Fluid Phase Equilibria 531 (2021) 112921

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

New Helmholtz Equation of State for HFO-1234ze(E) with

Comprehensive Assessment
I Made Astina a,∗, Galih Budiarso b, Richard Harrison c
a
Faculty of Mechanical and Aerospace Engineering, Institut Teknologi Bandung, Indonesia
b
PT Pupuk Kalimantan Timur, Indonesia
c
Agency and the Assessment and Application of Technology, Indonesia

a r t i c l e i n f o a b s t r a c t

Article history: Two issues of energy and environment cannot be separated in energy utilization systems. Using the
Received 2 September 2020 working fluids in the thermal systems has to be highly attained due to these fluids may affect to the
Revised 7 November 2020
energy efficiency, global warming, and ozone depletion. Trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E))
Accepted 7 December 2020
was developed to address the issue. This fluid can replace the use of R-134a which is available in com-
Available online 11 December 2020
mercial market. Reliable thermodynamic equation of state (EOS) for HFO-1234ze(E) plays important role
Keywords: on optimization and design of refrigeration and thermal power systems.
thermodynamic properties Helmholtz EOS is used as base of mathematical model because it is able to easily derive all thermo-
equation of state dynamic properties and reliable to represent for a wide range of fluid phase. A new EOS was developed
Helmholtz with a genetic algorithm combined with regression. The EOS represents thermodynamic properties of
HFO refrigerants HFO-1234ze(E) with average absolute deviation (AAD) of 0.043% for the ideal gas isobaric specific heat,
trans-1,3,3,3-tetrafluoropropene
0.084% for the liquid density, 0.39% for the vapor density, 0.096% for the vapor pressure, 0.11% and 1.0%
for the saturated liquid and vapor densities. The caloric properties can be represented within AAD of 13%,
1.5%, and 5.4% for the isochoric, isobaric, and saturated specific heats, respectively, and the ADD of the
speed of sound is 0.12% for liquid phase and 0.063% for vapor phase. The EOS also has proper behav-
ior of the second and third virial coefficients and has proper extrapolation trend for the caloric and PVT
properties. The EOS can be applied for temperature up to 600 K and pressure up to 100 MPa.
© 2020 Elsevier B.V. All rights reserved.

Introduction
Refrigerants which are more environmentally friendly to over-
come the problem of ozone depletion and global warming have
to be used in refrigeration and air conditioning systems. Fourth
generation refrigerants which are called as the Hydro Fluoro
Olefins (HFO) group having non-ozone depletion and a very low
global warming are very interesting to reveal from thermody-
namic aspects for developing high efficient systems. Trans-1,3,3,3-
tetrafluoropropene also called as HFO-1234ze(E) becomes interests
of this study since this refrigerant is a non-ozone depletion sub-
stance and has global warming potential of 6 [1]. It means that
the HFO-1234ze(E) is also materials that have little effect on global
warming. HFO-1234ze(E) has mildly flammable properties based
on the test results using the ASTM E681-04 standard [2].
Currently HFO-1234ze(E) is used as a refrigerant in chillers, air
conditioning in supermarkets and buildings, heat pumps, refrigera-
∗
Corresponding author.
E-mail address: astina@ftmd.itb.ac.id (I. Astina).
tors, vending machines, beverage dispensers, air dryers, and CO2
cascade systems in commercial cooling systems [3]. Its thermo-
dynamic properties are very important for developing refrigera-
tion systems or other thermal systems that utilizes this refriger-
ant. Optimal design of both systems can be developed if the ac-
curate thermodynamic properties are available. The optimal design
results have a good impact on energy utilization efficiencies. There-
fore, it is very important to develop new Helmholtz equation of
state (EOS) having high reliability for representing thermodynamic
properties of HFO-1234ze(E). In this paper, a new EOS of new gen-
eration refrigerant HFO-1234ze(E) is proposed.
Data Survey and Selection
Experimental data in single phase and at saturation state are
needed to develop the EOS which is valid for wide range fluid
phase. PVT and caloric data in the fluid phase have to be used
in order to get reliable EOS for wide range states. Thermodynamic
properties outside the range of experimental data can be extrap-
olated even though it does not rule out the possibility of accu-
racy that may still be low. Therefore, modeling data in single phase

https://doi.org/10.1016/j.fluid.2020.112921
0378-3812/© 2020 Elsevier B.V. All rights reserved.
I. Astina, G. Budiarso and R. Harrison Fluid Phase Equilibria 531 (2021) 112921

Table 1
Available thermodynamic property data for HFO-1234ze(E).

