-1-

THERMOPHYSICAL PROPERTIES OF
HFO-1234yf AND HFO-1234ze(E)
Yukihiro Higashi, Iwaki Meisei University, 5-5-1, Iino, Chuodai, Iwaki 970-8551, Japan
Abstract: Two kinds of refrigerants, HFO-1234yf (2,3,3,3-tetrafluoropropene) and HFO-1234ze
(trans 1,3,3,3-tetrafluoropropene) are strongly expected as a new candidate of zero-ODP and lowGWP working fluids for refrigeration and heat pump cycle. In order to develop the refrigerators and
air-conditioners using these refrigerants, basis thermophysical properties are necessary. In Japan, the
new research project collaborating with universities, national laboratories, and companies is on going
with supporting NEDO, Japan. In my laboratory, several thermophysical properties, i.e., critical
parameters (critical temperature Tc, critical density c, critical pressure Pc), vapor pressures, saturated
vapor and saturated liquid densities, PvT properties, isobaric specific heat capacities, and surface
tension, had already measured in the wide temperature and pressure ranges. In addition, the equations
of state for these two refrigerants have been formulated with an aid of the collaborating researchers.
In this presentation, not only the newest but also the most reliable information of thermophysical
properties for HFO-1234yf as well as HFO-1234ze will be reported.
Key Words: Thermophysical properties, Refrigerants, HFO-1234yf, HFO-1234ze(E)

INTRODUCTION

Since chlorofluorocarbons (CFCs) had been phased out under the Montreal Protocol, CFC alternative
refrigerants are searching for based on the condition of no chlorine atoms because of zero ODP. It
seemed that conversion from CFC refrigerant to HFC refrigerant or natural refrigerant had progressed
smoothly in the two decades. In Japan, HFC-134a for the refrigerant of mobile air conditioners, R600a (iso-butane) for the home refrigerators, and R-410A for the room air-conditioners, are most
commonly used for the CFC alternative. However, next serious global environmental problem is
concerning the refrigerant. It is the global warming problem. Although HFCs do not include chlorine
atoms and are very stable materials, the GWP value is high as well as R-410A (the mixture composed
of 50 mass% HFC-32 + 50 mass% HFC-125). As the result of their higher GWP values, not only
HFC-134a but also other HFCs have to convert to lower GWP refrigerants in order to keep the F-gas
regulation in EU countries to be started from 2011.
As for the low GWP refrigerants, hydrofluoro-olefins (HFOs), especially, HFO-1234yf
(CF3CF=CH2: 2,3,3,3-tetrafluoropropene) and HFO-1234ze(E) (CF3CH=CHF: trans-1,3,3,3-tetrafluoropropene) are recently focusing in the world. Both of these HFOs have low GWP values (HFO1234yf is 4[1] and HFO-1234ze(E) is 6[2]), and expecting as the next generation refrigerant. But no
reliable information on their thermophysical and transport properties is available as of now. In the
present study, the experimental information of thermophysical properties for HFO-1234yf and HFO1234ze(E) that are measured in the authors laboratory is reported.
2

CRITERIA FOR THE SELECTION OF NEXT GENERATION REFRIGERANT

Ozone depletion potential (ODP) values and global warming potential (GWP) values for several
refrigerants are summarized in Table 1. At the end of 1995, CFC was phased out under Montreal
Protocol. HCFCs are also phased out in the near future. In the chemical structure of HFCs, hydrogen
atoms add instead of chlorine atoms. Therefore the effect of flammability is increased. HFC-32 and
HFC-152a have the problem of flammability though its performance is good. HFC-23 and HFC-143a
have larger GWP values than other HFCs. HFC-125 has the merit to be the non-flammable refrigerant
but the cycle performance is low. Completely, merit and demerit is equal to.

