3.35 0.18 0.14 0.11 0.06

54 12

383 ÷ 420 385 ÷ 425

3.632 ÷ 6.741 4.344 ÷ 15.976

0.40 17.64

136cl + 104sv

253 ÷ 293 251 ÷ 381 368 ÷ 383 300 ÷ 380 310 ÷ 370 263 ÷ 368

0.097 ÷ 0.430 0.025 ÷ 0.969 2.760 ÷ 3.632 0.527 ÷ 3.462 0.703 ÷ 2.841 0.135 ÷ 35.0 0 0

0.06 0.14 1.49 0.05 0.07 –

313b 38 36 41

283 ÷ 363 370 ÷ 432 273 ÷ 333 310 ÷ 410

0.188 ÷ 34.026 1.845 ÷ 6.027 1.0 0 0 ÷ 30.050 Up to 5

0.09 0.09 0.14 N.A.

98 33 30 12

283 ÷ 363 360 ÷ 440 353 ÷ 413 310 ÷ 410

0.082 ÷ 0.436 0.944 ÷ 4.312 0.162 ÷ 2.734 up to 5

0.55 0.34 0.11 N.A.

356 ÷ 423 310 ÷ 410 300 ÷ 400

0.925 ÷ 3.531 0.263 ÷2.780 0.186 ÷ 2.309

2.24 N.A. 0.18

93 117 30 39

283 ÷ 363 215 ÷ 444 274 ÷ 333 329–440

0.133 ÷ 35.002 0.476 ÷ 24.079 1.0 0 0 ÷ 25.010 0.777 ÷ 9.765

0.04 0.01 0.02 0.65

60 43 33

308–373 350 ÷ 440 328–443

0.167 ÷ 0.693 0.255 ÷ 1.923 0.777 ÷ 9.770

0.41 0.05 7.74

5 25

444 440–444

3.858 ÷ 5.619 3.773 ÷ 8.632

0.02 2.02

243 323 323 280 425 280 280

0.011 – 0.108 0.579 ÷ 10.130 0.182 ÷ 9.927 1.0 0 0 ÷ 20.0 0 0 3.249 ÷ 5.056 0.482 ÷ 20.0 0 0 0.480 ÷ 20.0 0 0

0.15 – –

Pρ T

ρ

69cl+sv+scr 30cl + 33sv

7l + (6l + 6v )ncp 21l

sat

16 l

9 (12l + 10v )ncp 302

cl

+ 101

sv

10l 10l (9l + 13v )ncp 18l 7l

9l+ 10v 11l 22l

154sc+sv+sc 278cl+sv + 66ncp 50cl 10ncp + 21scr 50cl + 52sv 47cl

13l 11l + 4v 11l + 4v

÷ ÷ ÷ ÷ ÷ ÷ ÷

293 523 503 420 450 420 420

– –

No tables with experimental data. Only correlation. The paper reports 313 data selected amongst the 22,182 data actually measured and presented as supplementary material in the on-line version of the paper. b

S. Bobbo et al. / International Journal of Refrigeration 90 (2018) 181–201

189

Fig. 3. Distribution on the P−T plane of the available experimental PVT data for (a) R1234yf, (b) R1234ze(E), (c) R1234ze(Z) and (d) R1233zd(E).

R1234ze(E): PVT data for R1234ze(E) are reported in 14 different papers. 7 data sets include compressed liquid data, including some supercritical data, 6 include superheated vapor data, 1 supercrtical density data and 4 include saturated liquid data, while 1 data set is for near critical point saturated liquid and vapor density. Compressed liquid: Brown et al. (2012) report 270 data in the range of reduced temperatures between 0.74 and 0.923 and reduced pressures between 0.17 and 9.37. The deviations are quite low (AAD% = −0.07% with a maximum of 0.23%) but slightly increasing at pressures close to saturation. Grebenkov et al. (2009) report 20 density data (Tr = 0.74–0.97; Pr = 0.18–2.61, with relatively low deviations (AAD% = 0.55%, MAD% = 1.17%). Klomfar et al. (2012b) report 101 data in a wide region below the critical point, especially at low temperatures and high pressures (Tr = 0.54–0.92; Pr = 0.28–11.13). The deviations are very low

(AAD% = 0.04% with a maximum of 0.1%) in all the range of temperatures. McLinden et al. (2010) report a total of 42 density data (Tr = 0.63–0.999; Pr = 0.25–4.22). The deviations are very small in all the ranges of temperatures and pressures, with AAD% = 0.02 and maximum absolute deviation of 0.09%. The data reported by Qiu et al. (2013) are distributed in a wide subcritical region with reduced temperatures between 0.74 and 0.95 and up to very high reduced pressures, which range from 0.28 to 27.54. The deviations are quite low (AAD% = 0.07% and MAD% = 0.69%), but the data at pressures higher than 40 MPa (Pr = 11) are not included, because the EoS used in REFPROP is not valid in that region. Tanaka et al. (2010a) measured 26 density data in the ranges Tr = 0.81–0.967 and Pr = 0.55–1.38: the deviations are quite low (AAD% = 0.08%, with maximum absolute deviation of 0.26%), but slightly increasing with temperature and pressure. Yamaya et al. (2011a) measured 25 data in the ranges Tr = 0.71–0.994; Pr = 0.74–4.45. The devia-

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S. Bobbo et al. / International Journal of Refrigeration 90 (2018) 181–201

Fig. 4. Deviations of the experimental PVT data for (a) R1234yf, (b) R1234ze(E), (c) R1234ze(Z) and (d) R1233zd(E) from the values calculated with REFPROP database.

