Fluid Phase Equilibria 221 (2004) 103–111

A fundamental equation of state for 1,1,1,2-tetrafluoroethane

with an intermolecular potential energy background and
reliable ideal-gas properties
I Made Astina, Haruki Sato∗
School of Science for Open and Environmental Systems, Graduate School of Science and Technology,
Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan

Received 18 October 2003; received in revised form 18 March 2004; accepted 23 March 2004

Available online 10 May 2004

Abstract

A new Helmholtz fundamental equation of state for 1,1,1,2-tetrafluoroethane was developed by considering its unified relation with
intermolecular potential theory and its characteristics of the ideal curves. The equation is valid for temperatures from the triple point to 460 K,
and pressures up to 70 MPa, and it behaves in a qualitatively rational manner even in the region far from the range of existing experimental data.
The estimated uncertainties in the range of existing experimental data are 0.1% in density for the gaseous and liquid phases, 0.02% in the speed
of sound for the gaseous phase, 0.5% in the speed of sound for the liquid phase, and 0.8% in isochoric specific heat for the liquid phase. The
uncertainties of saturation properties are 0.05% in vapor pressure, and 0.25 and 0.5% in the densities of the saturated-liquid and saturated-vapor
states, respectively. The equation of state has reliable third virial coefficients making it possible to derive reliable thermodynamic properties
near saturation in the gaseous phase even at low temperatures that are useful to precisely design refrigeration and air-conditioning systems.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Alternative refrigerant; Equation of state; HFC refrigerant; Intermolecular potential theory; Thermodynamic properties

1. Introduction
Suitable refrigerants for retrofitting either existing refrig-
eration or air-conditioning systems should satisfy economic,
environment, and technical considerations. The alternative
refrigerant of 1,1,1,2-tetrafluoroethane (R134a or HFC134a)
has zero-ozone depletion potential and non-flammable
properties. This refrigerant can be used either as a pure
fluid or in a mixture to replace R12. Several equations of
state for R134a either a Helmholtz type [1–3] or a MBWR
type [4,5] have been proposed. The International Energy
Agency-Annex-18 has recommended the equation of state
by Tillner-Roth and Baehr [1] as an International Stan-
dard equation of state for the thermodynamic properties of
R134a.
In a previous study, a fundamental equation of state for
R32 was developed, it was pointed out that the behavior of
∗ Corresponding author.
E-mail address: hsato@sd.keio.ac.jp (H. Sato).
the second and third virial coefficients effect the derivation
of caloric properties from equations of state at low temper-
atures in the gaseous phase [6]. Reliable specific heats in
the gaseous phase play an important role on the thermody-
namic calculation in the field of refrigeration. The purpose
of this study is to establish a reliable fundamental equation
of state for R134a, which can accurately represent experi-
mental data, but is also consistent with thermodynamic the-
ory such as obtaining reasonable characteristics of the ideal
curves and the third virial coefficients based on intermolec-
ular potential model. This paper reports on a series of our
research on the development of fundamental equations of
state for HFC refrigerants.
2. Shortages of experimental data and solving strategy
Shortages may arise from a lack of reliable data for com-
plex thermodynamic properties. Reliable experimental data
should be recognized as a paradigm that cannot be sepa-
rated from thermodynamic theory. Either the shortage or

0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.03.004
104 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111

thermodynamic inconsistencies among experimental data The saturated-liquid density equation is,
might cause inaccurate representation by the fundamental

 
ρ T ti
4
equation of state especially in the region where experimental −1= Ni 1 − (2)
data are not available. We propose that a theoretical back- ρc Tc
i=1
ground should be considered to improve the reliability of
the equation of state especially in the region near saturation where c1 = 1.8689487, t1 = 1/3, c2 = 0.6531694, t2 =
and regions where experimental data are unavailable. 2/3, c3 = 0.22950915, t3 = 1, c4 = 0.7436063, and t4 = 5.
Reliable thermodynamic properties at low temperatures The saturated-vapor density equation is expressed as
in the gaseous phase are very essential in thermodynamic
 