2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan

-2Table 1: Ozone depletion potential (ODP) and global warming potential (GWP) of several refrigerants
Refrigerant
CFC-12
HCFC-22
HFC-23
HFC-32
HFC-125
HFC-134a
HFC-143a
HFC-152a
R-410A
R-407C
R-404A
Propane
iso-Butane
CO2
DME
HFO-1234yf
HFO-1234ze(E)

ODP
1
0.055
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0

GWP
10600
1810
14800
675
3500
1430
4470
124
1730
1530
3260
3
3
1
1
4
6

Comments
Phase out under Montreal Protocol
To be phased out because of chlorine atom
High GWP
Low GWP and high performance, but flammable
Low flammability, but high GWP and low performance
CFC alternative for mobile air conditioner
High GWP and high flammable
Low GWP, but high flammable
CFC alternative for room air conditioner, high GWP
High GWP
CFC alternative for large refrigeration system, high GWP
Natural refrigerant, but flammable
CFC alternative for domestic refrigerator, flammable
Natural refrigerant, no flammable, low GWP, but high pressure
Natural refrigerant, low GWP, but flammable
Low GWP, but softly flammable not stable (with double bond)
Low GWP, but softly flammable not stable (with double bond)

Natural refrigerants (Hydrocarbons, CO2, NH3 etc.) were expected as the next refrigerant
instead of HFCs. In Japan, domestic refrigerators are using iso-butane (R-600a) as the refrigerant for
NON-FLON domestic refrigerator. NON-FLON, whose name may be the English made in Japan,
means that this substance is not a hydrofluorocarbon. Iso-butane had been hated in the beginning
because of high flammability. But I am afraid that most of Japanese people use this substance though
they do not understand what is R-600a. That is to say, the commercial name of NON-FLON may be
more famous than the iso-butane in Japan. As the amount of refrigerant used for the domestic
refrigerator is small, R-600a is applicable for the home-refrigerator. But large refrigeration system for
multi-type air conditioner is not applicable because the amount of refrigerant is too large. Moreover it
is difficult for the mobile air-conditioner to use the hydrocarbons with high flammability.
Carbon dioxide may be considered as the reasonable selection environmentally. Carbon
dioxide has some environmental features, i.e., low GWP value, zero ODP value, and no flammability.
But if the cycle performance is considered, the thermophysical properties are not so adequate. First
problem is that the critical temperature is too low to compose the refrigeration cycle easily, especially
not for heat pump cycle but for refrigeration cycle. In addition, saturation pressure is higher than other
HFC refrigerants. The critical pressures of HFC refrigerants exist in between 3 MPa to 5 MPa except
HFC-32 to be 5.8 MPa. The critical pressure of carbon dioxide is 7.4 MPa at 31 degree Celsius.
Higher pressure needs the severe condition for mechanical design.
In conclusion, it is very difficult to find the best refrigerant among the pure substances. In the
present restriction, HFOs appears suddenly. HFOs satisfy that ODP is zero, GWP is low, and
flammability is weak. The remaining problem is the performance.
3.

EXPERIMENTAL APPARATUS FOR THERMOPHYSICAL PROPERTY

MEASUREMENTS IN IWAKI MEISEI UNIVERSITY

In Iwaki Meisei University, thermophysical property measurements for refrigerants and refrigerant
mixtures are continuing from 1980s. In Figure 1, the experimental apparatus in my laboratory are
summarized. Four kinds of apparatus are working in progress.
3.1

Saturated Density and Critical Point Measurements[3,4]

The measurements of the saturated vapor and liquid densities (vapor-liquid coexistence curve) near the
critical point were carried out by the observation of the meniscus disappearance. On the basis of these
results, the critical temperature and critical density are determined from the meniscus disappearing
level as well as the intensity of the critical opalescence. With this method, the critical parameters not
only for pure substances but also for mixtures can be determined.
2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,
17 19 February 2010, Tokyo, Japan