tions are quite high, especially at high temperatures and pressures: AAD% = 2.96%, MAD% = 8.06%. Superheated vapor: Brown et al. (2012) report 160 superheated vapor density data in the range Tr = 0.64–0.98. Relatively high deviations (AAD% = −0.63% with a maximum of 1.92%) are seen in the superheated vapor density data. Grebenkov et al. (2009) report 40 density data (Tr = 0.83–0.968; Pr = 0.16–0.37). The deviations are quite high and systematic (AAD% = 3.35%, MAD% = 6.19%). McLinden et al. (2010) report density data in the ranges Tr = 0.89– 1.098 and Pr = 0.30–0.994, with AAD% = 0.18% and MAD% = 5.41%. Tanaka and Higashi (2010b) report 204 data for the superheated vapor density in a relatively narrow range of reduced temperatures (Tr = 0.81–0.94), while reduced pressures range from 0.18– 0.63. The AAD% is 0.14% with MAD% = 0.45% and almost constant in all the range of temperatures. Yin et al. (2018) report

101 data in the ranges Tr = 0.82–0.976; Pr = 0.01–0.44. The deviations are quite small in these ranges, with AAD% = 0.11% and MAD% = 0.52%. Finally, 26 density data are reported by Zhang et al. (2016a) (Tr = 0.69–0.77 Pr = 0.03–0.11). Also in this case the deviations are very small, with AAD% = 0.6% and MAD% = 0.14%). Supercritical region: McLinden et al. (2010) report a total of 54 density data in the near critical region (Tr = 1.001–1.098; Pr = 1.00–1.86), with moderate deviations (AAD% = 0.40% and MAD% = 5.41%). Yamaya et al. (2011a) measured 12 data in the ranges Tr = 1.007–1.111; Pr = 1.196–4.399. These data are affected by very high deviations, especially in the near critical region and at high pressures: the AAD% is 17.64%, with a maximum absolute deviation of 34.08% at Tr = 1.11 and Pr = 1.994, i.e. the extreme experimental conditions.

S. Bobbo et al. / International Journal of Refrigeration 90 (2018) 181–201

Saturation: Saturated liquid or vapor density data are reported in 5 papers, for a total 68 data, most of them for saturated liquid. Gong et al. (2016a) report 10 liquid density data in the range Tr = 0.77–0.66 with very low deviations (AAD% = 0.06%, MAD% = 0.08%) in all the range. Grebenkov et al. (2009) report 10 liquid density (Tr = 0.66–0.996). with very small deviations (AAD% = 0.10%, MAD% = 0.40%) from REFPROP. Higashi et al. (2010) report 9 liquid and 13 vapor density data in the near critical region (Tr = 0.963–1.00), with experimental determination of the critical density. AAD% is 1.49%, with MAD = 4.05% in the critical region. These deviations are attributed to the difficulty for the EoS to adequately represent the critical region. Tanaka (2016a) measured 18 liquid density data in the range of reduced temperatures between 0.78 and 0.993, with AAD% = 0.05% and MAD% = 0.21%. Except for a couple of data, all the others show deviations below 0.1%. Finally, Tanaka et al. (2010a) report 7 saturated liquid density data in the range Tr = 0.81–0.967 with quite low deviations (AAD% = 0.07%, MAD% = 0.31%) in all the range. R1234ze(Z): PVT data for R1234ze(Z) are reported in 7 different papers. 4 data sets include compressed liquid data, 4 include superheated vapor data and 3 include saturated density data, of which 1 is for near critical point saturated liquid and vapor density. Compressed liquid: Fedele et al. (2014b) measured 22,182 data in the compressed liquid region even if the paper report 313 selected data. The full set of data is available as supplementary material in the on-line version of the paper. The data are distributed in the ranges Tr = 0.67–0.86 and Pr = 0.053–9.631, with AAD% = 0.09%, and MAD% = 0.27% However, a great part of the data are outside the range of validity of the equation of state used in REFPROP. Higashi et al. (2015) report 38 data of compressed liquid in the range of reduced temperatures between 0.87 and 0.867 and reduced pressures between 0.47 and 1.52, with AAD% = 0.09%, and MAD% = 0.5% and higher deviations in the critical region. Romeo et al. (2017) report 36 data in a relatively limited range of reduced temperatures (Tr = 0.65–0.79) and reduced pressures ranging from 0.28 to 8.51, with AAD% = 0.14% and MAD% = 0.36%. However, a great part of the data are outside the range of validity of the equation of state used in REFPROP. Superheated vapor: in Fedele et al. (2014b) 98 data are reported for superheated vapor for reduced temperatures between 0.72 and 0.89 and reduced pressures between 0.021 and 0.110. The deviations from REFPROP are AAD% = 0.55% and MAD% = 1.51%. Higashi et al. (2015) report 33 data of superheated vapor, distributed in the ranges Tr = 0.84–1.03 and Pr = 0.23–1.09, with higher deviations (AAD% = 0.34%, MAD% = 1.48%) and tend to increase with decreasing temperature. Sakoda et al. (2017) report 30 data with reduced temperatures between 0.83 and 0.976 and reduced pressures between 0.041 and 0.689. The deviations from REFPROP are AAD% = 0.11% and MAD% = 0.53%. Saturation: Higashi et al. (2015) report 20 data for density in the near critical region (9 for liquid and 10 for vapor in addition to the critical density). The data are distributed in the ranges Tr = 0.84– 1.00 and Pr = 0.23–1.00, with quite large deviations (AAD% = 2.24%, MAD% = 11.94%) but mainly close to the critical point, again probably due to the limit of the equation of state. Finally, 22 saturated liquid density data are reported by Tanaka (2016a) in the range of reduced temperatures between 0.71 and 0.945, with AAD% = 0.18% and MAD% = 0.39%. Kayukawa et al. (2012) measured 11 saturated liquid densities in the range Tr = 0.73–0.85, while Tanaka et al. (2013) report 41 compressed liquid density data and 12 superheated vapor density data in the same range. However, these papers are not available to the authors and thus are not included in the discussion. R1233zd(E): five papers report PVT data for R1233zd(E) for a total of 10 data sets: 4 of them include compressed liquid data, 3