No Data Reference Property Number Range Purity, mol %

1 Nicola et al. [5] Ps 78 223.1−353.08 K 99.5

2 Tanaka et al. [6] Ps 8 310−380 K 99.96
3 McLinden et al. [7] Ps 30 260.998–380.002 K 99.993
4 Gao et al. [8] Ps 12 310.15–365.15 K 99.995
5 Gong et al. [9] Ps 10 53.343–293.318 K 99.5
6 Yin et al. [10] Ps 15 303.146–373.137 99.9
7 Tanaka et al. [6] ρ’ 7 310−370 K 99.96
8 Higashi et al. [11] ρ’ 9 368.2–382.51 K 99.96
9 Tanaka [12] ρ’ 18 300–380 K 99.5
10 Gong et al. [9] ρ’ 10 253.343–293.318 K 99.5
11 Higashi et al. [11] ρ" 14 368.8−382.51 K 99.96
12 Tanaka et al. [6] PVT 26 310−370 K 99.96
13 McLinden et al. [13] PVT 136 240.002−420.007 K 99.993
14 Brown et al. [15] PVT 432 242.91−372.97 K 99.5
15 Tanaka and Higashi [15] PVT 204 310−360 K 99.96
16 Qiu et al. [16] PVT 131 283.55−362.96 K 99.9
17 Klomfar et al. [17] PVT 101 205.22−353.154 K 99.5
18 Zhang et al. [18] PVT 26 263.169–293.163 99.5
19 Yin et al. [10] PVT 101 313.143–373.161 99,9
20 Tanaka et al. [19] cp 26 310−370 K 99.96
21 Gao et al. [8] cp 95 310.15−365.15 K 99.995
22 Liu et al. [20] cp 130 313.465–392.769 99.95
23 Yamaya et al. [21] cv 37 270.15−425.15 K 99.96
24 Tanaka et al. [19] cs ’ 7 310−370 K 99.96
25 Gao et al. [8] cs ’ 12 310.15−365.15 K 99.995
26 Kano et al. [22] w 41 278.15−353.151 K 99.96
27 Lago et al. [23] w 24 259.98−360.03 K 99.5
28 Perkins McLinden [24] w 223 279.896−419.984 K 99.993

Fig. 1. Experimental PVT data in the single phase.

are expected to have a sufficient number and uniform distribution.
Table 1 gives summary of available PVT and caloric data of HFO-
1234ze(E) in the single phase and at saturation. Data distribution
in the single phase is shown in Figs. 1 and 2, respectively.
The experimental data at the saturation as shown in Table 1 is
unavailable from the triple temperature of 168.8 K up to 223 K
so that calculated data which were derived from previous avail-
able correlations [5,11,26] were used for modeling in this range.
As indicated in Fig. 1, the experimental PVT data are still scarcely,
especially for higher pressures than 40 MPa and states near the
triple point. The caloric data include isobaric and isochoric spe-
cific heats, and speed of sound in property modeling. The accu-
rate caloric data with large number and uniform distribution play
important role on development of the EOS. Experimental caloric