-3The main portion of the apparatus is composed of three high-pressure vessels. The optical cell
with two Pyrex windows is the main vessel in which the change of the meniscus behavior of the
sample mixture can be observed. The cylindrical body of this optical cell was made of 304 stainless
steel. The inner shape of this optical cell is barrel-shaped in order to make it easier to observe the
phenomenon of meniscus disappearance. The expansion vessel and supplying vessel are the
cylindrical vessels made of 304 stainless steel, and used to change the sample density in the optical
cell without new sample charge.
The apparatus was installed in a thermostated silicone-oil bath. The bath temperature can be
kept constant within a temperature fluctuation of 5 mK with two electric heaters of 1.5 kW and 300 W.
Temperature measurement was conducted by a 25 standard platinum resistance thermometer
calibrated against ITS-90 with the aid of a thermometer bridge. The thermometer was mounted in the
vicinity of the optical cell. The uncertainty of temperature measurements was estimated to be within
10 mK. The sample density was calculated from the sample mass and the inner volumes of the
pressure vessels by using expansion procedures. The uncertainty of the density measurement changes
in proportion to the number of expansion. The uncertainties of the density measurements were
estimated to be within 0.5 kgm-3 to 1.6 kgm-3.

Figure 1. Experimental apparatus in Iwaki Meisei University

3.2

Isobaric Specific Heat Capacity Measurements[5]

The isobaric specific heat capacity was determined using the thermal relaxation method. The sample
vessel is a cylindrical vessel with a metal-bellows whose volume can be varied from 33 cm3 to 43 cm3
to measure the density. The stainless-sheathed heater is installed at the lowest position of the sample
vessel, and four stainless-sheathed platinum resistance thermometer are set at different positions in the
sample vessel to measure the isobaric specific heat capacity. The sample vessel was inserted into the
pressure vessel. Nitrogen gas as pressure medium was filled between the sample vessel and the
pressure vessel. The sample was pressurized through the metal-bellows by pressurizing nitrogen gas,
and the sample pressure was kept constant. The pressure of nitrogen gas was measured by a precise
digital pressure gauge, and the sample pressure was set in consideration of the elastic deformation of
the metal-bellows with the uncertainty of 3 kPa. The displacement of the metal-bellows was detected
by a linear variable differential transformer. The pressure vessel was immersed in the thermostat with
silicone oil to keep the temperature of the pressure vessel constant. The temperature was measured by
2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,
17 19 February 2010, Tokyo, Japan

-4a 25 standard platinum resistance thermometer and precise thermometer bridge with the uncertainty
of 5 mK.
3.3

PvTx Isochoric Measurements

This is the new and simple apparatus for measuring the PvTx ( pressure volume temperature composition) properties along the isochore not only pure refrigerant but also mixtures. The vapor
pressure curve is also measured by this apparatus. Sample vessel is a cylinder made from stainless
steel whose volume is about 50 cm3. The pressure transducer is connected to the sample vessel
combined with high-pressure valves. A sample of known mass is filled in the sample vessel and is
expanded to the pressure sensor, which is evacuated in advance. The density of sample can be
determined from the mass of sample and the volume of sample system composed of the sample vessel,
pressure sensor, and their connecting tubes. The sample vessel and pressure transducer are immersed
in a thermostated silicone-oil bath. Temperature was measured with a 25 standard platinum
resistance thermometer against ITS-90 with an aid of thermometer bridge.
3.4

Surface Tension Measurements[6]

Surface tension is measured by the differential capillary-rise method. Two glass capillaries are placed
vertically in a pressure vessel composed of a thick-walled Pyrex glass tube. The travelling microscope
is used to measure the location of the bottom of the meniscus in each capillary through the window of
the thermostated bath. By using the difference of the heights in the capillaries and saturated vapor and
liquid densities, the surface tension can be calculated. Temperature is measured with a 100
platinum resistance thermometer with an uncertainty of 20 mK. The uncertainty of surface tension
measurement is estimated within 0.2 mN/m
3.5