191

include superheated vapor data, 1 includes saturated density data and 1 includes near critical point saturated vapor and liquid density data. It is worth to note that the equation of state implemented in REFPROP is based on PVT data sets of Mondejar et al. (2015), here below discussed. Compressed liquid: Fedele et al. (2018) report 93 data in the ranges Tr = 0.65–0.83 and Pr = 0.04–9.28. The deviations are quite low, being AAD% = 0.04% and MAD% = 0.12%. Mondejar et al. (2015) data cover the range of reduced temperatures between 0.49 and 1.012 and reduced pressures between 0.13 and 6.38. The deviations are very low, with a slight increase in the near critical region: AAD% = 0.006% and MAD% = 0.14%. Romeo et al. (2017) report 30 density data in the ranges Tr = 0.76–0.62 and Pr = 0.27– 6.63, with very small deviations from REFPROP (AAD% = 0.02%, MAD% = 0.06%). Tanaka et al. (2016) report 39 data in the ranges Tr = 0.75–1.002 and Pr = 0.21–2.589. The deviations almost constant, around 0.4%, at increasing temperatures, but clearly increase in the near critical point region (AAD% = 0.65%, MAD% = 4.34%). Superheated vapor: Fedele et al. (2018) report 60 data, distributed in the ranges Tr = 0.70–0.85 and Pr = 0.04–0.18. The deviations are relatively high even if not biased: AAD% = 0.5%, MAD% = 1.05%. 43 data are reported by Mondejar et al. (2015), with Tr = 0.80–1.003 and Pr = 0.07–0.51. The deviations are very low: AAD% = 0.05% and MAD% = 0.13%. Tanaka et al. (2016) report 33 data, many of them in the near critical region, with Tr = 0.97– 1.011 and Pr = 0.68–0.99. The deviations are very high with AAD% = 7.74% and MAD% = 31.84%. Supercritical region: Mondejar et al. (2015) report actually 5 data in this region, differently from the 4 declared in the paper. The data are all measured at Tr = 1.012, with reduced pressures varying from 1.02 and 1.49. The deviations are very small for all points, with AAD% = 0.02% and MAD% = 0.04%. Tanaka et al. (2016) report 25 data distributed in the ranges Tr = 1.002–1.011 and Pr = 1.000– 2.288. The deviations are quite significant, being AAD% = 2.02% and MAD% = 8.87%. Saturation: saturated liquid densities have been measured by Hulse et al. (2012), who report 13 data with reduced temperatures between 0.55 and 0.67. The deviations are relatively high (AAD% = 0.15%, MAD% = 0.38%) and slightly increasing at decreasing temperatures. 4.1.4. Specific heat capacity Table 7 reports the publicly available experimental heat capacity data identified in the peer-reviewed literature for three working fluids. The heat capacity data can be grouped into ideal gas heat capacity (c0p ), isobaric heat capacity (cp ) in the single phase region and at saturation conditions (cp, sat ), and isochoric heat capacity (cv ) in the single phase region. Isobaric heat capacities are the most frequently measured among the heat capacity properties. The most investigated working fluids are R1234yf (8 data sets for a total of 292 data points) and R1234ze(E) (7 data sets for a total of 332 data points), while only one data set is available for R1233zd(E). Fig. 5 shows the distribution of heat capacity data for R1234yf and R1234ze(E) in the P−T plane, while Fig. 6 shows the deviations of the experimental values from those calculated with REFPROP at the same conditions. Considering the estimated uncertainty for the calculated heat capacities is 5%, the diagram allows to highlight only the relative dispersion of the data. R1234yf: ideal gas heat capacity data are reported by Hulse et al. (2009) (13 data calculated from vibrational energies) and Kano et al. (2010) (6 data derived from speed of sound measurements). Liquid isobaric specific heat capacity data are reported by Gao et al. (2014a), Tanaka et al. (2010b) and Liu et al. (2017), while saturated liquid specific heat capacity has been measured by Tanaka et al. (2010b) and calculated by extrapolation by Gao

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S. Bobbo et al. / International Journal of Refrigeration 90 (2018) 181–201 Table 7 Available experimental data for the heat capacity of several HFO and HCFO refrigerants. ASHRAE designation

R1234yf

R1234ze(E)

R1233zd(E) a b c

References

Gao et al. (2014a) Hulse et al. (2009) Kano et al. (2010) Liu et al. (2017) Tanaka et al. (2010b) Gao et al. (2015) Kagawa et al. (2011) Kano et al. (2013) Liu et al. (2018) Tanaka et al. (2010c) Yamaya et al. (2011a) Hulse et al. (2012)

No. data cp 0

cp

cp

– 13 6a

74cl – – 154cl+scr 22cl 95cl 19sv – 130cl+scr 26cl – –

11l b – –

– – –

6l 12l b – –

– – – –

7l b – –

– 37cl –

– – – 6a – – – 11c

sat

T range (K)

P range (MPa)

305 ÷ 355 213 ÷ 573 278 ÷ 353 304 ÷ 373 310 ÷ 360 310 ÷ 365 303 ÷ 363 278 ÷ 353 313 ÷ 393 310 ÷ 370 270 ÷ 425 100 ÷ 10 0 0

1.500 ÷ 5.000 – – 1.510 ÷ 12.080 0.940 ÷ 5.0 0 0 1.560 ÷ 5.490 0.350 ÷ 1.300

cv

1.040 ÷ 10.090 2.0 0 0 ÷ 5.0 0 0 2.684 ÷ 15.976 –

Derived from speed of sound measurements. Calculated by extrapolation of cp to saturation pressure. Calculated with quantum mechanics.