ρ T ti
4
analysis due to the way compressors work. From mathe- ln = Ni 1 − (3)
matical and physical viewpoints, the second and third virial ρc Tc
i=1
coefficients play an important role because both virial co-
efficients have a large effect on the primary and secondary where N1 = −2.121593, t1 = 1/3, N2 = −6.502220, t2 =
derivatives of the Helmholtz free energy function with re- 1, N3 = −21.886138, t3 = 3, N4 = −80.75987, and t4 =
spect to density. This analysis substantiates a unified rela- 22/3.
tion of joining the intermolecular potential model with the
fundamental equation of state to be considered. This con-
sideration can provide reliable gaseous specific heats from 4. Input data preparation for modeling
the new fundamental equation of state.
By introducing the third virial coefficient into the re- Experimental data were assessed to prepare reliable sets
gression procedure, it is possible to reduce the degrees of of input data for modeling. The experimental uncertainty,
freedom for fitting the fundamental equation of state [6]. purity, and data distribution were considered. The selected
Several existing equations of state including the Interna- experimental data have a distribution as illustrated in Fig. 1.
tional Standard equation of state have both unreasonable The PVT data in the liquid phase were selected from Hou
gaseous specific heats at low temperatures and incorrect et al. [10] (357 points) and Tillner-Roth and Baehr [11] (282
Joule inversion curve in the region where experimental data points). The PVT data in the superheated-vapor phase consist
do not exist. of 341 points of Tillner-Roth and Baehr [10], 24 points of
Tillner-Roth and Baehr [11], and 53 points of Weber [13].
The PVT data in the supercritical phase used with 70 points
of Tillner-Roth and Baehr [12], 126 points of Tillner-Roth
3. Parameters and ancillary equations
and Baehr [11], 43 points of Hou et al. [10], and six points
of Weber [13].
Several parameters and ancillary equations are needed
Caloric properties as input data cover speed of sound,
for the development and implementation of the fundamental
isochoric specific heat, and saturated-liquid specific heat. All
equation of state. The parameters consist of the critical pa-
experimental isochoric specific heats in the liquid phase of
rameters, triple point, molecular mass, and gas constant. The
Magee [8] were selected as input data. Derived data for the
critical parameters are 374.083 K [7] for the critical temper-
saturated-liquid specific heat of Magee [8] were also used
ature, 509 kg m−3 [7] for the critical density and 4.048 MPa
in modeling. Speed-of-sound data in the liquid phase were
for the critical pressure (as an extrapolation result from the
selected from 206 points of Guedes and Zollweg [14], 226
vapor pressure equation). Other parameters are 169.85 K [8]
points of Takagi [15], and 48 points of Grebenkov et al.
for the triple temperature, 0.102031 kg mol−1 for the molec-
ular mass, and 8.314472 J mol−1 K−1 [9] for the gas con-
stant. 100
Three ancillary saturation equations for calculating vapor
pressures, saturated-vapor densities, and saturated-liquid 10
densities were established by considering the thermody-
1
p , MPa

namic consistency of the properties in the gaseous and

liquid phases and saturation. Since saturation density data
0.1
at low temperatures are scarce, the properties were iter-
atively fitted. The ancillary equation for vapor pressure 0.01
is,
  0.001
Tc
T ti
4
ps
ln = Ni 1 − (1) 100 150 200 250 300 350 400 450 500
pc T Tc
i=1 T, K

where N1 = −7.628631, t1 = 1, N2 = 1.734314, t2 = 1.5, Fig. 1. Points of the selected experimental data for developing a new
N3 = −2.591127, t3 = 2.5, N4 = −3.290324, and t4 = 5. fundamental equation of state for R134a. (䊐) cv ; (䊊) w; (䉫) PVT.
 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111 105

[16]. For the gaseous phase, the data consist of 23 points of
Hozumi et al. [17], and 94 points of Goodwin and Moldover
[18].
The calculated values from the ancillary equation for
PVT-saturation as well as the gaseous isochoric specific
heats and the second and third virial coefficients were added
to the input data. The PVT-saturation values were calculated
from the three ancillary saturation equations from the triple
point to the critical point. The isochoric specific heat values
were calculated from a virial equation of state developed in
our group [19] with an ideal-gas specific heat equation. The
second and third virial coefficients calculated from an inter-
molecular potential model were also added [19]. The critical
constraints were also included on regression.
5. New fundamental equation of state
The fundamental equation of state can be expressed us-
ing an ideal-gas part and a residual part. All thermodynamic
properties can be calculated from the fundamental equation
of state using thermodynamic relations. The derivation of
thermodynamic relations from a fundamental equation of
state can be conducted on the basis of the canonical ensem-
ble principle and the thermodynamic laws. Table 1 sum-
marizes the relations of the thermodynamic properties as
derivative functions from the fundamental equation of state.
If two properties for a pure fluid are known, other properties
can be determined. In the case where the two independent
parameters (density and temperature) are not known, iter-
ative strategy is required. For saturation, properties can be
calculated when just one property is known.
The ideal-gas part is established from the ideal-gas spe-
cific heat equation. The specific heat equation was estab-
lished by fitting data that were theoretically calculated by
Yokozeki et al. [20]. The specific heat equation was op-
timized with a genetic optimization method by introduc-
ing polynomial and Planck–Einstein terms. The ideal-gas
part was derived by integration of the ideal-gas specific
heat equation with an integral boundary condition deter-
mined by fitting the fundamental equation of state to a refer-
ence state of 200 kJ kg−1 and 1 kJ kg−1 K−1 for the enthalpy
and entropy values of the saturated-liquid at 273.15 K. The
ideal-gas part is written as,
 
