Fluid Phase Equilibria 347 (2013)

2227

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Fluid Phase Equilibria

ww w.e l s e v i e r. c o m / l o c a t e / u i d

An empirical extension for a generalized cubic equation of state,

applied to a pure substance with small molecules

F.

de J. Guevara-Rodrguez a,b, , Ascencin Romero-Martnez a,b,c

a

Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas 152, 07730 Mxico, Distrito Federal,
Programa de Ingeniera Molecular, Mxico
c
rea de investigacin en Termofsica, Mxico

Mxico

a r t i c l e
Article history:
Received 26 October 2012
Received in revised form 11
March 2013 Accepted 12 March
2013
Available online 21 March 2013
Keywords:
Non-cubic equation of
state Solid phase
Triple point
Phase
transition Pure
substance

i n f o

a b s t ra c t

An equation of state to describe the complete phase diagram of a pure substance is

developed. The equation of state is constructed by using a generic cubic equation plus
10
the term fT/(v e) . This term (where f > 0 and e are adjustable parameters) is the
attractive contribution of the solid phase. It has
a volume short-range contribution,
and extends the traditional use of a cubic equation, incorporating the thermodynamics
description of the solid phase, which allows to represent the experimental triple point,
the solidliquid, and the solidvapor phase transitions, together with the traditional
description of the liquidvapor transition. For the solidliquid phase coexistence at any
temperature, molar volume predictions of the solid phase dene a curve which never
connects to its corresponding liquid phase curve. This feature is in agreement with
experimental evidences that seem to not accept the existence of a solidliquid critical
point. Finally, calculations for the complete phase diagram for carbon dioxide and
argon were carried out in order to show the capabilities and features of the equation of
state, and these results were also compared with other predictions from the literature.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Mechanical equation of state (EOS) has been used to
describe thermodynamic properties of pure substances
and mixtures. In particular, a cubic EOS predicts quite
well the liquidvapor, and the liquidliquid phase
transition [119]. However, to describe the solid phase
of a substance with any of the cubic EOS is a complicated task. In the open literature, there are some
methods to tackle the problem of representing the solid
phase. As an example, cubic EOS has been used for
some particular mixtures, where the solid phase is
treated as a pure compound [20]. In other example, a
cubic
EOS
has
been
used
to
describe
the
thermodynamic properties of
a mixture of
molecular clusters of a simple substance [21,22].
In
this case, biggest molecular clusters are considered part
of the solid phase [23], which coexists with the
remaining part of the uid.
In the literature there are also reported some
equations of state, which were developed to predict the
solid phase, and all of them are non-cubic EOS. For
example, Yokozeki [24,25] modied the repulsive part of
the van der Waals equation introducing a second
discontinuity along the solidliquid phase transition. In
this way, the discontinuity avoids a critical point on the
melting curve [24].

Corresponding author. Tel.: +52 55 9175 8176.

E-mail address: fguevara@imp.mx (F. de J. Guevara-Rodrguez).

This EOS was used to predict the solid phase of some

substances, and is a very simple analytical equation,
but violates some physical restrictions due to the
discontinuity [26].
A second example is the non-cubic EOS developed
by Lee et al. [27]. They used the extended Veytsman
statistics and a lattice uid model, and the results with
their equation are in agreement with experimental
data for uid phases but underestimate the solid
phase density and the triple point temperature.
Perhaps, Kans work was the rst effort to develop a
unied EOS, which is able to represent the different
phase equilibria along the three most known states of
matter solid, liquid, and vapor of argon [28]. In his
work, the pressure is approached with some terms of
the Virial expansion. Thus, the rst three terms
correspond to a cubic EOS, which is modied by the
fourth term of order 9. In this way, the results with his
0378-3812/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2013.03.011

non-cubic EOS are in agreement with experimental data

of argon.
Another effort on this topic was the work from Wenzel
and Schmidt [29] who developed their EOS taking as
starting point the RedlichKwong equation, which is
modied with the term
6
cT /(v 0.97b) , where b, c, and are the parameters, v
and T are
the molar volume and the temperature, respectively.
Last term is the attractive contribution of the solid
phase, has a volume short- range, and is negligible in
the liquidvapor phase transition region. However, the
resulting melting curve shows a critical point as an
undesirable feature.
In this work, an EOS to represent the complete phase
diagram of a pure substance is proposed. The EOS is
basically a general cubic

2
3

F. de J. Guevara-Rodrguez, A. Romero-Martnez / Fluid Phase Equilibria 347

(2013)
2227

equation, which was reported elsewhere [19], and it is

10
modied by adding the term fT/(v e) . The last term
is the attractive con- tribution of the solid phase. The
main features of the resulting EOS
is described in Section 2, and the method to determine
its param- eters is described in Section 3. Furthermore,
the capabilities of the EOS are exhibited through the
calculation of the phase diagram for argon and carbon
dioxide, and its results are also shown in Section
3. Finally, the results are also compared with the results
obtained with other equations from the literature.