Fig. 5. Distribution on the P−T plane of the available experimental specific isobaric and isochoric heat capacity data for (a) R1234yf and (b) R1234ze(E).

et al. (2014a). Liu et al. (2017) report also 16 data in the supercritical region. While all single phase data deviate less than 5%, showing some agreement with the EoS, the data for saturated liquid show much higher deviations (MAD% = 35%) with systematic increase from lower to higher temperatures. It is worth noting that the data of Gao et al. (2014a) are in strong agreement with REFPROP (AAD% = 0.30%, MAD% = 0.93%). R1234ze(E): among the available data sets, 1 reports ideal gas heat capacity data (Kano et al., 2013), 3 report liquid isobaric specific heat capacity (Gao et al., 2015; Tanaka et al., 2010c and Liu et al., 2018), 1 isochoric specific heat capacity (Yamaya et al., 2011a), while 1 set reports superheated vapor isobaric heat capacity (Kagawa et al., 2011). Generally, the data deviate quite less than 5% from the EoS, except part of the data of Yamaya et al. (2011a), which deviate up to 12% for temperatures up to 385 K, but much more (from 31% to 58%) at temperatures from 385 K and 425 K (not shown in Fig. 6). Saturated liquid isobaric heat capacity values are calculated by extrapolation in two papers (Gao et al., 2015 and Tanaka et al., 2010c).

4.1.5. Speed of sound Table 8 reports the publicly available experimental speed of sound data identified in the peer-reviewed literature for four working fluids, namely R1234yf, R1234ze(E), R1234ze(Z), R1233zd(E). New data for R1234yf, R1234ze(E), R1233zd(E) and R1336mzz(Z) have been kindly anticipated to the authors and will be published shortly (McLinden and Perkins, 2018). The most investigated fluids are R1234yf and R1234ze(E), with 4 data sets each. However, the data of Gao et al. (2014b) for R1234yf are not accessible to the authors of this paper. Fig. 7(a) and (b) shows the distribution of the available data on the P−T plane, while Fig. 8(a) and (b) reports the deviations from REFPROP. R1234yf: Kano et al. (2010) reported 41 superheated vapor data in the range of reduced temperatures between 0.76 and 0.96 and reduced pressures between 0.007 and 0.12. The deviations from REFPROP (declared uncertainty below 0.1%) are AAD% = 0.008 and MAD% = 0.03, with very low absolute deviations in all the range of temperatures. 22 liquid phase speed of sound data were reported by Lago et al. (2011) in the ranges Tr = 0.71–0.979 and Pr = 0.59–

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193

Fig. 6. Deviations of the experimental specific heat capacity data for (a) R1234yf and (b) R1234ze(E) from the values calculated with REFPROP database. Table 8 Available experimental data for the speed of sound of several HFO and HCFO refrigerants. ASHRAE designation

References

No. data

T range (K)

P range (MPa)

AAD%

R1234yf

Gao et al. (2014b) Kano et al. (2010) Lago et al. (2011) McLinden and Perkins (2018) Kano et al. (2013) Lago et al. (2011) McLinden and Perkins (2018) Perkins and McLinden (2015) Lago et al. (2016) McLinden and Perkins (2018) Mondejar et al. (2015) McLinden and Perkins (2018)

N.A. 41sv 22cl 86cl 41sv 24cl 134cl 223sv 38cl 135cl 155sv 183cl

273 278 260 235 278 260 230 280 273 230 290 230

0.316 ÷ 2.520 0.025 ÷ 0.407 1.990 ÷ 6.060 0.637 ÷ 25.751 0.025 ÷ 0.403 1.960 ÷ 10.110 0.898 ÷ 36.704 0.080 ÷ 2.832 0.192 ÷ 25.059 0.135 ÷ 25.613 0.068 ÷ 2.073 0.674 ÷ 45.53

N.A. 0.01 0.19 0.70 0.04 0.23 0.04 0.60 3.90 0.61 0.06 –

R1234ze(E)

R1234ze(Z) R1233zd(E) R1336mzz(Z)

÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷

353 353 360 380 353 360 420 420 333 420 420 420

Fig. 7. Distribution on the P−T plane of the available experimental speed of sound data for (a) R1234yf and (b) R1234ze(E).

194

S. Bobbo et al. / International Journal of Refrigeration 90 (2018) 181–201

Fig. 8. Deviations of the experimental speed of sound data for (a) R1234yf and (b) R1234ze(E) from the values calculated with REFPROP database.