o δ
α (δ, τ) = ln + N0o + N1o τ + N2o τ −0.25
τ


5
+ Nio ln{1 − exp(−bio τ)} (4)
i=3

Table 1
Thermodynamic relations of the Helmholtz free energy function
Property Relation
p(δ, τ)
Compressibility factor Z= = 1 + δαrδ
ρRT
Fugacity f(δ, τ) = p exp{αr + δαrδ − ln(1 + δαrδ )}

cp (δ, τ) cv (δ, τ) (1 + δαrδ − δταrδτ )2

Isobaric specific heat = +
R R (1 + 2δαrδ + δ2 αrδδ )
cv (δ, τ)
Isochoric specific heat = −τ 2 (αoττ + αrττ )
R
Isothermal compressibility κ(δ, τ)ρRT = {1 + 2δαrδ + δ2 αrδδ }−1
−(δαrδ + δ2 αrδδ + δταrδτ )
Joule–Thomson coefficient µ(δ, τ)Rρ =
(1 + δαrδ − δταrδτ )2 + cv (δ, τ)/R(1 + 2δαrδ + δ2 αrδδ )
   
cs (δ , δ , τ) cv (δ , τ) (1 + δδ αrδ − δ ταrδτ )  r 1 dps (δ , δ , τ)
Saturated-liquid specific heat = + r  r  × 1 + δ αrδ − δ ταδτ − 
R R (1 + 2δ αδ + δ2 αδδ ) Rρc δ dT
Second virial coefficient B(τ)ρc = limδ→0 αrδ
h(δ, τ)
Specific enthalpy = τ(αoτ + αrτ ) + 1 + δαrδ
RT
s(δ, τ)
Specific entropy = τ(αoτ + αrτ ) − (αo + αr )
R
g(δ, τ)
Specific Gibbs free energy = 1 + αo + αr + δαrδ
RT
u(δ, τ)
Specific internal energy = τ(αoτ + αrτ )
RT
cp (τ)
o
co (τ)
Specific heat of ideal gas = 1 − τ 2 αoττ = 1 + v
R R
w2 (δ, τ)M r 2 r (1 + δαrδ − δταrδτ )2
Speed of sound = 1 + 2δαδ + δ αδδ +
RT cv (δ, τ)/R
Third virial coefficient C(τ)ρc2 = limδ→0 αrδδ
 ∂α   ∂α    
∂2 α ∂2 α ∂2 α ρ Tc
Abbreviations: αδ = ∂δ τ , ατ = ∂τ δ , αδδ = ∂δ2 τ
, αττ = ∂τ 2 δ
, αδτ = ∂δ∂τ , δ= ρc , τ= T .
106 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111