2. Equation of state

The state of a uid is dened by its temperature (T),

molar vol- ume ( v), and pressure (P). These
thermodynamic variables are not independent because
they are related through mechanical EOS. The EOS,
which is proposed, has the following structure
RT
A(T )
=

v b
(v c)(v
d)

P(T, v)
with

fT

(1)

(v
10

e)
)

A(T

aT

(e/RT

1),

(2)
where R is the gas constant, and {a, b, c, d, e, f, } is
the set of param- eters, which depends on the uid.
The methodology to evaluate the parameters will be
described later.
If f = 0, Eq. (1) becomes a cubic EOS. However, in
general, two cases have to be considered: f = 0 and f >
0 together with b > e. For the case when f > 0, the last
term of Eq. (1) has a volume short-range nature, which
is related to the attractive contribution of the solid
phase, and modies the liquidvapor coexistence
obtained by the cubic EOS. Perhaps, a possible
microscopic mechanism, which could explain the origin
of the above attractive term, is the conjecture of
Debenedetti et al. [30] who argue that an effective
pair potential, attractive at the nearest distances and
repulsive at a second near- est distance, induces a
liquid phase where its structure collapses

Fig. 1. Schematic representation of a typical phase coexistence

diagram (solid curve), which can be constructed using Eq. (1). The
dashed curve corresponds to the spinodal curve.

transformation of the liquid phase into the solid phase

could be continuous, and the melting curve must nish
at the critical point. In this work, Eq. (1) does not have a
critical point for the solidliquid coexistence, and this is
illustrated in Fig. 1 with an indenite solid branch, which
never connects its corresponding liquid branch.
Moreover, for a high temperature, Eq. (1) can be
rewritten as

P
lim

R
=

(v e)

into a solid phase at high pressures, and therefore, the

solidliquid
coexistence is established.
The schematic representation of the pressurevolume
diagram,
which could be obtained using Eq. (1), is illustrated in
Fig. 1. In this gure, outer solid curve is the phase
coexistence diagram and the inner dashed curve is the
spinodal curve. Eq. (1) has two particular points which
fulll

vc

P(Tc,
(3a)

P =
v c

0;

(3b)

2
P = 0.
.

v2

(3c)

Pc

10

(4)

Eq. (4) could describe a solidliquid coexistence for a

proper set
of parameters, and therefore, the critical point does not
exist. On the other hand, the behavior of any uid at
high temperatures could be approached with a hard
sphere model. Thus, the solid transition of the ideal uid
is a rst order transition, and its solidliquid critical point
does not exist [32]. In this work, the solidliquid critical
point is not a feature of Eq. (1). Moreover, we cannot
conclude nothing about the existence of the solidliquid
critical point for a real uid.
Contrary to our Eq. (1), solidliquid critical point is a
consequence for other equations from literature
[33,27,28,21,29].
Finally, the method to determine the parameters of the
EOS will be described in the next section.