1.79. The deviations from REFPROP (declaring an uncertainty of 0.5% for speed of sound in the liquid phase) are AAD% = 0.19% and MAD% = 1.84%, with much higher deviations in the near critical region. McLinden and Perkins (2018) measured 86 data for the compressed liquid in the ranges Tr = 0.64–1.033 and Pr = 0.19–7.61, with systematic negative deviations from REFPROP (AAD% = 0.70%, MAD% = 2.23%). R1234ze(E): 2 sets of data is available for liquid phase speed of sound (Lago et al., 2011 and McLinden and Perkins, 2018) and 2 sets for vapor phase speed of sound (Kano et al., 2013 and Perkins and McLinden, 2015). REFPROP declares an uncertainty of 0.2% in the liquid phase and of 0.05% in the vapor phase. 41 data in the vapor phase are reported by Kano et al. (2013), with reduced temperature between 0.73 and 0.923 and reduced pressures between 0.007 and 0.111. The deviations from REFPROP are low in all these ranges, being AAD% = 0.04% and MAD% = 0.06%. Lago et al. (2011) report 24 data in the ranges Tr = 0.68–0.941 and Pr = 0.54–2.78, with AAD% = 0.23% and MAD% = 1.87. However, excluding the data at 360 K, the deviations are much lower: AAD% = 0.06 and MAD% = 0.17. McLinden and Perkins (2018) measured 134 data for the compressed liquid in the ranges Tr = 0.60– 1.098 and Pr = 0.25–10.11, with quite scattered deviations from REFPROP (AAD% = 0.60%, MAD% = 2.01%), even if several points are out of the range of validity of the reference EoS. Finally, Perkins and McLinden (2015) reported 223 vapor phase speed of sound data in the ranges Tr = 0.73–1.098 and Pr = 0.022–0.78. The deviations from REFPROP are low in all these ranges, with AAD% = 0.04% and MAD% = 0.13%. R1234ze(Z): it is worth noting that the only set of data available for this fluid (Lago et al., 2016) is in strong disagreement with REFPROP (AAD% = 3.90%, MAD% = 4.71%), notwithstanding the very low uncertainty (U%) declared for the measurements (U% = 0.046%). Even if it must be considered that many data are out of the limit of validity of the EoS and thus they were not considered in the calculation of the deviations, this suggest some limits in the reference EoS. 4.2. Transport properties Transport properties influence heat and mass transfer processes and play a key role in properly designing components, particu-

larly heat exchangers, and optimizing overall system performance. Among transport properties, thermal conductivity, viscosity, and surface tension are the most important, particularly for modeling boiling and condensation heat transfer processes and pressure drop. Similarly, to what was done above for thermodynamic properties, the following discussion provides the references which report experimental data for the above-mentioned transport properties for each halogenated olefin refrigerant, with special mention given to the number of experimental data and the temperature and pressure ranges of the various data sets. 4.2.1. Thermal conductivity Thermal conductivities were measured for only three fluids, namely R1234yf, R1234ze(E), and R1234ze(Z) (Table 9). Perkins and Huber (2011) measured the thermal conductivity in both compressed liquid and superheated vapor regions for R1234yf and R1234ze(E) in the range of temperature from 242 K to 344 K and from 203 K to 344 K, respectively. The pressure ranges for both sets of measurements varied from 0.1 MPa to 23 MPa. A total of 790 data points were reported for R1234yf and a total of 903 data points were reported for R1234ze(E). Grebenkov et al. (2009) measured the thermal conductivity of R1234ze(E) in the compressed liquid region (94 data) and the superheated vapor region (84 data). The measurements were performed at temperatures from 252 K to 407 K and pressures from 0.049 to 20 MPa. Measurements for R1234ze(Z) were performed by Ishida et al. (2015) at saturation conditions for the liquid phase region (21 data points for the temperature range from 283.54 K to 343.57 K) and for the vapor phase region (24 data points for the temperature range from 283.45 K to 353.46 K). 4.2.2. Viscosity Table 10 reports the publicly available experimental viscosity data contained in the peer-reviewed literature for four fluids, namely R1234yf, R1234ze(E), R1234ze(Z) and R1233zd(E). However, for R1234ze(Z) the papers of Kariya et al. (2015) and Kariya et al. (2017) report only correlations and graphical representations for the 2 sets of experimental data in the subcooled liquid and superheated vapor regions, while for R1233zd(E) only one data set consisting of only 6 data points is available. The distribution of the available data on the P−T plane is shown in Fig. 9(a) and (b),

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195

Table 9 Available experimental data for the thermal conductivity of several HFO and HCFO refrigerants. ASHRAE designation

R1234yf R1234ze(E) R1234ze(Z)

References

Perkins and Huber (2011) Perkins and Huber (2011) Grebenkov et al. (2009) Ishida et al. (2015)

No. data

λ

λsat

311cl + 479sv 452cl + 451sv 94cl + 84sv –

– – – 21l + 24v

T range (K)

P range (MPa)

242 203 252 283

0.1 ÷ 23 0.1 ÷ 23 0.046 ÷ 20

÷ ÷ ÷ ÷

344 344 407 353

Table 10 Available experimental data for the viscosity of several HFO and HCFO refrigerants. ASHRAE designation R1234yf

R1234ze(E)

R1234ze(Z) R1233zd(E) a

References Cousins and Laesecke (2012) Dang et al. (2015a) Dang et al. (2015b) Hulse et al. (2009) Meng et al. (2013) Yamaguchi et al. (2009)a Zhao et al. (2014) Cousins and Laesecke (2012) Grebenkov et al. (2009) Meng et al. (2013) Zhao et al. (2014) Kariya et al. (2015)a Kariya et al. (2017)a Hulse et al. (2012)

No. data sat l

20 25cl 8sv 39cl 110cl 94 10sat l 20sat l 35cl + 18sv 119cl 9sat l (N.A.)cl+sv N.A. 6cl

T range (K)

P range (MPa)

247 ÷ 340 283 ÷ 321 274 ÷ 338 257 ÷ 307 243 ÷ 363 263 ÷ 323 293 ÷ 365 247 ÷ 340 257 ÷ 369 243 ÷ 373 295 ÷ 373 283 ÷ 363 290 ÷ 440 270 ÷ 380

0.115 ÷ 1.911 0.591 ÷ 1.302 0.105 0.326 ÷ 2.109 Saturation ÷ 30.0 0 0 0.100 ÷ 1.960 At saturation 0.072 ÷ 1.499 0.990 ÷ 6.080 Saturation ÷ 30.0 0 0 At saturation 0.180 ÷ 1.350 0.500 ÷ 3.000 0.100 ÷ 1.350

No tables with experimental data. Only correlation.