2
I. Astina, G. Budiarso and R. Harrison
Fig. 2. Experimental caloric data in the single phase.
data were obtained from several literatures as listed in Table 1 and
the data distribution is given in Fig. 2. The caloric data have the
narrower range and scarcely distribution compared to the PVT
data.
Thermodynamic Modeling and Main Parameters
A new EOS was developed with the genetic optimization pro-
cedure and multi-property regression and the method was detailly
reported in previous paper [26]. It was applied for HFC refrigerants
in previous papers [27–30] and HC refrigerants in previous papers
[31,32]. Three main steps are involved on development of the EOS.
The first step is to develop an ideal gas isobaric specific heat equa-
tion by conducting the genetic optimization procedure and then
integrate it two times to get an ideal part of the EOS. The sec-
ond step is to develop a residual part of the EOS by conducting
genetic optimization procedure and multi property regression. In
data preparation of saturation properties for multi property regres-
sion, there ancillary equations are developed by conducting the ge-
netic optimization procedure. Third step is to fit the best EOS into
a reference state.
Main parameters are molar mass M = 114.04 g/mol, universal
gas constant R = 8.314462618 J/mol•K [33]. The critical point used
is experimental data from Higashi et al. [11]. The critical point is
3632±3 kPa of critical pressure (Pc ), 382.51±0.01 K of critical tem-
perature (Tc ), and 486±3 kg/m3 of critical density (ρ c ), which was
determined for purity of 99.96% mol/mol. The triple point refers to
the measurement result of Nicola et al. [4] with value of 168.8±0.8
K for purity of 99.9% mol/mol. A reference state for the EOS refers
to recommendation of the International Institute of Refrigeration
by taking the specific enthalpy and entropy values of 200 kJ/kg and
1 kJ/kg•K, respectively, for the saturated liquid of 273.15 K.
Ancillary Equations
Ancillary equations consist of equations for saturated vapor
pressure, saturated liquid and saturated vapor densities. The an-
cillary equations were iteratively developed to support modeling
3
Fluid Phase Equilibria 531 (2021) 112921
Helmholtz EOS. The equations can accurately calculate saturation
properties and will be useful in deriving thermodynamic properties
from the EOS. The vapor pressure (Ps ) relation as function of tem-
perature (T) is represented in Eq. (1). Variables and coefficients in
the equation are θ = (1 - 1/τ ), τ = Tc /T, D1 = -7.4934, D2 = 1.4734,
D3 = -1.9544, and D4 = -4.0283. Minimum term number in the
equation was selected without reducing its accuracy. The same rea-
son is also for other ancillary equations.
P   
= τ D1 θ + D2 θ 1. 5 + D3 θ 2. 5 + D4 θ 4. 7
s
ln (1)
Pc
The second ancillary equation is aimed for the saturated liq-
uid density (ρ  ) as written in Eq. (2). The equation has function
of temperature and its variable and coefficients are θ = (1 - T/Tc ),
E1 = 1.2715, E2 = -4.6242, E3 = 5.8278, and E4 = 0.57890.
 
ρ
− 1 = E1 θ 0. 1 + E2 θ 0. 2 + E3 θ 0. 3 + E4 θ 2. 5 (2)
ρc
The last ancillary equation purposed is the saturated vapor den-
sity (ρ  ) as written in Eq. (3). The equation has function of tem-
perature with variable and coefficients are θ = (1 - T/Tc ), F1 = -
0.30974, F2 = -5.1155, F3 = -13.783, and F4 = -62.234.
 
ρ 
ln = F1 θ 0.1 + F2 θ 0.6 + F3 θ 2.1 + F4 θ 5.7 (3)
ρc
Helmholtz Equation of State
The Helmholtz EOS is represented in dimensionless as result of
Helmholtz free energy (A) divided by a gas constant (R) and tem-
perature (T). The EOS is notated by α and consists of two parts, i.e.
ideal part (α o ) and residual part (α r ). Its value is a summation re-
sult of the ideal part and the residual part (α = α o + α r ). The EOS
has function of density (ρ ) and temperature (T) and it is explic-
itly represented in the two dimensionless parameters i.e., reduced
density δ =ρ /ρ c and inverse reduced temperature τ =Tc /T, where
ρ c and Tc are critical density and temperature, respectively. All of
the thermodynamic properties can be derived from the Helmholtz
EOS.
I. Astina, G. Budiarso and R. Harrison Fluid Phase Equilibria 531 (2021) 112921

Table 2 thermodynamic properties can be derived when a mathematical

Numerical coefficients and constants
function of the Helmholtz free energy is known.
of the Eqs. (4) and (5).