2
4

F. de J. Guevara-Rodrguez, A. Romero-Martnez / Fluid Phase Equilibria 347

(2013)
2227
The rst of them, which
is labeled
as C1 in Fig. 1,
3. Method
corresponds to the critical point of the liquidvapor
phase coexistence. In this case, the last term in the Eq.
All parameters from Eq. (1) are strongly related to the
(1) is negligible and the critical point is determined
specic substance under study, and all of them are
practically with the cubic EOS. Moreover, the phase
exclusive for the sub- stance. In this section the method
diagram for the liquidvapor coexistence, which is
to determine the parameters
is presented.
obtained with Eq. (1), can be practically approached
Parameters of the cubic EOS are rstly determined. This
with the cubic EOS.
step is the starting point of the method. The procedure
On the other hand, the second point, which is
was reported elsewhere [19], but here, it is also
labeled as C2 in Fig. 1, is not a critical point of the uid,
presented in Section
it has a negative pressure, and it could be used to
3.1. After that, the parameters f, and e, which are related to
locate the melting region and the triple point.
the attractive contribution of the solid phase in Eq. (1),
In the literature, there are not reported experimental
are determined using the experimental triple point data
evidences of a critical point for the solidliquid phase
of the substance. This is the second step, and its details
coexistence. However, in the work of Elenius and
are presented in Section 3.2. Finally, the calculations for
Dzugutov [31], theoretical evidence of
a solidliquid
the phase diagram of argon and carbon dioxide are
critical point is suggested through the molecularpresented in Section 3.3, and both cases are used to
dynamics simulation of a monoatomic system. In their
show the features of our EOS. The results, which are
work, a liquid-crystal phase coexists with the liquid
derived with our EOS,
phase [31]. Thus, the

Table 1
Experimental data of the liquidvapor critical point of some
substances are pre- sented [34]. The last column corresponds to the
critical compressibility (Zc = Pcv c/RTc ).

Zc

Table 2
Experimental data of the acentric factor (exp), and the molar
volume
v
(exp)
v
/vc of the saturated vapor phase at the reduced temperature T/Tc
= 0.7 for some substances are in the rst two columns. Parameters c
and , which are in the last two columns, have been calculated using
Eq. (5), though a minimization process for 6vv |(vv

v(exp)
v

vv Neon
/vc
Argon
Xenon
Methane
Nitrogen
Ethane
Propane
Freon-12
Acetylene
Benzene
Carbon
dioxide
Ammonia

44.
1
2
8
1
9
1
2
3

26.5
50.0
58.3
46.4
34.0
49.1
42.6
41.3
62.4
49.2
73.8
112.
9
34.1

0
3
7
3
8
3
0
5
6
3
0
4
0
4
8
5
0
6
4
5
2

Freon-113
n-Hexane
Water
Ethyl
acetate

41.8
74.5
118.3
99.0
92.2
141.8
196.0
215.2
113.2
256.9
94.0
72.5
325.1
368.3
56.7
286.3

30.3
221.
2
38.5

Neon
Argon
Xenon
Methane
Nitrogen
Ethane
Propane
Freon-12
Acetylene
Benzene
Carbon
dioxide
Ammonia
Freon-113
n-Hexane
Water
Ethyl
acetate

3.1. Cubic equation

Parameters from the cubic EOS are determined as the
rst step. For the case (f = 0), the set of parameters of
the cubic EOS is {a, b0, c0, d0, }, and Eq. (1) is rewritten
as
(5)

3.1.1. Critical point

Eq. (5) must fulll Eqs. (3a)(3c) at the liquidvapor
critical point. From these equations, the parameters b0,
c0, and d0, are determined, and their analytical
expressions (see Section 2.1 in Ref.

b0

=
c0

Zc 1 + c

(6a)Zc
Zc

(1/2)c

,
+

=
Zc

d0

vc

Zc (1/2)c c
=
Zc

where
Pcv c
Zc =

3
c =

RTc

;
(7a)

A(Tc )Pc
.
(7b)
R2Tc2

(3/4)
;

(exp)
0.
037
0.

1
9.
2
1.
2
2.
2
2.
2
3.
2
8.
3
4.
3
4.
3
6.
3
9.
3
8.
4
6.
4
3.
4
9.
6
1.
6
0.

0.00
003
2
0.01
6
0.03
6
0.10
0
0.16
0
0.17
5
0.18
8
0.20
7
0.22
4
0.25
2
0.25
5
0.29
9
0.34
4
0.36
7

/RTc

0.794143
95
0.804155
05
0.803155
06
0.803155
16
0.813165
15
0.823143
05
0.833044
05
0.834154
06
0.842043
04
0.843154
16
0.842153
95
0.853154
05
0.852154
05
0.862154
05
0.863154
05
0.863155
05

0.2755
4372
0.2657
7083
0.2816
8381
0.3064
6062
0.2684
2372
0.2993
6270
0.3199
7260
0.3354
6551
0.2928
8455
0.3157
5120
0.3402
6183
0.2949
1224
0.3127
7050
0.2913
3364
0.3409
8143
0.3709
7859

3.1.2. Saturated vapor pressure @ T/Tc = 0.7

Parameters c, and , are determined by using
experimental data of the saturated vapor pressure of
the uid at the reduced temperature T/Tc = 0.7. In
this case, the acentric factor, (exp), and the reduced
v
(exp)

molar volume of the saturated vapor, v

/vc , are used
as inputs. Experimental data of those properties for
some uids are
included in Table 2. Parameters c, and , must fulll

vv

P(T, v) dv = P

(vv vl );

(8a)

vl
(exp)

P
log10( ) 1;
Pc

(8b)

v(exp)
v

[19])
are

| and 6 |( (exp) )/(exp) |.