Fig. 9. Distribution on the P−T plane of the available experimental viscosity data for (a) R1234yf and (b) R1234ze(E).

while the deviations from REFPROP are reported in Fig. 10(a) and (b). R1234yf: it is the most investigated fluid, for which 7 data sets are available, consisting of a total of 306 data points both in the single phase region and at saturation conditions. Considering the declared uncertainty of REFPROP in calculating the viscosity of R1234yf is based simply on a comparison with Hulse et al. (2009) and is estimated to be ±10%, a systematic analysis of the available data sets is not performed here. It is enough to highlight how all the reported data deviate less than 10% from the equation used in REFPROP and are, within this limit, in relative agreement each other. The only exception is given by saturated liquid kinematic viscosity of Zhao et al. (2014) which show deviations higher

than 10% at the highest temperatures. It is worth noting that the data of Yamaguchi et al. (2009) for R1234yf are not accessible to the authors of the present paper. R1234ze(E): 4 data sets are available, again both in the single phase region and at saturation conditions, for a total of 201 data points. Grebenkov et al. (2009) report 35 data in the compressed liquid region and 18 in the superheated vapor region. Fig. 10(b), shows that only the data of Cousins and Laesecke (2012) for saturated liquid and those of Grebenkov et al. (2009) in the compressed liquid region deviate less than 3% from REFPROP. All the other sets, especially the one of Meng et al. (2013) and those of Grebenkov et al. (2009) in the vapor region, show much higher

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Fig. 10. Deviations of the experimental viscosity data for (a) R1234yf and (b) R1234ze(E) from the values calculated with REFPROP database. Table 11 Available experimental data for the surface tension of several HFO and HCFO refrigerants (all data are for the saturated liquid). Fluid

References

No. data

T range (K)

R1234yf

Tanaka and Higashi (2010a) Zhao et al. (2014) Kondou et al. (2015) Grebenkov et al. (2009) Tanaka and Higashi (2013) Zhao et al. (2014) Kondou et al. (2015) Hulse et al. (2012) Kondou et al. (2015)

29 10 11 4 23 9 13 3 10

273 293 273 253 273 295 273 273 279

R1243zf R1234ze(E)

R1234ze(Z) R1233zd(E)

÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷

338 365 352 313 333 373 350 323 350

deviations, highlighting some disagreement between the available sets of data. 4.2.3. Surface tension Table 11 reports the publicly available experimental saturated liquid surface tension data contained in the peer-reviewed literature for five fluids, namely R1234yf, R1243zf, R1234ze(E), R1234ze(Z), and R1233zd(E). Only one data set is available for R1243zf and R1234ze(Z), while two data sets are available for R1234yf and R1233zd(E) and three for R1234ze(E) (however, two data sets consists of only 3 and 4 data points, respectively). 5. Thermodynamic and transport properties of mixtures As we did above for the single-component fluids, a wide ranging search of the publicly available literature was conducted for binary blends containing at least one HFO as one of the components. Again, special emphasis was placed on papers published in peer-reviewed journals catalogued by the International Scientific Indexing (ISI) server. Table 12 provides the identified references that report experimental data for binary blends, together with the reported measured properties. As a general comment, based on the analysis of the various references considered, it is evident that almost all the investigated blends contain either R1234yf or R1234ze(E) as one of the components. In fact, both the R1234yf and R1234ze(E) based blends are found in more than 30 papers, where both thermodynamic

and/or transport properties are measured. In particular for the R1234yf-based blends, R1234yf was combined with another HFO (R1234ze(E)), with some of the most widely used HFCs and PFCs (R14, R23, R32, R125, R134a, R152a, R143a, R218, R227ea, R161, R23, R245cb), with hydrocarbons (R600a, R290) and natural gases (R717, R728, R740, R744). On the other hand for the R1234ze(E)based blends, R1234ze(E), besides the already mentioned blend with R1234yf, it was combined with commonly used HFCs (R32, R134, R134a, R152a), with hydrocarbons (R600a, R290, R50) and with natural gases (R744 and R728). A limited number of papers also report blends containing R1234ze(Z), R1123, or R1225ye(Z) as one of the components.

5.1. VLE for the R1234yf-based blends As a general comment on the VLE experimental measurements, excluding R1234yf + R134a, R1234yf + R152a, R1234yf + R218, R1234yf + R290, R1234yf + R717 and R1234yf + R600a nonazeotropic behavior was observed in the entire range of the measured temperatures for the studied binary blends. In particular, the R1234yf + R32 and R1234yf + R125 binary blends were measured in the temperature range from 273 K to 333 K by Kamiaka et al. (2013) and both the Peng-Robinson (PR) Equation of State (EoS) and a Helmholtz-type EoS were derived. Maximum temperature glides of 8 K and 3–4 K was estimated for R1234yf + R32 and R1234yf + R125, respectively. In addition, the R1234yf + R32 was also measured in the temperature range from 283 K to 323 K by Hu et al. (2017b) that used the Peng–Robinson Stryjek–Vera (PRSV) EoS with both the van der Waals (vdW) onefluid mixing rule and the Wong–Sandler (WS) mixing rule with the non-random two-liquid (NRTL) activity coefficient model. The R1234yf + R143a and R1234yf + R227ea binary blends were measured in the temperature range from 283 K to 323 K by Hu et al. (2013) and Hu et al. (2014a), respectively, and the PR EoS with vdW mixing rules were used to correlate both of these data sets. The R1234yf + R161 binary system was measured in the temperature range from 283 K to 323 K by Chen et al. (2015a, 2015b) and Hu et al. (2017b). They used the PR EoS and the PRSV EoS, respectively, with both the vdW one-fluid mixing rule and the Wong– Sandler (WS) mixing rule with the non-random two-liquid (NRTL)