i ηio Nio
Assessments of the Equation of State
1 0 -5.9472607
2 1 8.9615296
3 0.38949999 7.7326340 Assessment of the new EOS was conducted as long as the de-
4 2.1661999 7.4102623 velopment in order to find the best one as a proposed EOS. As-
5 4.9593000 6.7620840 sessment includes its accuracies to produce thermodynamic prop-
erty values compared to the experimental data and the values cal-
culated from other EOS. The values from the new EOS are used
The ideal part was resulted from an ideal gas isobaric specific as a baseline to represent relative deviations and visualization as-
which has relation as given in Eq. (4) with numerical coefficients sessment of each property. Extrapolations of the properties, inter-
and constants are given in Table 2. The good equation from the molecular behavior, and characteristic curves were also assessed to
optimization just has Einstein-Planck term. This equation was inte- judge reliability of the EOS.
grated to find the ideal part and get a mathematical relation con- The new EOS represents ideal gas isobaric specific heat as
sisting of the polynomial and Einstein-Planck terms with two in- shown in Fig. 3. Large deviations occur at higher temperatures
tegration constants that refers to a reference state. The ideal part when compared to the equation of Kano et al. [22]. The data of
can be written in Eq. (5) with numerical coefficients and constants Kano et al. derived from the speed of sound measurement can be
given in Table 2. represented with average absolute deviation (AAD) of 0.043%. Ac-
  curate representation can be performed from 275 K up to 355 K as
cop (τ ) 
5
exp −ηio τ consequence of the available data for developing the ideal part of
τ η 
2
= Nio 2 io  2 (4)
R 1 − exp −ηio τ the EOS is only from 278.15 K up to 353.15 K. Most results of ideal
i=3
gas isobaric specific heat have a good accuracy respect to EOS of
Thol and Lemmon [25] and EOS of Akasaka [34].

2 
5    Figs. 4–6 show deviations of the available experimental data
α o (δ, τ ) = ln δ − ln τ + Nioτ ηi + Nioln 1 − exp −ηio τ
o

and relations respect to the new EOS for the vapor pressure, the
i=1 i=3 saturated liquid and saturated vapor densities, respectively. The
(5) large uncertainty data at lower temperatures cause a large devi-
The residual part can be finally written in Eq. (6) with nu- ation effect on the new EOS. The vapor pressure ancillary equation
merical coefficients and constants given in Table 3. It consists of has a high accuracy within STDEV of 0.024% from the new EOS. As
17 terms, with 8 polynomial terms and 9 exponential terms. The shown in Fig. 4, AAD of the vapor pressure for ten point data from
terms of the residual part have the same number as the residual Gong et al. [9] is 0.29% with maximum absolute deviation (MAD)
part developed by Akasaka [34], but more terms compared to Thol of 1.0% and standard deviation (STDEV) of 0.42%. A wide tempera-
and Lemmon [25] having only 16 terms. ture range of 223 K to 380 K for vapor pressure data were reported
by Nicola et al. [5] and McLinden et al. [7] with data total of 78

8 
13
and 30 points, respectively. Both reported data can be accurately
ϑi
α r (δ, τ ) = Ni δ di τ ti + Ni δ di τ ti exp −(δ ) represented by the new EOS. The data of Nicola et al. have AAD of
i=1 i=9
0.14% and MAD of 1.0%. The data of McLinden et al. have AAD of

17
0.037% and MAD of 0.10%. When the new EOS is compared with
ϑ
+ Ni δ di τ ti exp −βi (δ −
i ) i − γi (τ − μi )ϕi (6) the Wagner correlation [5] and Thol and Lemmon [25] shows that
i=14
it performs mean values for lower temperatures and slightly bet-
Table 4 summaries mathematical relations of thermodynamic ter results for ambient temperature up to the critical point. Four
properties derived from Helmholtz free energy. These relations can sources of experimental data are available near the critical point.
also be found our previous paper [27–32]. The Helmholtz free en- The data reported by Tanaka et al. [6], Gao et al. [8], Tanaka [12],
ergy is represented in dimensionaless by dividing with product of and Yin et al. [10] have AAD of 0.034%, 0.031%, 0.062%, and 0.027%,
the gas constant and absolute temperature. In principally, all of the respectively. Nevertheless the new EOS has good accuracy in pre-

Table 3
Numerical coefficients and constants of the residual part.

