ZHANG・IWASHITA・SANADA：Soave-Redlich-Kwong Adiabatic Equation for Gas-loaded Accumulator 65 

研究論文

Soave-Redlich-Kwong Adiabatic Equation for Gas-loaded Accumulator＊

Shuce ZHANG＊＊, Hiromu IWASHITA＊＊＊, Kazushi SANADA＊＊＊＊

　In this paper, a Soave-Redlich-Kwong adiabatic equation of real gas charged in accumulators is proposed. The Soave-
Redlich-Kwong equation is the most accurate real gas model for representing accumulator behavior, but it is relatively
complex mathematical equation. For simulating accumulator dynamic behavior, it has been used by combining with a
thermal time constant model. The mathematical procedure for the Soave-Redlich-Kwong equation for the adiabatic equation
is described in this paper. The Soave-Redlich-Kwong adiabatic equation is discussed by comparing the van der Waals
adiabatic equation. By comparing representative gas models, the Soave-Redlich-Kwong adiabatic equation is found to be
valid.
Key words：Gas-loaded accumulator, Adiabatic process, Soave-Redlich-Kwong equation, van der Waals equation, Benedict-
Webb-Rubin equation, Thermal time constant

molecular volume into account, real gas models have been

1．Introduction
　Selection of accumulator size and prefill pressure have
been discussed by many researchers. A typical practice is to
assume that the process involved is isothermal, adiabatic, or
polytropic1）. Isothermal operation maintains a constant
temperature, which requires the rate of expansion and
compression of the gas at such a rate that the gas
temperature inside the accumulator remains relatively
constant throughout the entire cycle. For the adiabatic
operation, the gas temperature inside the accumulator
increases or decreases at a high rate due to the rapid
compression or expansion of the gas. However, in practical
processes, the temperature is increasing during charge
process and decreasing during discharge process. A concept
of polytropic change is used to describe the phenomena,
where the polytropic exponent n is used to compensate the
inaccuracy for calculating accumulator. For the polytropic
exponent of the currently employed gas, nitrogen, the value
has been predicted by experiment according to charging and
discharging time and average working pressure .
Simultaneously, for taking intermolecular forces
　　　＊
Manuscript received September, 12, 2017
　　＊＊
Graduate School of Engineering
Yokohama National University

（Tokiwadai 79-5 Hodogaya-ku, Yokohama, Kanagama, 240-
8501, Japan）
（E-mail：zhang-shuce-hc@ynu.jp）
　＊＊＊
College of Engineering Science
Yokohama National University
＊＊＊＊
Faculty of Engineering
Yokohama National University
presented and developed by researchers. Modeling of
thermodynamic behavior of fluid over the whole range of
temperatures, densities and pressures is not an easy task. At
low pressure, the isotherms are fairly easily modeled with
something like the ideal gas model. However, at higher
density the behavior becomes more difficult to model with a
simple equation3）. As the first correction to the ideal gas
equation, the van der Waals equation was developed for
engineering purposes4）. The two most commonly used cubic
equations of state are the Redlich-Kwong5） and Soave’s
modification of the Redlich-Kwong equation of state（Soave-
Redlich-Kwong equation6））
. These models were developed
by modifying the van der Waals equation, and it has been
applied in a commercial software.
　It is necessary to consider the energy balance in
accumulator. The nitrogen gas in accumulator has internal
energy which receives heat energy from the environment
and performs work to the working fluid. Predicting
thermodynamic loss is necessary. Otis has presented a
2）
thermal time constant model which has been combined with
and the Beattie-Bridgman equation of state to describe the heat
transfer from the accumulator wall7）-8）. It is relatively easy to
use the van der Waals equation of state. Its isothermal model
and the adiabatic model are also easy to obtain
mathematically. However, the Soave-Redlich-Kwong equation
has relatively complex mathematical expression. The
adiabatic equation has not been found. Therefore, for
calculating accumulator, only one possibility was to combine
the Soave-Redlich-Kwong equation with the thermal time
constant model to carry out numerical integration. The
purpose of this paper is to propose an adiabatic expression of

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66 日本フルードパワーシステム学会論文集

the Soave-Redlich-Kwong equation. According to this condition, the van der Waals adiabatic
　Section 2 is the nomenclature and section 3 gives equation has been founded：