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197

Table 12 Available experimental data for the binary systems containing HFO. Base component 2nd component R1234yf R1234ze (E) R32 (difluoromethane)

Property CP PVTx CP PVTx CP cp cv PVTx

σ μ

VLE

R125 (pentafluoroethane)

λ μ

VLE R134 (1,1,2,2-tetrafluoroethane) VLE R134a CP (1,1,1,2-tetrafluoroethane) PVTx

σ μ

R 152a (1,1-difluoroethane) R143a (1,1,1-trifluoroethane) R227ea (1,1,1,2,3,3,3-eptafluoropropane) R161 (fluoroethane) R23 (trifluoromethane) R245cb (pentafluoropropane) R600a (isobutane) R290 (propane)

VLE VLE

μ

VLE VLE VLE VLE VLE VLE PVTx PVTx VLE

R50 (methane) R744 (carbon dioxide)

R728 (nitrogen) R14 (tetrafluoromethane) R218 (octafluoropropane) R740 (argon) R717 (ammonia) Total

PVTx CP cv PVTx SLE VLE PVTx VLE VLE VLE VLE VLE

R1234yf

Higashi (2016) Higashi (2016) Akasaka et al. (2013)

Akasaka et al. (2013) Kayukawa (2011) Kobayashi et al. (2011) Cui et al. (2016) Tanaka et al. (2010d) Cui et al. (2016) Arakawa et al. (2010) Dang et al. (2015a) Dang et al. (2015b) Kamiaka et al. (2013)) Hu et al. (2017b)

R1234ze (E) Higashi (2016) Higashi (2016)

R1234ze (Z)

R1225ye(Z)

R1123

Brown et al. (2016)

Kobayashi et al. (2010) Tanaka et al. (2011) Yamaya et al. (2011b) Tanaka et al. (2011) Jia et al. (2016)

Higashi and Akasaka (2016)

Higashi and Akasaka (2016)

Cui et al. (2016) Tanaka and Higashi (2013) Tanaka et al. (2010d) Cui et al. (2016)

Koyama et al. (2010) Hu et al. (2017c) Hu et al. (2017d) Miyara et al. (2010)

Dang et al. (2015a) Dang et al. (2015b) Kamiaka et al. (2013) Dong et al. (2013) Akasaka et al. (2015) Chen et al. (2015a, 2015b) Bi et al. (2016) Bi et al. (2016) Kamiaka et al. (2013) Hu et al. (2014b) Yang et al. (2016b) Hu et al. (2013) Hu et al. (2014b)

Zhang et al. (2017)

Zhang et al. (2017) Bi et al. (2016) Bi et al. (2016) Yang et al. (2013)

Chen et al. (2015a, 2015b) Hu et al. (2017b) Madani et al. (2016) Kochenburger et al. (2017) Yang et al. (2016a) Hu et al. (2014c) Dong et al. (2012) Brown et al. (2017) Brown et al. (2017) Cao et al. (2017) Brown et al. (2016) Zhang et al. (2016a) Zhong et al. (2018) Zhang et al. (2016b) Zhong et al. (2017) Dong et al. (2011) Qi et al. (2014) Brown et al. (2014) Juntarachat et al. (2014) Juntarachat et al. (2014) Yamaya et al. (2011a) Di Nicola et al. (2012b) Di Nicola et al. (2013b) Di Nicola et al. (2013a) Di Nicola et al. (2013c) Di Nicola et al. (2013d) Juntarachat et al. (2014) Brown et al. (2014) Kochenburger et al. (2017) Kochenburger et al. (2017) Kochenburger et al. (2017) Kochenburger et al. (2017) Zhao et al. (2017) 45 34

activity coefficient model. The R1234yf + R161 binary system was found to be near-azeotropic. The R1234yf + R23 binary system was measured in the temperature range from 254 K to 348 K by Madani et al. (2016). Both the PR EoS, incorporating the Mathias–Copeman alpha function, combined with the NRTL excess free energy model and Wong–Sandler mixing rules, and the PC-SAFT EoS were adopted to correlate the experimental data. The critical locus line was also predicted. The same system was also measured in the temperature range from

Zhang et al. (2016)

Brown et al. (2016) Gong et al. (2016b)

3

1

2

193 K to 273 K by Kochenburger et al. (2017). For the data elaboration, the PR EoS with the vdW and Mathias–Klotz–Prausnitz (MKP) mixing rules and the Mathias–Copeman (MC) alpha function. The same authors measured also R1234yf + R728, R1234yf R740 and R1234yf + R14 in the temperature ranges from 173 K to 273 K. The same data elaboration models were also adopted. The R1234yf + R744 binary system was measured in the temperature range from 283 K to 353 K by Juntarachat et al. (2014). The PR EoS was adopted to correlate the experimental data, while