i di ti βi
i ϑi γi μi ϕi Ni

1 1 0.223 - - - - - - 6.5061869 × 10−01

2 1 0.755 - - - - - - -5.5932404 × 10−01
3 2 0.85 - - - - - - 1.0064775 × 10+01
4 2 0.95 - - - - - - -1.2457731 × 10+01
5 2 1.24 - - - - - - 1.8911764 × 10+00
6 4 1.1 - - - - - - 5.5592277 × 10−02
7 4 1.75 - - - - - - -7.2430133 × 10−03
8 4 2.535 - - - - - - 1.4796176 × 10−03
9 1 2.06 - - 1 - - - -1.2013428 × 10+00
10 1 1.95 - - 2 - - - -2.0040287 × 10−01
11 2 7.45 - - 2 - - - -1.4457318 × 10−01
12 3 2.97 - - 1 - - - 1.0934001 × 10−01
13 6 2.3 - - 1 - - - -1.8087592 × 10−02
14 1 1.13 1.5 0.35 2 1.25 0.5 2 1.6187241 × 10−02
15 1 1.35 1 0.5 2 1.5 0.5 2 -6.9932775 × 10−02
16 1 1.75 1.61 0.87 2 1.37 0.642 2 3.5073320 × 10−03
17 2 1.5 0.75 0.75 2 0.75 0.75 2 -9.1576210 × 10−02

4
I. Astina, G. Budiarso and R. Harrison Fluid Phase Equilibria 531 (2021) 112921

Table 4
Main relation of thermodynamic property from Helmholtz free energy.

Property Relations

Compressibility and Pressure Z = p(δ, τ )/(ρ RT ) = 1 + δαδr

Helmholtz free energy α = A/(RT ) = α o + α r
Ideal gas isobaric specific heat cop (τ )/R = 1 − τ 2 ατo τ = 1 + cvo (τ )/R
(1 + δαδr − δτ αδτ
r
)2
Isobaric specific heat c p (δ, τ )/R = cv (δ, τ )/R +
(1 + 2δαδr + δ 2 αδδ
r )

Isochoric specific heat cv (δ, τ )/R = −τ 2 (ατo τ + ατr τ )

−(δαδr + δ 2 αδδ
r
+ δτ αδτ
r
)
Joule-Thomson coefficient μ(δ, τ )Rρ =
(1 + δαδr − δτ αδτ
r )2 + c (δ, τ )/R (1 + 2δα r + δ 2 α r )
v δ δδ
 
cv ( δ  , τ ) (1 + δ  αδr − δ  τ αδτ r
)
cs (δ  , τ )/R = + ×
 R ( 1 + 2 δ  α r  + δ 2 α r  )
δ  δδ
Saturated-liquid specific heat , τ )
  1 d p ( δ
1 + δ  αδr − δ  τ αδτ
r
−
Rρc δ  dT
Second virial coefficient B(τ )ρc = lim αδr
δ →0
Specific enthalpy h (δ, τ )/(RT ) = τ (ατo + ατr ) + 1 + δαδr
Specific entropy s(δ, τ )/R = τ (ατo + ατr ) − (α o + α r )
Specific internal energy u(δ, τ )/(RT ) = τ (ατo + ατr )
(1 + δαδr − δτ αδτr
)2
Speed of sound w2 (δ, τ )M/(RT ) = 1 + 2δαδr + δ 2 αδδ
r
+
cv (δ, τ )/R
Third virial coefficient C (τ )ρc2 = lim αδδ
r
δ →0
 
ps (δ  , δ  , τs ) ρ  ρ  δ
Vapor pressure =  ln  + α r − α r
RT s ρ − ρ  δ
Abbreviations:
         
∂α ∂α ∂ 2α ∂ 2α ∂ 2α ρ Tc
αδ = , ατ = , αδδ = , ατ τ = , αδτ = ,δ= ,τ =
∂δ τ
∂τ δ
∂ δ2 τ
∂τ 2 δ
∂ δ∂ τ ρc T

Fig. 3. Deviations of the ideal gas specific heat from the new EOS.

dicting the vapor pressure near the critical point. Unavailable data ture range of the testing data used. Values derived from equation
at lower temperature down to the triple point causes judgment of of Higashi et al. [11] have large deviations at lower temperatures,
realibility of available EOS for that range that still need to wait va- but values from the EOS of Thol and Lemmon [25] and Akasaka
por pressure measurements. However, choosing the new EOS is to [34] have deviations less than 1% excluding critical region if com-
evaluate thermodynamic properties in that range is safe way to re- pared to the new EOS. It is similar condition for experimental sat-
duce error. urated liquid data for lower temperature down to the triple point,
Very few experimental data are available for the saturated liq- i.e. scarely available data. The choice to use the new EOS for that
uid density and all of the data are higher than 300 K as shown range is safe way to reduce error.
in Fig. 5. The saturated liquid density ancillary equation has good The deviations of the saturated vapor density are shown in
accuracy within STDEV of 0.18% from the new EOS. Regarding sta- Fig. 6. The saturated vapor density ancillary equation has accuracy
tistical assessments of the experimental data, the data of Higashi within STDEV of 0.34% from the new EOS. The available experi-
et al. [11] have AAD of 2.0%, MAD of 7.3% and STDEV of 3.2%, oth- mental data are very scarely. This condition is worse than available
erwise the data of Tanaka et al. [6], Tanaka [12], and Gong et al. data for the vapor pressure and saturated liquid density. The data
[9] have an AAD of 0.27%, 0.35%, and 0.033%, respectively. These from Higashi et al. [11] in critical region are difficult to fit in re-
results indicate that the EOS has good accuracy over the tempera- gression process. Their data have AAD of 1.8%, MAD of 3.3%, and