Sample Purity of HFO-1234yf and HFO-1234ze(E)

The sample of HFO-1234yf was supplied from Daikin Industries Ltd., Japan. The purity of HFO1234yf was stated 99.99 mol%. The components of impurity are 20 mol ppm air, 20 mol ppm CO2, 30
mol ppm other HFCs, and 30 mass ppm H2O. Whereas, the sample of HFO-1234ze(E) was supplied
from Central Glass Co., Japan. The purity of HFO-1234ze(E) is 99.96 mol%. Most of measurements
were made by using the sample without further purification. However, for the vapor pressure
measurements of HFO-1234ze(E), the sample was degassed a few times by freeze-thaw cycling with
liquefied nitrogen.
4.

THERMOPHYSICAL PROPERTIES OF HFO-1234yf AND HFO-1234ze(E)

4.1

Critical Parameters and Acentric Factors[7-9]

Critical temperature and critical density for HFO-1234yf and HFO-1234ze(E) were determined from
the observation of the meniscus disappearance in consideration of the meniscus disappearing level as
well as the intensity of the critical opalescence. Critical pressure was calculated from their vaporpressure correlation by extrapolating to the critical temperature determined by the author. Acentric
factor, which is the important parameter to predict the thermophysical properties by the cubic equation
of state, was calculated from the vapor-pressure correlations by using the critical temperature and
critical pressure. Critical parameters and acentric factor of HFO-1234yf and HFO-1234ze(E) are
summarized in Table 2.
Table 2: Critical parameters and acentric factor of HFO-1234yf and HFO-1234ze(E)
Critical temperature [K]
Critical pressure [kPa]
Critical density [kg/m3]
Critical molar volume [cm3/mol]
acentric factor

HFO-1234yf[7]
367.85
3382
478
239
0.280

HFO-1234ze(E) [8]
382.51
3632
486
235
0.296

2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan

-5-

4.2

Saturated Densities and Vapor Pressures[7-9]

Saturated liquid and vapor densities for HFO-1234yf and HFO-1234ze(E) were measured by the
observation of meniscus disappearance. The experimental results of HFO-1234yf and HFO1234ze((E) are plotted in Figure 2 with my previous data for other refrigerants. In Figure 2, it is found
that:
(1) The coexistence curves for two HFOs exists higher temperature position than the other
refrigerants.
(2) The location of coexistence curve for HFO-1234yf is close to HCFC-22, whereas that for
HFO-1234ze(E) is close to CFC-12.
(3) The saturation densities of hydrocarbons, propane and iso-butane, locate lower position
than the other refrigerants.
Vapor pressures for HFO-1234yf and HFO-1234ze(E) were measured by using the apparatus
of isobaric specific-heat capacity measurements. The experimental results of HFO-1234yf and HFO1234ze((E) are plotted in Figure 3 with the vapor pressure curves for other refrigerants. In Figure 3, it
is found that:
(1) The location of vapor-pressure curve for HFO-1234yf is very close to HFC-134a.
(2) The vapor pressures of HFO-1234ze(E) are relatively lower than the other refrigerants.
(3) The location of vapor pressure curve for HFO-1234yf and HFO-1234ze(E) is in between
propane and iso-butane.

420

HFO-1234yf
HFO-1234ze(E)
HFC-134a

iso-Butane

HFC-125
HFC-32
Propane
iso-Butane

Temperature / K

400
HFO-1234ze(E)

380

HFC-134a
Propane
HFO-1234yf

360

HFC-32

HFC-125

340

320
0

200

400

600

800

1000

-3

Density / kg m

Figure 2. Saturated densities for several refrigerants including HFO-1234yf and HFO-1234ze(E)

2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan

-6-

6000

Vapor Pressure / kPa

HFC-32

5000
R-410A

4000

R-290

HFC-134a

HFC-125

3000

R-600a

2000
1000
0

240

280

320

360

400

Temperature / K
HFO-1234yf

HFC-125

Propane

HFO-1234ze(E)