（ ）
introduction of representative real gas models. In section 4, avdWm2
（V－mbvdW）＝const ⑵
H
P＋
the Soave-Redlich-Kwong adiabatic equation is derived. In V2
section 5, the proposed adiabatic equation is validated by where the adiabatic exponent is expressed by：
comparing with representative real gas models. The R
H＝ ＋1 . ⑶
conclusion is made in section 6. Cv
3.2　Benedict-Webb-Rubin equation of state
2．Nomenclature
　Gas pressure is related to gas temperature and gas volume
avdW ： Parameter of van der Waals equation by the Benedict-Webb-Rubin equation of state11）-13） which
（
a T） ： Parameter of Soave-Redlich-Kwong equation was shown to be in remarkable agreement with the data
b ： Parameter of Soave-Redlich-Kwong equation published by the NBS for nitrogen14） for the entire range of
bvdW ： Parameter of van der Waals equation interest for accumulator applications9）. The expression of this
C ： Constant equation of state is as follows：
Cv ： Specific heat at constant volume
（ ）
C0
m2 B0RT－A0－　　 3
H ： Adiabatic exponent mRT T2 m（b 0RT－a0）
P＝ ＋ ＋
m ： Amount of gas V V2 V3
 ⑷
n ： Polytropic exponent m2γ －mVγ
（ ）
2

3
m c0 1＋　　　 e 2
6
P ： Absolute pressure m a0 α V2
＋ 6 ＋ 3 2
Q ： Heat energy V V T
R ： Gas constant where A0, B0, C0, a0, b0, c0, α and γ are Benedict-Webb-Rubin
S ： Entropy parameters.
T ： Absolute temperature 3.3　Soave-Redlich-Kwong equation of state
U ： Internal energy 　In physics and thermodynamics, the Redlich-Kwong
V ： Gas volume equation of state is an empirical, algebraic equation that
v ： Mole volume relates temperature, pressure, and volume of gases. It is
κ ： Parameter of Soave-Redlich-Kwong equation generally more accurate than the van der Waals equation
ω ： Acentric factor and the ideal gas equation at temperatures above the critical
Subscript temperature. It was presented by Otto Redlich and Joseph
0 ： Initial value Neng Shun Kwong in 1949. It showed that a two-parameter,
c ： Critical property cubic equation of state could well reflect reality in many
situations, standing alongside the much more complicated
3．Real gas models
Beattie-Bridgeman model15） and Benedict-Webb-Rubin
3.1　van der Waals equation of state equation that were used at the time. The Redlich-Kwong
　Gas equation of state properly expresses thermal motion equation has undergone many revisions and modifications,
with considering mass of molecule. The accumulator gas is for either improving its accuracy in terms of predicting gas-
often modeled as ideal gas which does not exist. Ideal gas phase properties of more compounds, as well as in better
model fails to account for intermolecular force and molecular simulating conditions at lower temperatures, including vapor-
volume. The gas in the accumulator assumed to be ideal in liquid equilibria. The Soave-Redlich-Kwong equation fitted
many cases has shown to result in large errors9）-10）. To experimental vapor-liquid data well and could predict phase
account for the volume that a real gas molecule takes up and behavior of mixtures in the critical region. The Soave-Redlich-
the intermolecular attraction, the van der Waals equation of Kwong equation of state is given by the expression：
state is formulated as mRT a T）m2 ,
（
P＝ －  ⑸
V －mb V

（ ）
（V＋mb）
avdWm2
⎩―⎨―⎧

P＋ （V－mbvdW）＝mRT where
V2  ⑴
1 9 2
avdW＝ vc,　bvdW＝ RTcvc
⎩―⎨―⎧
⎩―⎨―⎧

1
R2T 2c
（ ）
3 8 T 2 , ⑹
a T）＝0.4274
（ 1＋k 1－ 　　
Pc Tc
It is known that the entropy is constant in adiabatic condition.

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 ZHANG・IWASHITA・SANADA：Soave-Redlich-Kwong Adiabatic Equation for Gas-loaded Accumulator 67

RTc where
b＝0.08664 , and ⑺
Pc

⎩―⎨―⎧
⎩―⎨―⎧
1 1
kR2Tc T － 2
（ ） （ ）
∂a（T） T 2 . ⒄
k＝0.480＋1.57ω－0.176ω . 2
⑻ ＝－0.4274 　　 1＋k 1－ 　　
∂T Pc T c Tc
The Pitzer’s acentric factor ω of nitrogen gas is assumed as
0.04. The super-critical cohesion parameters for the Soave- Combining Otis’s model of Eq.（15）with Eq.（16）and（17）
, it
Redlich-Kwong equation of state were adjusted by fitting is possible to mathematically analyze the accumulator gas
cohesion parameters to the reliable Joule-Thomson inversion charge and discharge processes by numerical integration.
curve data by Mehdi Ghanbari and Gholam Reza Check16）：
4．Derivation of adiabatic model of SRK
⎩―⎨―⎧

T 2
0.480＋1.57ω－0.176ω； ≤ 1 　The Soave-Redlich-Kwong adiabatic equation is derived in
Tc
k＝  ⑼
11 2 T this section as follows. First law of thermodynamics is
（0.480＋1.57ω－0.176ω ）；T ＞1
15 c
expressed as：
The modified parameter k was fit with a coefficient of 11/15 dU＝dQ－PdV. ⒅
for super-critical region. For the nitrogen gas using in gas- The entropy is defined as：
loaded accumulator, the operating temperature is commonly dQ .
ds＝  ⒆
larger than its critical temperature （126.2K）
, thus, the T
function of k with 11/15 is employed in this paper. Combining Eq.（18）and Eq.（19）yields：
3.4　Thermal time constant model dU＝Tds－PdV. ⒇
　The Otis’s thermal time constant model introduced a The volume partial differential of Eq.（20）under constant
thermal time constant τ to express the functional relation of temperature is：

（∂V ）＝T（∂V ）－P.

temperature with time： ∂U ∂S


（ ）
T T
dT T －T T ∂P dv ，
＝ wτ － c
dt v ∂T v dt  ⑽
From Maxwell relations, we know that

（∂V ）＝（∂T ）.

where the definition of thermal time constant is given by the ∂S ∂P

expression： T V

mcv . Then the Eq.（21）can be deformed as：

τ＝  ⑾
hA
It is necessary to employ a gas model to evaluate the term of （∂V
∂U
）＝T（∂T
T
∂P
）－P. V


（∂P/∂T）
v in the second part of the right side of Eq.（10）
. For Substituting Eq.（16）and the Eq.（5）into Eq.（23）yields：
the nitrogen gas sealed in accumulator, the mole number of
（ ）∂U m2a（T） Tm2 ∂a（T）
＝ －  
nitrogen gas m is constant. Because the mole volume is ∂V T V（V＋mb） V （V＋mb） ∂T
defined as： The total differential of internal energy is expressed by：

（∂T
∂U
）dT＋（∂V
∂U
） dV.
V
v＝ m , ⑿ dU＝ 
V T

therefore The definition of specific heat at constant volume is：

（ ）
dv 1 dV . 1 ∂U
⒀ Cν＝
m ∂T V  
＝ .
dt m dt
The condition of constant mole volume is identical to the Substituting Eq.（24）and Eq.（26）to Eq.（25）yields：
constant volume condition. Hence,
dU＝ （∂T
∂U
）dT＋（∂V
∂U
） dV
（∂T
∂P
）＝（∂T ）
∂P . V T
⒁ 2
 
v V
m ∂a（T） dV
＝mCνdT＋ －T
a（T）
Then the Otis’s model can be written as： （V＋mb）
V ∂T

Combining Eq.（20）with Eq.（27）to delete dU and solving

（ ） m dt .
dT Tw－T T ∂P 1 dV
＝ － ⒂
dt τ cv ∂T V for the total differential of entropy dS yield：
Thus, for calculating Otis’s model, the term（∂P/∂T）
v can be m2
TdS－PdV＝mCνdT＋
expressed by the Soave-Redlich-Kwong equation of state： V（V＋mb）
 
（ ）
∂P mR m2 ∂a
（T）, ∂a（T）
＝ －  ⒃ × （ －T
a T） dV
∂T V V－mb V（V＋mb） ∂T ∂T

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1 ∂a（T）
mCν 1 m2
（ ）
－
dS＝ dT＋ P＋ V bCν ∂T
. 
T T （V＋mb）
V Z＝ 　　　　　
V＋mb
 

（ ）
∂a（T） 　For calculating charge and discharge processes by the
× a －T
（T） dV
∂T Soave-Redlich-Kwong adiabatic equation, it is necessary to
Substituting the pressure P of Eq.（5）into Eq.（29）yields： calculate temperature during the processes. To calculate the
mCν mR temperature, a function can be built by the Soave-Redlich-
dS＝ dT－ dV
T V－mb Kwong equation：
 
（ ） （ ）
1 m2 m ∂a
（T） V－mb a（T）m2
+ － dV g（T）＝T－ P＋  
V V＋mb b ∂T mR （V＋mb）
　　　　　　　　　　　
V
Integrating both sides of the above equation yields： The temperature value can be obtained by computing the
1 ∂a（T）
root of the nonlinear equation：
⎩―⎨―⎧
⎩―⎨―⎧

R －

（ （）V＋mb ）
bCν ∂T
V
＋S0  （ ＝0
g T） 
Cν
S＝mCν ln T
（V－mb）
　　　　　　　　　 　　　　　

　The constant C in Eq.（35）can be calculated by the adiabatic

The temperature expression by the Soave-Redlich-Kwong initial condition：
equation is：

T＝
V－mb
mR （ P＋
V
（T）
a m2 .
（V＋mb）

）  （
P　
C＝ 　 0＋
V（V
0
a（T0）
0
m2
＋mb）
　　　　　　　　　
H
（V0－mb）

） 
（
1 ∂a（T）
）
（ ）
－
Substituting Eq.（32）into Eq.（31）yields： V0 bCν ∂T T＝T0
× 　　　　　　
V0＋mb

（ ）
⎩―⎨―⎧

R
1 （T）
a m2 1＋
Cν
S＝mCν ln P＋ （V－mb） Eq.（35）can be rewritten as：
mR （V＋mb）
　　　　　　　　　　　
V
  a（T）m2 C
＝
⎩―⎨―⎧

1 ∂a（T） P＋
（ ）
－
V
× 　　　　　　
bCν ∂T V（V＋mb） 1 ∂a（T）
 
＋S0
（ ）
－
V＋mb H V bCν ∂T
（V－mb） 　　　　　　
V＋mb
It is known that the entropy is constant for adiabatic The pressure P is expressed by：
condition. In Eq.（33）
, the constant entropy means that the a（T）m2 C
∴ P＝－ ＋
term inside the natural logarithm brackets is constant. V（V＋mb） 1 ∂a（T）
bCν ∂T  
（ ）
－
H V
According to this condition, the following formula is founded （V－mb） 　　　　　
V＋mb
for adiabatic process： Combining the solution of the Eq.（38）for temperature, it is
possible to calculate the pressure of adiabatic process if the

（ ）
1 ∂a（T）

（ ）
R －
2 1＋ V bCν ∂T
P＋ （ a T）m corresponding volume is known.
Cν
（V－mb） 　　　　　　
V＋mb
（V＋mb）
　　　　　　　　　　　
V  
5．Considerations
＝const
According to this expression form and substituting the 　Calculation of adiabatic process by the Soave-Redlich-
definition of adiabatic exponent H of Eq. （3） into above Kwong adiabatic equation proposed in this paper is carried
equation, the Soave-Redlich-Kwong adiabatic equation can be out and the results are shown in Fig. 1. As an assumption of
written as： the calculation, it is assumed that the initial condition at the

（ ）
1 ∂a（T） point A is 34MPa, abs. in gas pressure, 2.67×10－3m3（2.67L）

（ ）
2 －
（T）m
a H V bCν ∂T
P＋ （V－mb） 　　　　　　 ＝const in gas volume, and 293.5K in gas temperature. The top plot
（V＋mb）
　　　　　　　　　　　
V V＋mb
presents gas absolute pressure as a function of gas volume.
　The volume term of the Soave-Redlich-Kong adiabatic By gas expanding, the gas pressure decreases to the point B.
equation（V－mb） is identical to that of the van der Waals In the middle plot, gas absolute temperature is shown. It is a
H

adiabatic equation. The pressure term of the Soave-Redlich-
Kwong adiabatic equation is slightly different from the
pressure term of the van der Waals adiabatic equation.
However, both adiabatic equations include the product of a
pressure term and a volume term. In the Soave-Redlich-
Kwong adiabatic equation, an additional term Z is included：
discharge process and gas absolute temperature also
decreases. In the bottom, the additional term Z of Eq.（36）is
plotted. The term Z shows around 0.9 during this process.
　Parameters （ , b, and ∂a
a T） （T）
/∂T of the Soave-Redlich-
Kwong equation are plotted in Fig. 2. In the figures, the
parameter values of the van der Waals equation are noted.
During the discharge process, while the van der Waals

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 ZHANG・IWASHITA・SANADA：Soave-Redlich-Kwong Adiabatic Equation for Gas-loaded Accumulator
Fig. 1　Discharge process of gas-loaded
accumulator calculated by the Soave-
Redlich-Kwong adiabatic equation
Fig. 2　Comparison of parameters during discharge process
第49巻　第３号
69
parameters avdw and bvdw are constant, the Soave-Redlich-
Kwong parameters （
a T）increases. The parameter b of the
Soave-Redlich-Kwong equation is constant. The value of ∂a
（T）
/∂t is negative from the initial point A to the final point B.
　In the Otis’s thermal time constant model, the heat losses
are considered17）. This means the process is no longer
assumed as adiabatic. In this study, the thermal time-constant
model is couple with the Soave-Redlich-Kwong equation, Eq.
（5）
, and the Benedict-Webb-Rubin equation, Eq.（4）
. The
Benedict-Webb-Rubin coefficients predicted by ASAMI are
applied in this paper18）. A PV-diagram of charge process is
shown in Fig. 3. Parameter values of experiment of charge
and discharge processes carried out by Miyashita, et. al.19） are
referred for simulation in this paper. Operating time is 10
seconds and the surrounding temperature is 293K. The initial
condition A is 4.4MPa, abs. and 7.4×10－3m3 （7.4L）
. The
thermal time constant τ is assumed to be 20 seconds for the
Otis’s models coupled with the Soave-Redlich-Kwong
equation and the Benedict-Webb-Rubin equation. According
to Otis’s research, the value of τ were determined referring to
experimental results18）. Circle symbols and triangle symbols
are calculated results by the Soave-Redlich-Kwong adiabatic
equation（SRK）and the van der Waals adiabatic equation
（vdW）
, respectively. The dot line and dash line represent the
Otis’s thermal time constant models combined with the
Soave-Redlich-Kwong equation and the Benedict-Webb-Rubin
equation, respectively. By charging, the gas volume decreases
and the gas pressure increases from the initial point A to the
point B. The calculated results of the Soave-Redlich-Kwong
adiabatic equation show a good agreement with the other
representative gas models.
　The comparison results of discharge process are plotted in
Fig. 4. The initial condition A is 34.5MPa, abs. and 2.65×10－3m3
（2.65L）
. The operating time is 10 seconds and the surrounding
temperature is 301K. The thermal time constant τ is assumed
Fig. 3　Comparison of charge process of accumulator
estimated by different gas models
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70 日本フルードパワーシステム学会論文集
Fig. 4　Comparison of discharge process
estimated by different gas models
to be 15 seconds for the Soave-Redlich-Kwong equation and 7
seconds for the Benedict-Webb-Rubin equation. The value of τ
was also determined referring to experimental results. In this
discharge case, thermal time constant values of the Soave-
Redlich-Kwong equation and the Benedict-Webb-Rubin are
different, because of curve fitting. By discharge, the gas
volume increases and the gas pressure decreases. The
calculated results of the Soave-Redlich-Kwong adiabatic
equation show a good agreement with the other
representative gas models.
　The Soave-Redlich-Kwong adiabatic equation shows
accurate calculated results of charging and discharging
processes. From comparison of these results, the proposed
Soave-Redlich-Kwong adiabatic equation is successfully
validated.
　In the thermal time constant model, heat transfer is
considered. Therefore, this model cannot simulate pure
adiabatic process. Adiabatic assumption of gas equation of
state, which describes gas thermodynamic properties without
transfer of heat, provides a conceptual basis in
thermodynamics. In some cases, the thermodynamic
properties vary very similarly as adiabatic process, the
physical process occurs so rapidly that there is no enough
time for the transfer of energy, thus the Soave-Redlich-
Kwong adiabatic equation can be employed to express the
assumption models. In this paper, as the comparison of the
Soave-Redlich-Kwong equation with thermal time constant
model shows, this equation can be used as a reference to
study thermal time constant model combined with various
gas models.
6．Conclusion
　For commercial applications, according to equation of state
and operating conditions, accurate prediction of accumulator
performance and design of accumulator size for efficient
第49巻　第３号 ―6―
operation are significant topics. In this paper, the adiabatic
expression of Soave-Redlich-Kwong was presented. A lack of
mathematical expression for the SRK equation of state, that
is, a lack of SRK adiabatic equation, has been solved by this
research. This contribution is important for mathematical
modeling of accumulator. The combination of Soave-Redlich-
Kwong equation with Otis’s thermal time constant model
was presented as well. Adiabatic models（van der Waals
equation and Soave-Redlich-Kwong equation）and thermal
time-constant model that considered heat losses were
compared with each other. It has been found that the Soave-
Redlich-Kwong adiabatic equation shows consistency.
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