5
I. Astina, G. Budiarso and R. Harrison
Fig. 4. Deviations of the vapor pressure from the new EOS.
Fig. 5. Deviations of the saturated liquid density from the new EOS.
STDEV of 2.1% compared to the values derived from the new EOS.
The new EOS can represent mean saturated vapor density values
of EOS of Thol and Lemmon [25] and Akasaka [34] in the range of
from the triple point up 360 K. The choice to use the new EOS is
better way as long as unvailable experimental data.
Assessment of thermodynamic EOS for densities in single phase
can be divided into liquid and vapor densities. Deviations of the
vapor density derived from the EOS respect to temperature and
pressure are shown in Fig. 7. The vapor density deviations have
a greater value due to the large experimental data uncertainty. The
vapor density data are 587 points taken from 5 experimental study
results. The closer states to the critical point, the greater deviation
resulted as shown from the data of McLinden et al. [7] and for
a range of temperature 340–420.01 K and pressure 1.0956–6.7408
MPa have AAD of 0.42%, MAD of 3.3%, and STDEV of 0.77%. The
others are data of Brown et al. [14], Tanaka and Higashi [16], Zhang
et al. [18], and Yin et al. [10] which have AAD of 0.68%, 0.22%,
0.30%, and 0.15%, respectively.
6
Fluid Phase Equilibria 531 (2021) 112921
The total experimental data of liquid density is 570 points taken
from 5 experimental study results. The deviations in the liquid
phase have small values as shown in Fig. 8. The deviations increase
when the state approaching the critical point as shown by the data
from McLinden et al. [7] and Qiu et al. [15]. The data of McLinden
et al. have AAD of 0.041%, a MAD of 0.081%, and STDEV of 0.020%
for the compressed liquid, but have AAD of 0.062%, MAD of 3.6%,
and STDEV of 1.0% for supercritical region. The maximum deviation
from the McLinden et al. occurs in data close to the critical point.
The data of Qiu et al. has AAD of 0.086%, MAD of 0.93%, and STDEV
of 0.13%. The data from Tanaka et al. [6] have AAD of 0.16%, MAD of
0.45%, and STDEV of 0.14%. The deviations of the other experimen-
tal data have smaller value because the state is far from the critical
point. These data include Brown et al. [14] and Klomfar et al. [17],
each of which have an AAD of 0.078% and 0.054%, respectively.
Ability of the EOS for presenting the isochoric specific heat (cv )
is indicated in Fig. 9. Data of Yamaya et al. [21] consist of 37 points
in a range of 270.15–425.15 K and 2.684–16.163 MPa. The data have
I. Astina, G. Budiarso and R. Harrison Fluid Phase Equilibria 531 (2021) 112921

Fig. 6. Deviations of the saturated vapor density from the new EOS.

Fig. 7. Deviations of the vapor density from the new EOS.

Fig. 8. Deviations of the liquid density from the new EOS.