HFC-134a

iso-butane

HFC-32

R-410A

Figure 3. Vapor pressures for several refrigerants including HFO-1234yf and HFO-1234ze(E)

Figure 4. Surface tensions for several refrigerants including HFO-1234yf and HFO-1234ze(E)

2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan

-74.3

Isobaric Specific Heat Capacity and Surface Tension[7,10-12]

Isobaric specific heat capacities for HFO-1234yf and HFO-1234ze(E) were measured in the
compressed liquid region as well as the saturated liquid region. Experimental data were obtained in
the pressure range up to 5 MPa and in the temperature range between 310 K and 370 K. Experimental
data could not represent in this paper in the relation of the space. The data and figures will be
published in the journals[10,11].
Surface tension for HFO-1234yf and HFO-1234ze(E) were measured by differential capillaryrise method. Surface tension is the important thermophysical properties of fluids to analyze the heat
transfer solutions with boiling and condensation state in heat exchanger. The experimental results of
HFO-1234yf and HFO-1234ze((E) are plotted in Figure 4 with the calculated results for other
refrigerants. As the surface tension can not calculate from the equation of state, this information is
very valuable.
5

EQUATION OF STATE AND PRESSURE-ENTHALPY DIAGRAMS

As the final stage of our research, we are tackling to formulate the accurate equation of state. This
work is collaborating with Prof. Ryo Akasaka, Kyushu Lutheran College, Japan. The functional form
and comparisons with experimental data are summarized in the publication[13,14]. On the basis of our
experimental data, i.e., critical parameters, vapor pressures, saturated densities, PvTx properties, and
isobaric specific heat capacity, new equation of state for HFO-1234yf[13] and HFO-1234ze(E)[14] were
proposed. By using these equations of state, the saturation lines for several refrigerants are drawn on
pressure-enthalpy diagram in Figure 5.
From this diagram, the performance of refrigeration cycle can be discussed. The heat of
vaporization of HFO-1234yf as well as HFO-1234ze(E) is not so large, and is smaller than the heat of
vaporization of R-134a, R-410A, and hydrocarbons. In consideration of the refrigeration effect, both
of HFO-1234yf and HFO-1234ze(E) are not good for pure refrigerant. If HFOs use as the next
generation refrigerant, it is necessary to propose the best combination of mixtures to make clear the
global environmental problem as well as system performance of refrigeration cycle.
420

400
isobutane

380

360

propane

T (K)

340

R32

320

300
R125
R410A

280

R134a
260

240
100

HFO1234yf
HFO1234ze(E)
200

300

400

500

600

700

h (kJ kg )

Figure 5. Saturation line on pressure-enthalpy diagrams for several refrigerants

including HFO-1234yf and HFO-1234ze(E)

2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan

-86

CONCLUSION

The thermophysical properties of HFO-1234yf and HFO-1234ze(E) are summarized. In the present
stage, only a few experimental data is available. After the experimental work for thermophysical
properties and transport properties are progress, more reliable equation of state will be developed. As
the authors opinion, it is too difficult to find the next generation refrigerant from pure substances. The
best combination among HFCs, HFOs, and HCs should be expected in the next generation.
The author is grateful to Daikin Industries Ltd., Japan and Central Glass Co. Ltd. Japan for furnishing
and analyzing the high-grade sample of HFO-1234yf and HFO-1234ze(E), respectively. The author is
also thankful to Dr. K. Tanaka of Iwaki Meisei University and Prof. R. Akasaka of Kyushu Lutheran
College for collaborating this research. In addition, the author thanks to Messers T. Ichikawa, G.
Takahashi, and K. Takahashi, graduate students of Iwaki Meisei University for their valuable
assistance in carrying out the experiments.
7

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2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan