ISSN 0386-1678

Report of the Research Institute of Industrial Technology, Nihon University

Number 91, 2007

Mollier Diagram for R-744 + HFE-170 by use of an Equation of State

Tomoya TSUJI* and Toshihiko HIAKI**
( Received June 12, 2007 )
Abstract
Binary interaction parameter in the mixing rule for a van der Waals equation of state was optimized
with just one experimental datum of density for a gas mixture, carbon dioxide (R-744) + dimethyl ether
(HFE-170), at 377.59 K. Using the parameter, Mollier diagram were drawn in the pressure range from 4
to 20 MPa, and the temperature from 322.04 to 377.59 K. A necessary thrust power was evaluated under
the assumption of a refrigerating system repeating isentropic / isothermal compression and expansion in
the same range of pressure and temperature.
Keywords: Alternative refrigerant, Mollier diagram, Equation of state, Necessary thrust power

1. Introduction
Mollier diagram is widely used in mechanical engineering to design engine, heat exchanger, refrigerating
system, and so on. The diagram is generally drawn by
equation of state or that of absolute enthalpy based on
a huge number of the experimental data. However, the

available diagram is almost for pure substances, and

that for mixtures is few except for some refrigerants
composed of hydrochlorouorocarbons. In this study,
we proposed a new working uid, carbon dioxide (R744) + dimethyl ether (HFE-170), for an earth friendly
refrigerating system.
Table 1 show the physical properties1) for a conven-

Table 1 Physical Properties1) of Refrigerants, R-22, R-744, and HFE-170

R-22

R-744

HFE-170

Formula

CHClF2

CO2

CH3OCH3

Critical Temperature Tc [K]

369.3

304.1

400.0

Critical Pressure Pc [MPa]

4.97

7.38

5.24

* Associate Professor, Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon
University
** Professor, Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University

Tomoya TSUJI and Toshihiko HIAKI

tional refrigerant, R-22, and alternative ones, R-744,

and HFE-170. However, R-744 has the lower critical
temperature, and the higher critical pressure. Then, the
conventional refrigerating systems should be reconstructed or improved. Otherwise, the critical properties
of HFE-170 are similar to those of R-22, and it has been
used for an aerosol propellant. Then, the combustibility
should be overcome for the refrigerant. Tsang et al.2)
have measured vapor-liquid equilibrium for R-744 +
HFE-170. According to the report, the optimized binary
interaction parameter, in the mixing rule in equation of
state, suggested that a peculiar interaction should be
exited between R-744 and HFE-170. Since HFE-170
will be stabilized by addition of R-744, a gas mixture of
R-744 + HFE-170 will be widely used as a new working
uid. In this study, The binary interaction parameter,
in the mixing rule of equation of state, was optimized
from just one datum of density at 377.59 K. Using the
parameter, Mollier diagram was drawn for the gas mixture, R-744 + HFE-170. A necessary thrust power was
also evaluated under the assumption of a refrigerating
system repeating isentropic / isothermal compression
and expansion in the pressure range from 4 to 20 MPa,
and the temperature from 322.04 to 377.59 K.

2. Experimental Section
2.1 Materials
R-744 was purchased from Takachiho Trading Co.
Ltd., Tokyo, with the stated purity of 99.99+ %. HFE170 was purchased from Taiyo Petroleum Gas Co. Ltd.,
Tokyo, with the stated purity of 99.9+ %. All chemicals
were used without further purication.
2.2 Procedure and equipments
Fig. 1 shows a schematic diagram of an apparatus
for P-V-T measurement. The apparatus was based on
a constant volume method. The equipment and procedure of measurement have been already described
elsewhere3), 4). The cell employed was made of stainless
steel. The inner volume, and the vacant mass was about
63 cm3 and 0.67 kg, respectively. The precise inner
volume was determined with an accuracy of 0.0004
cm3 by weighing the mass of the cell lled with pure
water at 298.15 K. The mass was measured with a direct
reading balance (EXACT AV 1581, Japan) by a minimum capacity of 0.1 mg and a maximum of 1 kg. The

7
6

11
4
2

5
1
3

10

1: High Pressure Cell 2: Oil Bath 3: Agitator 4: Thermistor Thermometer 5: Heater 6: Air Chamber
7: Vacuum Pump 8: Ribbon Heater 9: Pressure Sensor 10: High Pressure Mercury U-tube 11: Dead
Weight Tester:
Fig. 1 Schematic Diagram of the Experimental Apparatus

Mollier Diagram for R-744 + HFE-170 by use of an Equation of State

experimental temperature was set to 377.59 K, and the

precise temperature was measured by a thermistor thermometer (Technoseven D461, Yokohama, Japan) within
a precision of 0.01 K. The pressure was monitored
by a pressure sensor (Erich Brosa EBM 1408-0325,
Germany) with an accuracy of 10 kPa. The precise pressure was determined by a dead weight tester (Nagano
Keiki PD22, Tokyo) with an accuracy of 2 kPa. In the
pressure measurement, a mercury U-tube was used to
isolate the experimental system, the dead weight tester
and its pressure medium, silicon oil.
3. Results and Discussion
3.1 P-V-T relationship and Mollier diagram
Fig. 2 is the experimental result of P-V-T relationship
for a gas mixture, R-744 + HFE-170, with the HFE-170
concentration of 48.36% at 377.59 K. Then, the vertical
axis, z, indicates compressibility factor given by the
following equation.
Pv
z=
RT

(1)

In the gure, the experimental data of pure R-744, and

the standard data by Span et al. [5] were also illustrated.
As shown in the gure, the experimantal data agreed
well with those of literature. Therefore, the reliability

Compressibility factor z [-]

0.8

377.59 K
0.6

exp. (This work)

CO2

RT
a
P = 2
v- b v

The temperature and molar volume dependences of

vdW equation is simple, so the physical properties can
be easily evaluated. In eq. (2), a and b is the attractive
and the excluded volume parameter, respectively. The
parameters, for pure substance, were conventionally
evaluated by its critical temperature and pressure.
27R2T c,i2
ai =
64Pc,i

calc.

(5)

bi + bj
b = xi x j
i j
2

(6)

where a binary interaction parameter, kij, was optimized

with the experimental data.
In Fig. 2, the correlation result was also illustrated. The
optimized value was kij = -0.028.
The results suggested a strong interaction between a
carbon atom of R-744 and an oxygen of HFE-170.
Fig. 3 showed our consideration for the molecular
interaction.

vdW eq.

H
4

(4)

a = xi x j (1 ki j )(ai aj )0.5

Span et al.

RT c,i
bi =
8Pc,i

(3)

As described before, the critical temperature and

the pressure for R-744 and HFE-170 were listed in
Table 1.
For the mixture, so called conventional type mixing
rule, vdW one uid model, was employed.

[kij = -0.028]

0.2
0

(2)

CO2 + CH3OCH3
[CH3 OCH3 48.36 mol%]

std.

0.4

was conrmed. Though the P-V-T measurement was

carried out for the mixture at a pressure, the precision
was thought to be maintained even for the mixture.
In this study, Mollier diagram was drawn by use of
equation of state. The equation employed was the van
der Waals (vdW) equation.

O
C

H
C

HH

Pressure [MPa]

Fig. 2 P-V-T relationship for R-744 + HFE-170 at 377.59 K

(HFE-170: 48.36 mol%)

Fig. 3 Interaction between R-744 and HFE-170

Tomoya TSUJI and Toshihiko HIAKI

The thermodynamic relations, for drawing Mollier

diagram, were described below:
Generally, molar entropy, s, and molar enthalpy, h, were
given by ideal and excess ones.
s = sid + sE

h = hid + hE

(7)

(8)

where the entropy and enthalpy in ideal gas state, sid

and hid, were calculated from the integration of isobaric
molar heat capacity in ideal gas state, Cpid.
s id (T,P) = s ref (Tref ,Pref ) +

id
p

dP

dT R

T
P

Tref

(9)

Pref

h id (T ) = h ref (Tref ) + C idp dT

(10)

Tref

where, Tref , and Pref is the refference temperature and

pressure. In this study, the reference was dened to
be 298.15 K and 101.33 kPa. The isobaric molar heat
capacity for the gas mixture in ideal gas state was given
by the following relation.

where g E is the excess molar Gibbs free energy given by

the following relation similar to that of the enthalpy.
g E = RT

dP
(z 1)
P

(15)

Pref

where hE and g E should be converted to hE(v, T ) and

g E(v,T) considering the variables in vdW eq. The conversion was carried out by using the following relation.
dz
dP
dv

=
P
z
v

(16)

Fig. 4 shows the vapor-liquid equilibrium for R-744

+ HFE-170 reported by Tsang et al. [1] at 322.04 and
377.59 K, respectively. According to the literature data,
a homogeneous gas phase was maintained for the mixture with the HFE-170 concentration of 8.00 mol %.

(11)

id
C idp = xi C p,i
i

where Cp,iid is the isobaric molar heat capacity for pure

substance, and it was given by the following cubic
equation with temperature1).
(12)

C p,iid = C pa,i + Cpb,iT + C pc,iT 2+ C pd,iT 3

The value of these parameters can be available in the

literature1).
Table 2 listed the value of the parameters for R-744
and HFE-170. Otherwise, the excess molar entropy and
the enthalpy, sE and hE, were given by the following
relation.
hE g E
s E = (13)
T

h E = RT 2

z dP

T P P

Pref

(14)

Fig. 4 Vapor-Liquid Equilibrium for R-744 + HFE-170 at

322.04 and 377.59 K (Data from Tsang et al.,)

Table 2 Coefcient for Isobaric Molar Heat Capacity in ideal gas state1)

Substance

Cpa,i [J/molK]

Cpb,i [J/molK2]

Cpc,i [J/molK3]

C pd,i [J/molK4]

R-744

1.980 x101

7.344x10-2

-5.602x10-5

1.715x10-8

HFE-170

1.702x101

1.791x10-1

-5.234x10-5

-1.918x10-9

Mollier Diagram for R-744 + HFE-170 by use of an Equation of State

Fig. 5 shows the Mollier diagram, the mutual relationship among T, P, s and h, for gas mixture R-744 +
HFE-170 in the pressure from 0 to 25 MPa, the temperature from 320 to 400 K, and the molar volume from
8x10-5 to 1x10-3 m3/mol.

3.2 Design of Refrigerating System

In this study, a necessary thrust power was evaluated
for a hypothetic refrigerating system.

Fig. 5 Mollier Diagram for R-744 + HFE-170 (HFE-170: 8.00 mol%)

Tomoya TSUJI and Toshihiko HIAKI

Fig. 6 shows the refrigerating system assumed in this

study. For the simplicity in the calculations, the working uid employed was a homogeneous gas mixture
of R-744 + HFE-170 with the HFE-170 concentration
of 8.00 mol%. In the refrigerating cycle, isentropic /
isothermal compression and expansion were repeated in
the pressure range from 4 to 20 MPa, and the temperature from 322.04 to 377.59 K. As shown in the Mollier
diagram, the cycle can be drawn with bold lines on
diagram. The cycle was represent as a rectangle in T-s
diagram, because the height and the width correspond
to the isothermal and isentropic process, respectively.
Therefore, a coefcient of performance (COP), , was
given by the following relation.
q
TL
=
=
TH TL W

(17)

where TL and TH are inside and outside temperature of

refrigeration chamber, q, heat ow rate, W necessary
thrust power for the refrigerating system.
Fig. 7 shows a dimension of refrigerating chamber
assumed in this study. The refrigerating chamber was a
cube shape with the inner edge of 1 m long. The inside
and outside temperature was assumed to be 322.04 and
377.59 K, respectively. Then, the heat ow rate was
given by the following relation.
q = UA (TH TL )

(18)

where U is overall coefcient of heat transfer, A effective area of heat transfer. In this study, the value was
assumed to be 720 J/m2sK.

Fig. 6 Hypothetic Refrigerating System assumed in this

Study

Otherwise, a necessary thrust power, W, was given by

the following relation.
(TH TL )s
Vn
W =

Mw

(19)

where n is frequency, and overall efciency in the

compressor, Mw average molecular weight of working uid. The value of the efciency assumed to be
100.0 % for simplicity in the calculation. The exhaust
volume of compressor, V, was assumed to be 500 cm3.
Under the condition of the exhaust in the compressor,
the value of density, , was regarded as that at 4 MPa
and 322.04 K.
Using eqs. (16)-(18), the frequency was evaluated to
be 3432 r.p.m. In case of using a working uid just
composed of pure R-744, the frequency was to be
3501 r.p.m. at the same temperature and the pressure.
Therefore, the addition of HFE-170 is slightly effective
for decreasing a necessary thrust power.
Acknowledgement
This study was supported by a Grant-in-Aid for
Scientic Research (C), No. 1756066, from Japan
Society of the Promotion of Science. The authors
wish to thank College of Industrial Technology, Nihon
University, for an additional nancial support of this
study. The authors acknowledge Ms. Noriko Hoshi, and
Mr. Takeshi Yamaguchi, who were graduated students of
master degree, for their assistance of measurements.

Fig. 7 Temperature Prole and Dimension of Refrigerating

Chamber assumed in this Study

Mollier Diagram for R-744 + HFE-170 by use of an Equation of State

References
1) Reid, R. C., Prausnitz, J. M. and Poling, B. E., The
Properties of Gases & Liquids 4th ed., McGrawHill, 1986
2) Tsang, C. Y., Streett, W. B.,Vapor-liquid Equilibrium
in the system Carbon dioxide/Dimethyl ether,
J. Chem. Eng. Data, 26, 155, 1981
3) Tsuji, T., Honda, S., Hiaki, T., Hongo, M.,
Measurement of P-V-T Relationship for Carbon
Dioxide+n-Butane and Carbon Dioxide+i-Butane

in the vicinity of the critical point, J. Supercritical

Fluids, 13, 15, 1998
4) Tsuji T., Tanaka, S., Hiaki, T., P-V-T-x relationship
for CO2+C4H10 and CO2+iC4H10 binary gas mixtures
and the partial molar volume of C4H10 and iC4H10 at
360.00 K, J. Supercritical Fluids, 29, 215, 2004
5) Span R., Wagner W., A New Equation of State for
Carbon Dioxide Covering the Fluid Region from
Triple-Toint Temperature to 1100 K at Pressures up
to 800 MPa, J. Phys. Chem. Ref. Data, 25, 1509,
1996

Tomoya TSUJI and Toshihiko HIAKI

R-744 + HFE-170 Mollier

R-744HFE-170
1 van der Waals 4
25 MPa 322.04 377.59 K Mollier

Mollier Diagram for R-744 + HFE-170 by use of an Equation of State

Biographical Sketches of the Authors

Tomoya Tsuji was born on March 1963. He nished Doctor Course, Graduate School
of Tohoku University, and then received his Doctor degree of Engineering. After graduation, Dr. Tsuji has been belonging to Department of Applied Molecular Chemistry,
College of Industrial Technology, Nihon University. Now, he is an associate professor,
and his current work is measurement and prediction of phase equilibrium in chemical
engineering, especially research on physical properties of a new energy and refrigerant.
He is a member of The Society of Chemical Engineers, Japan (SCEJ), The Japan Society
of Mechanical Engineers (JSME), The Society of Separation Process Engineering, Japan
(SSPEJ), Japan Society of Thermophysical Properties (JSTP), The Society of Polymer
Science, Japan, and The Japan Society of High Pressure Science and Technology. He
participates some committees established by Liquied Petroleum Gas Center (LPGC) or
The High Pressure Gas Safety Institute of Japan (KHK).

Toshihiko Hiaki was born on February 1955. He graduated from Doctor Course,
Graduate School of Nihon University, and received his Doctor degree of Engineering.
Dr. Hiaki is a professor of the Department of Applied Molecular Chemistry, College of
Industrial Technology, Nihon University. His research topics are measurement, correlation
and theoretical interpretation of Physico-Chemical properties, and advanced application
of water, for the optimum design and operation of sustainable chemical processes. He is
a chairman of the Fundamental Physico-Chemical properties division of the Society of
Chemical Engineers, Japan (SCEJ), a general affairs chairman of the Society of Separation
Process Engineers, Japan (SSPEJ). He is a member of the American Chemical Society
(ACS), the American Institute of Chemical Engineers (AIChE), the Japan Society of
Thermophysical Properties, the Japan Petroleum Institute, and the Society of Sea Water
Science, Japan.