7
I. Astina, G. Budiarso and R. Harrison
Fig. 9. Deviations of isochoric specific heat in the liquid phase of Yamaya et al. [21] from the new EOS.
Fig. 10. Deviations of isobaric specific heat in the liquid phase from the new EOS.
AAD of 13% and MAD of 55%. This large AAD is obtained due to
large deviation in the temperature range of 385–425 K is located
in the supercritical region.
Isobaric specific heat (cp ) deviation distribution in the liquid
phase from the 3 data sources are shown in Fig. 10. All of most
data of Tanaka et al. [19] and Gao et al. [8] have the same range
of 310–370 K and 1.5–5.5 MPa. Data from Tanaka et al. have AAD
of 1.97% and MAD of 5.2%, while the data of Gao et al. have AAD
of 0.74% and MAD of 2.7%. A wider range data owned by Liu
et al. [20] is ranged in pressures of 1.04–10.09 MPa and temper-
atures of 313.465–392.769 K. The data have AAD of 2.3% and MAD
of 5.5%.
The saturated specific heat (cs ’ ) data used to assess the new
EOS are 2 sources of Tanaka et al. [19] and Gao et al. [8]. The data
are entirely near the critical point having deviations as shown in
Fig. 11. The EOS can represents closer to the data of Gao et al. com-
pared with the data of Tanaka et al. Data of Tanaka et al. haves an
AAD of 10% and a MAD of 21%, on the other hand the data of Gao
et al. have an AAD of 2.8% and a MAD of 8.3%.
Fig. 12 shows deviations of the sound of sound (w) data in the
vapor phase and Figs. 13 shows deviations of the sound of sound
data in the liquid phase. Available data of Kano et al. [22] and
Perkins and McLinden [7] were compared to the EOS. The data
of Kano et al. have narrow temperature and pressure ranges of
278.15–353.151 K and 0.02529–0.40292 MPa. The data have AAD
8
Fluid Phase Equilibria 531 (2021) 112921
of 0.031%, MAD of 0.19%, and STDEV of 0.051%. On the other hand,
the speed of sound data that reported by Perkins and McLinden
have AAD of 0.069%, MAD of 0.22%, and STDEV of 0.077%. Available
data of the liquid phase speed of sound are only from one source
of Lago et al. [23] with having AAD of 0.71%, MAD of 3.6%, and
STDEV of 0.93%. These results indicate that deviations of the liq-
uid phase sound of sound are greater than that of the vapor phase
according to most general measurement data.
The second and third virial coefficients derived from the EOS
and the comparative results of the calculations of other EOSs are
shown in Fig. 14. The accuracy of the calculated results of the virial
coefficients are not the main objective of developing this EOS, but
the behavior resulting from the virial coefficients is the main goal.
In development, analytic data of the second and third virial coeffi-
cients by Yin et al. [10] were used. The data have a limited temper-
ature range of 313.145–373.155 K so that additional calculated data
used refer to equation reported by Pitzer and Curl [35]. It shows
that the second virial coefficient (B) follows behavior of the virial
coefficients of the other two EOSs. The curvature of the second
virial coefficient towards the negative direction at lower tempera-
ture, but the value achieved is not lower than the virial coefficient
from the results of other EOSs. The analytic data of Yin et al. are
compared to the virial coefficient values derived of the new EOS
and give AAD of 2.5% and MAD of 5.5%. The curve goes assimp-
totly to the zero value line at high temperatures. It means that the
I. Astina, G. Budiarso and R. Harrison Fluid Phase Equilibria 531 (2021) 112921

Fig. 11. Deviations of the saturated liquid specific heat from the new EOS.

Fig. 12. Deviations of the speed of sound in the vapor phase from the EOS.

Fig. 13. Deviations of the speed of sound in the liquid phase of Lago et al. [23] from the new EOS.

second virial coefficient of the new EOS already meet the expected
behavior curve.
Results of the third virial coefficient (C) show a different be-
havior between the coefficients from EOS of Thol and Lemmon
[25] and EOS of Akasaka [34]. The result of Thol and Lemmon
shows similar behavior, on the other hand the result of Obey and
Vera [36] shows a good behavior and very close with values from
the EOS of this study, but it was not found in the result of Akasaka.
The result of Akasaka shows that the third virial coefficient at low
temperature has a positive value so that the result is not valid due
to inconsistent to intermolecular potential theory. The statistical
results show that the data of Yin et al. [10] have AAD of 29% and
MAD of 55% for the calculation of the new EOS.
Extrapolation in a range of experimental data must be able to
be derived from EOS. It is intended to reveal that reliability of the
thermodynamic properties predicted by using the EOS. However,

9
I. Astina, G. Budiarso and R. Harrison Fluid Phase Equilibria 531 (2021) 112921

Fig. 14. Comparison of second and third virial coefficients from the new EOS.