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the PC-SAFT EoS was unable to replicate the critical points of the pure components. The critical loci of R1234yf + R744 and R1234ze(E) + R744 were also measured. The R1234yf + R245cb binary system was measured in the temperature range from 283 K to 313 K by Yang et al. (2016a). A small deviation with Raoult’s Law was found, and the PR EoS with the vdW mixing rule was used to calculate both the vapor and liquid phase fugacity coefficients. Regarding the blends for which azeotropic behavior was found, the R1234yf + R134a mixture, characterized by Kamiaka et al. (2013), shows an azeotropic point at a composition of 50/50 wt%, with a relatively small temperature glide (approximately 0.2 K). The R1234yf + R152a system, characterized by Hu et al. (2014b), clearly exhibits positive deviation from Raoult’s Law combined with azeotropic behavior. The binary blend also shows nearazeotropic behavior over the complete range of composition and temperature (283 K–323 K). The temperature glide was less than 0.4 K. The data were correlated with the PR EoS coupled with the vdW mixing rules. The R1234yf + R218 system, characterized by Kochenburger et al. (2017), was measured at temperatures of 223 K and 273 K. The results were correlated using the PR EoS with the vdW and MKP mixing rules and the MC alpha function. The system shows a positive azeotropic behavior. The R1234yf + R290 system was measured by Zhong et al. (2017) within the temperatures from 253 K to 293 K. The experimental data were correlated by the PR-vdW model and PR-HVNRTL model. An azeotropic behavior was observed at compositions of R1234yf approximately from x = 0.26 to x = 0.28. The R1234yf + R717 was experimentally investigated at temperatures from 243 K to 283 K. The VLE and VLLE data were regressed by the PR-MHV2-NRTL model (MHV: modified Huron Vidal). The homogeneous or heterogeneous azeotropic behaviors were found for the systems concerned over the temperature ranges investigated. Finally, azeotropic behavior was found also at a mole fraction of approximately 0.88 of R1234yf for the R1234yf + R600a system, characterized by Hu et al. (2014c), for the measured temperature range (from 283 K to 323 K). The data were correlated with the PR EoS coupled with both the vdW and the WS mixing rules. R1234yf was also considered as base fluid for ternary systems. In particular, two sets of measurements, both obtained using a recirculation apparatus, are present in the open literature. R134a + R1234yf + DME measurements by Han et al. (2015) were obtained from 253 to 323 K and were correlated by the PR equation of state with the Linear Combination of Vidal and Michelsen (LCVM) mixing rule and the NRTL model. No azeotrope in this ternary mixture was detected. R134a + R1234yf + R600a measurements by Hu et al. (2016) were obtained from 283 to 323 K and the experimental data were compared with the predicted data by the PR equation of state with both the vdW and the WS mixing rule. 5.2. VLE for the R1234ze(E)-based blends Many researchers performed both thermodynamic and/or transport properties measurements of R1234ze(E) + R32 binary blends. The VLE measurements for these blends showed non-azeotropic behavior over the entire measured temperature range. Hu et al. (2017c, 2017d) measured their data over the temperature range from 283 K to 323 K and correlated their data using the Peng– Robinson–Stryjek–Vera (PRSV) equation of state coupled with the WS mixing rule and the NRTL activity coefficient model. Azeotropic behavior was found for the R1234ze(E) + R134 blends, characterized by Dong et al. (2013), R1234ze(E) + R152a blends, characterized by Yang et al. (2013), R1234ze(E) + R600a

blends, characterized by Dong et al. (2012), and R1234ze(E) + R290 blends, characterized by Dong et al. (2011) and Qi et al. (2014). All the blends listed above were measured over the temperature range from 258 K to 288 K, excluding the R1234ze(E) + R290 blend which was measured over the temperature range from 258 K to 283 K. The correlation of the VLE results was always carried out by means of the PR EoS and the Huron–Vidal (HV) mixing rules involving the NRTL activity coefficient model. Azeotropic compositions were estimated at mole fractions from 0.62 to 0.66 of R134 over the temperature range from 258 K to 288 K, at mole fractions from 0.344 to 0.381 of R600a over the temperature range from 258 K to 288 K and at mole fraction from 0.83 to 0.847 of R290 over the temperature range from 258 K to 283 K. R1234ze(E) was also considered as base fluid for ternary systems. In particular, one set of measurement, again obtained using a recirculation apparatus, is present in the open literature: R32 + R161 + R1234ze(E) by Hu et al. (2017d). R32 + R161 + R1234ze(E) measurements were obtained from 283 to 323 K and the experimental data were compared with the predicted data by the PRSV equation of state combined with the WS mixing rule and the NRTL activity coefficient model was used to predict the ternary VLE data by using the parameters of binary mixtures. 5.3. VLE for the R1234ze(Z)-based blends The VLE of R1234ze(Z) were measured with two different hydrocarbons (R600a and R290) and with R134 in recent papers. The R1234ze(Z) + R600a binary system was characterized by Zhang et al. (2016), at temperatures from 303 K to 353 K. The PR-vdW and PR-HV-NRTL models were employed to describe the VLE properties of the blends that exhibit azeotropic behavior, estimated with the proposed models at mole fractions from 0.68 to 0.72 of R600a for the measured temperatures range. The R1234ze(Z) + R290 binary blend was characterized by Gong et al. (2016b), at temperatures from 253 K to 293 K. The PR-vdW and PR-HV-NRTL models were employed to describe the VLE properties of the blends which exhibit zeotropic behavior over the measured temperature range. The R1234ze(Z) + R134 binary blend was characterized by Zhang et al. (2017b), at temperatures from 303 K to 343 K. The experimental results were correlated by the PR equation of state with the HV mixing rule involving the NRTL activity coefficient model. Azeotropic behavior can be observed at four temperatures from 303.150 K to 333.150 K, while zeotropic behavior was found at 343.150 K. 6. Conclusions The paper reports the publicly available literature of experimentally-determined data for a number of important thermodynamic and transport properties of several halogenated olefin working fluids and their mixtures. For each property and fluid, the articles published in peer-reviewed journals are considered and analyzed in terms of the number of experimental data they contain and the temperature and pressure ranges of the measurements. The analyses show that only two fluids, namely R1234yf and R1234ze(E), have been extensively investigated in terms of the thermophysical properties considered herein. For R1234ze(Z), a large amount of thermodynamic property data is available; however, many fewer transport properties are available. R1234yf and R1234ze(E) are also components of the largest number of mixtures studied so far, even if in general the data available for mixtures are quite scarce. This paper demonstrates the need for further experimental studies of the thermophysical properties

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