Table 2 Table 3
Numerical coefficients and parameters of the residual part (Eq. (5)) Summary of comparisons for saturation density measurements
i di ti Ni Source Range, N AADa BIASa STDa Nout
T (K)
1 1 0.5 1.832124209 × 100 First author Ref.
2 1 1.125 −2.940698861 × 100
3 1 3.25 5.156071823 × 10−1 Saturated-liquid density
4 2 0.5 2.756965911 × 10−1 Aoyama [7] 372–374 4 1.1 −1.1 0.65 –
5 2 1.875 1.225264939 × 100 Defibaugh [54] 245–370 26 0.12 0.035 0.18 –
6 2 2.75 −6.486749497 × 10−1 Basu [21] 239–372 9 0.29 −0.19 0.45 –
7 3 1.625 −9.286738053 × 10−1 Fukushima [22] 325–357 3 0.37 −0.31 0.38 -
8 3 2.125 3.920381291 × 10−1 Fukushima [23] 244–292 7 0.10 0.071 0.10 –
9 4 1.125 1.056692108 × 10−1 Fukushima [47] 370–374 8 0.057 0.057 0.017 2
10 1 3.75 −7.586523371 × 10−1 Higashi [24] 359–374 8 0.98 0.22 1.9 –
11 2 1.5 −1.198140136 × 100 Hou [10] 180–360 12 0.14 −0.14 0.20 –
12 3 0.75 −2.878260390 × 10−1 Kabata [25] 343–374 12 0.65 0.48 1.4 –
13 2 9 −9.723032379 × 10−2 Maezawa [26] 200–370 25 0.13 −0.11 0.13 –
14 3 8.5 5.307113358 × 10−2 Morrison [27] 268–368 12 0.21 −0.21 0.24 1
15 4 5.5 −4.681610582 × 10−2 Niesen [30] 316–370 12 0.18 −0.18 0.18 –
16 4 32 −9.604697902 × 10−3 Padua [57] 198–298 5 0.069 0.016 0.13
17 5 23 6.668035048 × 10−3 Takahashi [28] 258–306 7 0.14 0.14 0.039 –
18 6 31 2.361266290 × 10−3 Yokoyama [29] 252–367 21 0.10 −0.011 0.18 –
Saturated-vapor density
Aoyama [7] 373–374 7 1.2 0.13 1.63 –
Fukushima [22] 371–374 9 1.4 −0.81 2.5 2
where the numerical coefficients and parameters are N0o = Fukushima [23] 294–371 6 0.24 −0.24 0.34 –
10.78497786, N1o = 8.612977410, N2o = −24.37548384, Higashi [24] 362–374 6 1.9 −0.31 2.9 –
N3o = 7.451784998, N4o = −4.239239505, N5o = Kabata [25] 361–374 15 2.8 0.48 4.8 3
6.445739825, b3o = 4.103830338, b4o = 2.561528683, and Morrison [27] 298–368 8 5.6 4.8 7.0 –
Niesen [30] 316–370 12 0.43 0.35 0.57 –
b5o = 2.084607363. It should be noted that this relation is Weber [13] 320–368 5 0.17 −0.16 0.25 –
empiric equation, therefore, the Planck–Einstein terms in 

a AAD = (1/n) n |∆ |; STD =

the equation do not relate to the fundamental frequencies of i=1 i {1/(n − 1)} ni=1 (∆i − BIAS)2 ;

molecules of the fluid. BIAS = (1/n) ni=1 ∆i ; n: number of data included in evaluation; ∆ =
The residual part was optimized from multi-property re- 100(Y − Ycal )/Ycal ; and Y: an evaluated property.
gression and its functional form was selected in accordance
with a genetic optimization method. The genetic optimiza-
tion method for optimizing both the ideal gas and residual
parts was originally developed in a series of this study [6].
The residual part was finally adopted as,
Table 4


9

12 Summary of comparisons for vapor pressure measurements
αr = Ni δdi τ ti + Ni δdi τ ti exp(−δ)
Source Range, N AADa BIASa STDa Nout
i=1 i=10 T (K)
First author Ref.


15

18
+ Ni δdi τ ti exp(−δ2 ) + Ni δdi τ ti exp(−δ3 ) (5) Arita [31] 273–323 3 0.057 −0.057 0.025 –
i=13 i=16 Baehr [32] 303–373 37 0.019 −0.015 0.015 2
Baroncini [33] 243–359 64 0.25 0.15 0.24 –
where the numerical coefficients and parameters are given Basu [21] 211–369 32 0.35 0.25 0.58 –
in Table 2. Blanke [34] 175–374 53 0.11 −0.030 0.13 –
Fukushima [22] 262–372 41 0.13 −0.029 0.19 –
Goodwin [35] 214–313 57 0.033 0.020 0.038 –
Hou [10] 180–360 10 0.42 0.40 0.76 2
6. Assessments and discussions Kubota [36] 253–373 25 0.23 0.013 0.29 –
Maezawa [26] 280–350 13 0.38 −0.0077 0.61 –
Thermodynamic properties were calculated from the new Magee [37] 180–350 19 0.26 −0.057 0.42 –
Morrison [27] 268–368 12 0.084 0.034 0.13 1
fundamental equation of state to judge the reliability, espe-
Niesen [30] 316–370 12 0.074 0.057 0.054 –
cially for reproducing experimental data and for satisfying Piao [38] 308–368 51 0.012 −0.11 0.080 5
thermodynamic consistency from a theoretical viewpoint. Tillner-Roth [39] 170–232 33 0.55 0.54 0.74 –
Thermodynamic property values calculated from the new Weber [13] 313–373 22 0.021 −0.020 0.012 –
fundamental equation serve as a baseline to express the de- Wilson [40] 211–369 32 0.36 0.24 0.61 –
Zhu [41] 279–363 43 0.093 −0.032 0.11 –
viations. The statistical results from these assessments are
a
given in Tables 3–5. The statistical definitions used for evalu- The same as definition in Table 3.
 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111 107

Table 5
Summary of comparisons for measurements in single phase
Source Phase Range N AADa BIASa STDa Nout
First author Ref. p (MPa) T (K)

Density
Baroncini [33] G 0.18–1.9 263–359 46 0.52 0.40 0.46 –
Basu [21] G 1.1–6.7 317–448 28 0.43 −0.15 0.61 2
Blanke [34] L 0.86–4.6 180–233 44 0.045 0.045 0.036 –
Defibaugh [54] L 0.80–6.5 242–372 924 0.083 0.083 0.092
Dresner [41] G 0.28–57.8 333–423 121 0.058 −0.0061 0.090 –
Fukushima [22] L, G 0.55–5.7 294–424 63 0.39 0.098 0.56 2
Hou [10] L 0.75–70.9 180–380 429 0.16 −0.15 0.18 –
Klomfar [55] L 1.0–56 204–310 89 0.13 0.13 0.032 –
Maezawa [26] L 0.51–2.0 280–340 10 0.15 −0.15 0.038 –
Magee [8] L 2.58–34.9 187–343 150 0.059 −0.038 0.062 –
Morrison [27] L 0.70–5.8 279–367 121 0.085 −0.039 0.14 –
Qian [43] G 0.13–1.9 320–340 21 0.025 0.022 0.027 –
Tillner-Roth [11] L 0.73–16 243–413 432 0.097 0.0075 0.17 1
Tillner-Roth [12] G 0.09–16 293–453 411 0.058 −0.0001 0.12 –
Weber [13] G 1.2–5.3 321–423 56 0.067 −0.052 0.087 –
Yamamoto [44] G −3.1 273–363 38 0.19 −0.19 0.29 –
Zhang [45] G 0.13–1.9 320–340 21 0.026 0.017 0.029 –
Zhu [46] G 0.14–1.3 283–353 42 0.38 0.091 0.44 –
Speed of sound
Beckermann [52,53] G 0.025–0.50 260–420 245 0.021 −0.010 0.029 –
Goodwin [18] G 0.006–0.6 233–340 94 0.023 −0.023 0.014 –
Grebenkov [16] L 0.1–16 296–351 48 0.36 0.26 0.30 –
Guedes [14] L 0.1–70 179–380 206 0.47 0.11 0.78 –
Hozumi [17] G 0.01–0.25 273–298 23 0.028 −0.028 0.012 –
Takagi [15] L 0.08–31 243–333 237 0.29 0.29 0.18 11
Isobaric specific heat
Saitoh [48] L 1.0–3.0 276–356 31 0.72 0.72 0.32 –
Sato [49] L 1.0–3.0 276–350 31 0.73 0.95 2.67 2
Isochoric specific heat
Magee [8] L 2.6–35.9 387–343 150 0.32 0.05 0.44 –
a The same as definition in Table 3.

ation are as follows: AAD—average of absolute values of de- Representations of density deviations in the single phase
viations; BIAS—average of deviations; and STD—standard are shown in Figs. 5 and 6. The density deviations in the
deviation. Each formulation of the definitions are given as superheated-vapor states are shown in Fig. 5 for pressures
noted in the tables. lower than the critical pressure and in the liquid phase are
The new fundamental equation of state accurately rep-
resents the ideal-gas property as shown in Fig. 2. The 1.0
theoretical background data of Yokozeki et al. [20] can 0.8
be well represented from 120 to 1000 K. In compari- 0.6
Deviation of cp o, %

son with other existing equation of state, the new equa- 0.4
tion of state superiorly reproduces the ideal-gas isobaric 0.2
specific heat. The most reliable specific heats can be 0
-0.2
represented with deviation less than 0.1% over a wide
-0.4
range.
-0.6
The representation of saturation properties of the new fun- -0.8
damental equation of state is shown in Figs. 3 and 4. Fig. 3 -1.0
shows the deviations of vapor pressure and saturation tem- 100 300 500 700 900 1100
perature from the new equation of state. The most reliable T, K
measurements are represented with an uncertainty of 0.05%
(0.8 kPa) in vapor pressure and 0.003% (14 mK) in satura- Fig. 2. Deviation of the ideal-gas isobaric specific heat from the new
fundamental equation of state. (䊐) Goodwin and Moldover [18]; (䊊)
tion temperature. Saturated-liquid and saturated-vapor den- Sato et al. [50]; (䉫) Yokozeki et al. [20]; (----) Piao et al. [5]; (——)
sities are represented within 0.2 and 0.5%, respectively, as Tillner-Roth and Baehr [1] and Span and Wagner [3]; (—+—) Huber
shown in Fig. 4. and Ely [2,4]; (—䊉—) Chen et al. [56].
108 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111

0.4 0.4
0.2 0.2
ps , %

0
0
Deviation of r , %

-0.2
Deviations

-0.2
-0.4
-0.4 0.1 1 10 100
p , MPa
0.04 0.4
0.02 0.2
Ts , %

0 0
-0.02 -0.2
-0.04 -0.4
150 200 250 300 350 400 450
150 225 300 375
T, K
T, K

Fig. 6. Deviations of density in the liquid phase from the new fundamental
Fig. 3. Deviations of vapor pressure and saturation temperature from the
equation of state. (䉫) Magee [37]; (×) Tillner-Roth and Baehr [11]; (䊐)
new fundamental equation of state. (䊐) Magee and Bowley [37]; (×)
Blanke et al. [34]; (&) Morisson and Ward [27].
Fukushima et al. [22]; (䉫) Baehr and Tillner-Roth [32]; (+) Baroncini
et al. [33]; (䊊) Weber [13]; (&) Tillner-Roth [39]; (——) Tillner-Roth
and Baehr [1]; (----) Span and Wagner [3].
2
1
cp , %

0.4 0
Saturated liquid
0.2 -1
Deviations

0
Deviations of r , %

-2
-0.2
-0.4 2
1
2
cv , %

Saturated vapor 0
1
-1
0
-2
-1
-2 150 200 250 300 350 400
T, K
150 225 300 375
T, K
Fig. 7. Deviations of specific heats in the liquid phase from the new
Fig. 4. Deviations of saturated-liquid and saturated-vapor densities from fundamental equation of state. (䉫) Magee [8]; (×) Saitoh et al. [48].
the new fundamental equation of state. (䉫) Yokoyama and Takahashi
[29]; (+) Maezawa et al. [26]; (䊊) Higashi [24]; (䊐) Hou et al. [10];
(䊉) Niessen et al. [30]; (&) Fukushima et al [22]; (×) Takahashi et al. for the liquid phase, and 0.3% for supercritical phase. As
[28]; (——) Tillner-Roth and Baehr [1]; (----) Span and Wagner [3]. shown in these figures, the data of Tillner-Roth and Baehr
[11,12] and Magee [37] are well reproduced.
shown in Fig. 6 for temperatures lower than the critical tem- Assessment results for caloric properties of both speed of
perature. The deviations in the supercritical phase are also sound and specific heat are shown in Figs. 7 and 8. The most
shown in Figs. 5 and 6. Densities can be represented with an accurate speed-of-sound measurements are represented with
uncertainty of 0.1% for the superheated-vapor states, 0.08% an uncertainty of 0.02% for the gaseous phase, and 0.5%

0.4 3 Liquid phase

2
0.2 1
0 0
Deviation of w , %

-0.2 -1
Deviation of r , %

-0.4 -2
0.01 0.1 1 10 100 -3
p , MPa 0.10
0.4 Gaseous phase
0.05
0.2 0
0 -0.05
-0.2 -0.10
-0.4 150 200 250 300 350 400
200 250 300 350 400 450 T, K
T, K
Fig. 8. Deviations of speed-of-sound measurements from the new funda-
Fig. 5. Deviations of density in the gaseous phase from the new funda- mental equation of state. (䊐) Guedes and Zollweg [14]; (+) Grebenkov
mental equation of state. (&) Zhu et al. [41]; (䊐) Zhang et al. [45]; (×) et al. [16]; (×) Takagi [15]; (&) Goodwin and Moldover [18]; (䊊) Hozumi
Tillner-Roth and Baehr [12]; (䉫) Dresner and Bier [42]. et al. [17].
 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111 109

1.0 1.4

100 MPa
1.2 5
0.5
Deviation of cs' , %

7
-1 -1

4
cv , kJ·kg ·K

1.0 2.5
0 1.5
1
0.5
0.8
0.1
-0.5 cvo
0.01
0.6
-1.0
150 200 250 300 0.4
150 200 250 300 350 400 450 500 550
T, K
T, K
Fig. 9. Deviations of saturated-liquid specific heat from the new funda-
mental equation of state. (䉫) Magee [8]. Fig. 12. Isobaric lines of isochoric specific heat from the new fundamental
equation of state.

0.50
-2

Huber and Ely [2] 3.5

C , dm ·mol

0.25 Huber and Ely [4]

5
3.0
6

0 Piao et al. [5]

-0.25 Tillner-Roth and Baehr [1] 4
-1 -1

2.5 7
cp , kJ·kg ·K

This work
-0.50
10
0 2.0
[4] [2] Huber and Ely [4]
-1

Huber andand
ElyEly 15
Huber
B , dm ·mol

-0.25
1.5 100 MPa
-0.5 Piao et al. [5]
3

Tillner-Roth and Baehr [1] 1.5 2.5

1
-0.75 This work 1.0 0.5
0.1
-1 cpo
0 100 200 300 400 500 0.5
T, K 150 200 250 300 350 400 450 500 550
T, K
Fig. 10. Second and third virial coefficients from several equations of
state. (䊊) Yokozeki et al. [20]. Fig. 13. Isobaric lines of isobaric specific heat from the new fundamental
equation of state.

for the liquid phase. On the other hand, specific heats are
reproduced with an uncertainty of 0.8% in the liquid-phase relationship between the virial coefficients and the behavior
isochoric specific heat, and 1.0% in liquid-phase isobaric of the gaseous specific heat is important as discussed in our
specific heat. The saturated-liquid specific heats such as the reports on R32 [6] and R125 [51].
data of Magee [8] are reproduced with an uncertainty of The extrapolation of thermodynamic properties was in-
0.6% as shown in Fig. 9. vestigated from isobaric lines of specific heat and speed
Consistency with intermolecular potential behavior can be of sound, and isothermal lines of pressure respect to vol-
revealed from the second and third virial coefficients, which ume. These representations are shown in Figs. 12–15.
are shown in Fig. 10. Both coefficients can be represented
rationally. Gaseous specific heats are shown in Fig. 11. A
1600
1400
1.1
This work 1200
1.0 2 MPa
Tillner-Roth and Baehr [1] 1000
w , m·s-1
-1 -1

0.9 Piao et al. [5]

cv , kJ·kg ·K

1
800 100 MPa
0.5 Huber and Ely [4]
0.8 70
0.25 600
0.01

50
0.0001 MPa
0.1

0.1 35
0.7 400 25
0.5

15
1.5
1

7 10
2.5

0.6 200
Huber and Ely [2] 5
0.5 0
150 200 250 300 350 400 450 500 150 200 250 300 350 400 450 500 550
T, K T, K

Fig. 11. Specific heats in the gaseous phase from several equations of Fig. 14. Isobaric lines of speed of sound from the new fundamental
state. equation of state.
110 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111

100 tively. By introducing these values into the pressure relation

500 K (compressibility factor), a critical pressure of 4.04806 MPa
10
340
was obtained. These values are very close to the critical val-
1 290 ues selected in this study.
p , MPa

260
0.1 240
220
205
0.01
190
180
0.001 170 K
0.0001
0.0001 0.001 0.01 0.1
3 -1
v , m ·kg
Fig. 15. Pressure–density–temperature diagram from the new fundamental
equation of state.
These results indicate that the extrapolations are properly
represented—the isochoric and isobaric specific heats in-
crease and speed-of-sound values decrease when the state
is close to the critical point. Furthermore, the new equa-
tion of state also reasonably represents the characteristics
of the ideal curves as shown in Fig. 16. In comparison
with the International Standard equation of state for R134a
(Tillner-Roth and Baehr [1]), the new equation of state
can represent all ideal curves of the compression factor,
but the International Standard equation of state suffers in
the representation of Joule inversion curve. By consider-
ing the reasonable characteristics of the ideal curves, it
is shown that the new equation of state can be accepted
for calculating thermodynamic properties with high accu-
racy, even in the region where experimental data are not
available.
Independent critical parameters of density and tempera-
ture can be obtained from the fundamental equation of state
by taking the primary and secondary differentials of pres-
sure with respect to volume in accordance with the critical
constraint conditions, i.e., both of the differential values are
zero. The critical temperature and density were calculated
from the new equation of state by introducing these two con-
straint conditions, resulting in the values of 374.083 K and
509 kg m−3 for the critical temperature and density, respec-
1000
100 Ideal curve
Joule-Thomson inversion curve
p/pc
7. Conclusion
A fundamental equation of state for R134a was estab-
lished with reasonable second and third virial coefficients
1 10 100 owing to the use of a theoretical background using in-
termolecular potential theory. Characteristics of the ideal
curves were also involved in an assessment to find an ac-
ceptable fundamental equation of state such that the struc-
tural function of the new equation of state is reasonable and
the effect of experimental systematic errors can be avoided.
The equation of state can provide rational thermodynamic
properties even at very low temperatures, near saturation
in the gaseous phase, and in the region beyond the region
where experimental data are available. Gaseous specific
heats near saturation are reasonably represented without
any thermodynamic inconsistency.
The new fundamental equation of state is valid for tem-
peratures from the triple point to 460 K and pressures up
to 70 MPa and it behaves in a qualitatively rational manner
even in the region far from the range of existing experimen-
tal data. The estimated uncertainties in the range of exist-
ing experimental data are 0.1% in density for the gaseous
and liquid phases, 0.02% in speed of sound for the gaseous
phase, 0.5% in speed of sound for the liquid phase, and 0.8%
in isochoric specific heat for the liquid phase. The uncer-
tainties of saturation properties are 0.05% in vapor pressure,
and 0.25 and 0.5% in densities for the saturated-liquid and
saturated-vapor phases, respectively. The equation of state
has reliable third virial coefficients making it possible to de-
rive reliable thermodynamic properties near saturation in the
gaseous phase even at low temperatures that are useful to
precisely design refrigeration and air-conditioning systems.
List of symbols
a specific Helmholtz free energy
B second virial coefficient
c specific heat
Joule inversion curve C third virial coefficient
f fugacity
g specific Gibbs free energy
h specific enthalpy

10
N number of data
Saturation line p pressure
1
Boyle curve R gas constant
s specific entropy
0.1 T temperature
0.1 1 10 u specific internal energy
T /T c
v specific volume
Fig. 16. Comparisons of ideal curves. (—) The new fundamental equation w speed of sound
of state; (----) Tillner-Roth and Baehr [1]. Z compressibility factor
 I M. Astina, H. Sato / Fluid Phase Equilibria 221 (2004) 103–111 111

Greek letters [19] K. Narukawa, A. Mizuoka, H. Sato, in: Presented at 14th Symposium
on Thermophysics Properties Boulder, Colorado, 2000.
α reduced Helmholtz free energy,
[20] A. Yokozeki, H. Sato, K. Watanabe, Int. J. Thermophys. 19 (1998)
α = αo + αr , α = a/RT, 89–127.
δ reduced density, ρ/ρc [21] R.S. Basu, D.P. Wilson, Int. J. Thermophys. 10 (1989) 591–603.
κ isothermal compressibility [22] M. Fukushima, N. Watanabe, T. Kamimura, Trans. JAR 7 (1990)
µ Joule–Thomson coefficient 243–256.
[23] M. Fukushima, Trans. JAR 8 (1991) 65–75.
ρ mass density
[24] Y. Higashi, Int. J. Refrig. 17 (1994) 524–531.
τ inverse reduced temperature, Tc /T [25] Y. Kabata, S. Tanikawa, M. Uematsu, K. Watanabe, Int. J. Thermo-
phys. 10 (1989) 605–615.
Subscripts [26] Y. Maezawa, H. Sato, K. Watanabe, J. Chem. Eng. Data 35 (1990)
c critical parameter 225–228.
[27] D. Morrison, D.K. Ward, Fluid Phase Equil. 62 (1991) 65–86.
out rejected
[28] K. Takahashi, Y. Takaishi, K. Oguchi, in: Proceedings of 15th Japan
p process at constant pressure Symposium on Thermophysics Properties, 1994, pp. 141–144.
s saturation [29] C. Yokoyama, S. Takahashi, Fluid Phase Equil. 67 (1991) 227–
v process at constant volume 240.
[30] V.G. Niesen, L.J. Van Poolen, S.L. Oucalt, C.D. Holcomb, Fluid
Phase Equil. 97 (1994) 81–95.
Superscripts
 [31] K. Arita, T. Tomozawa, Y. Nakagawa, Y. Yoshida, Fluid Phase Equil.
saturated-liquid state 63 (1991) 151–156.
 saturated-vapor state [32] H.D. Baehr, R. Tillner-Roth, J. Chem. Thermodyn. 23 (1991) 1063–
o ideal-gas part 1068.
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Meeting, IIR, Herzlia, 1990, pp. 5–7.
[34] W. Blanke, G. Klingenberg, R. Weiss, Int. J. Thermophys. 16 (1995)
1143–1153.
Acknowledgements [35] A.R.H. Goodwin, D.R. Defibaugh, L.A. Weber, Int. J. Thermophys.
13 (1992) 837–854.
The authors would like to thank Dr. Eric. W. Lemmon, [36] H. Kubota, T. Yamashita, Y. Tanaka, T. Makita, Int. J. Thermophys.
10 (1989) 629–637.
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