Fig. 15. Extrapolation curves of PVT and caloric properties from the new EOS.

if the accuracy of the EOS is better at representing experimental
data and the extrapolation is reasonable, then the EOS is reliable.
Fig. 15 shows extrapolation curves for the thermodynamic prop-
erties of PVT, isochoric and isobaric specific heats, and speed of
sound. The curves were plotted from the triple point up to tem-
perature of 600 K and pressure of 100 MPa. Proper patterns are
shown for either for PVT or caloric properties.
Characteristic curves are presented in the Cartesian diagram
with the y-axis in the ratio of pressure to the critical pressure,
while the x-axis is a ratio of temperature to the critical temper-
ature. Pattern of the curves formed by the new EOS meets the
proper shape which is a continuously smooth curve and closing
to a center arbitrary of the diagram as shown in Fig. 16. Continu-
ous curvature of the characteristic curve means that the EOS has
good reliability to extrapolate in an application range as shown
in the diagram. In addition, the ideal gas and Boyle curves must
form an asymptot at the same temperature value [37]. All of
these conditions achieved by all of the characteristic curves means
that the new EOS has reliability in extrapolating thermodynamic
properties.

10
I. Astina, G. Budiarso and R. Harrison
Fig. 16. Characteristic curves derived from the new EOS.
Conclusion
The Helmholtz EOS of thermodynamic properties for HFO-
1234ze(E) was developed and consists of two parts i.e. the ideal
gas part and the residual part. The EOS uses IIR as a reference
state. In addition to the EOS, three ancillary equations for satura-
tion properties were also developed. The EOS can be applied from
the triple point up to temperature of 600 K and pressure of 100
MPa. The EOS was assessed with respect to the available data and
compared to existing EOS. The EOS has better reability than the
existing EOS at saturation and can keep consistencies with inter-
molecular potential theory.
The EOS has AAD of 0.043%, MAD of 0.12%, and STDEV of 0.064%
for the ideal gas isobaric specific heats. The liquid phase densities
are represented with AAD of 0.084%, MAD of 1.1%, and STDEV of
0.11% and the vapor phase densities with AAD of 0.39%, MAD of
3.6%, and STDEV of 0.61%. The vapor pressures have AAD of 0.27%,
MAD of 1.8%, and STDEV of 0.36%. The saturated liquid densities
are reproduced with AAD of 0.11%, MAD of 0.64%, and STDEV of
0.20%, on the other hand the saturated vapor densities are repro-
duced with AAD of 1.0%, MAD of 3.8%, and STDEV of 1.5% relative
to the available data closing the critical point. The isochoric specific
heats have AAD of 13%, MAD of 56%, and STDEV of 17%. The iso-
baric specific heats have an AAD of 1.5%, MAD of 5.5%, and STDEV
of 1.8%. The saturated specific heats of the EOS have AAD of 5.4%,
MAD of 21%, and STDEV of 5.2%. The speed of sound derived from
the EOS have AAD of 0.12%, MAD of 3.6%, and STDEV of 0.31% in
the liquid phase and AAD of 0.063%, MAD of 0.22%, and STDEV of
0.077% in the gaseous phase.
Credit Author Statement
All persons who meet authorship criteria are listed as authors,
and all authors certify that they have participated sufficiently in
the work to take public responsibility for the content, including
participation in the concept, design, analysis, writing, or revision
of the manuscript. Furthermore, each author certifies that this ma-
terial or similar material has not been and will not be submitted
to or published in any other publication before its appearance in
Fluid Phase Equilibria.
11
Fluid Phase Equilibria 531 (2021) 112921
Authorship contributions
Category 1
Conception and design of study: I Made Astina, Galih Budiarso;
Acquisition of data: Galih Budiarso, Richard Harrison;
Analysis and/or interpretation of data: I Made Astina, Galih Bu-
diarso.
Category 2
Drafting the manuscript: I Made Astina, Galih Budiarso
Revising the manuscript critically for important intellectual
content: I Made Astina, Galih Budiarso, Richard Harrison
Category 3
Approval of the version of the manuscript to be published: I
Made Astina, Galih Budiarso, Richard Harrison.
Declaration of Competing Interest
None.
Acknowledgment
This study is part of a research funded by P3MI Institut
Teknologi Bandung with contract no: 922/SK/I1.C08/PL/2019.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.fluid.2020.112921.
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