(exp)

0.300
0.297
0.286
0.290
0.298
0.274
0.272
0.278
0.275
0.270
0.275
0.243
0.274
0.264
0.233
0.253

are also compared to the results obtained with other

equations of state from literature.

A(T
P(T, v) = RT
,

v b
)

(
v

c
)(
v

0
0
d 0)
where A(T) is given by Eq. (2).

(exp)

)/vv

v v.

(8c)

where vl is the molar volume of the liquid phase, vv is

the molar
volume of the vapor phase, and P is the common
pressure at the liquidvapor phase coexistence. Eqs.
(8b) and (8c), are restrictions for the common pressure
(P) and the molar volume of the saturated vapor (vv). In
this way, cubic EOS parameters are determined, and the
resulting parameters values from the above procedure
are also given in Table 2.

(6b)

,
c (3/4)
,

3.2. Equation of state (f > 0)

(6c)

The cubic equation (f = 0), which has been determined

in the previous section, is the basis to construct the
EOS for f > 0. For a
given set of parameters, an iterative procedure is
applied to Eq. (1) to approach the experimental
temperature and pressure values of the triple point of
the substance under study. Each step, which is
Parameters b0, c0, and d0, are functions of the
critical com- pressibility, Zc, which is obtained from
experimental data at the liquidvapor critical point of

the substance. For example, experi- mental data at

the critical point of some substances are presented in
Table 1. Furthermore, the parameters b0, c0, and d0,
are also func- tions of c. In Eq. (7b), c is related to
the function A(T) at the critical temperature. Thus,
from Eq. (2), and Eq. (7b), c is determined with two
parameters, namely, a and . However, c will be used
instead of a for the remaining part of the work. Thus,
c and will be determined using the saturated vapor
pressure at the reduced temperature, T/Tc = 0.7.

repeated in the procedure, is divided into two parts. In

the rst part, the parameters b, c, and d, are
calculated, and Eq. (1) must fulll Eqs. (3a)(3c) for
the critical point. In the second part, parameters c, ,
f, and e, are estimated using a minimization process
of the differences between the experimental and
calculated values of temperature and pressure at the
triple point of the substance. The parameters of Eq.
(1) are determined by using two steps, and therefore,
both steps must be repeated until all parameters
converge to the solution. The details will be described
in the following subsections.

3.2.1. Critical point

In general, the attractive contribution of the solid
phase is prac- tically negligible in the liquidvapor
phase transition region, and

Table 3
Experimental reduced temperature and pressure at the triple point of
some substances.
P

(exp)

trp

Neon [35]
Argon [3638]
Xenon [39]
Methane [40]
Nitrogen [41]
Acetylene [42]
Benzene [43]
Carbon dioxide [44,45]

0.0
16
0.0
13
0.0
14
0.0
02
0.0
03
0.0
20
0.0
01
0.0
70

(exp)

/Pc

Ttrp /Tc

0.5531
0.5554
0.5570
0.4758
0.5000
0.6304
0.4953
0.7120

P
V

therefore, the parameters b, c, and d, are almost b0, c0,

and d0. Thus, the parameters are approached by using
b = b0 + b;

(9a)

c = c0 + c;

(9b)

d = d0 + d.
(9c)
The differences b, c, and d, are very small, and
the EOS can be approached by using the linear
approximation, i.e.
P0
P0
P(T, v) P (T, v)
d,
b +
c

+
0
P0
c0
0
+ (10)
b

Fig. 2. Isotherm curve, pressure vs molar volume at a temperature

above but close to the triple point temperature. The upper dashed
line is the common pressure for the solidliquid phase transition, Psl .
Plv corresponds to the common pressure for the liquidvapor
transition, and it is the lower dashed line.

The triple point of Eq. (1) must approach to the triple

point of the

d0
where P0(T, v) is Eq. (1) with b = b0, c = c0, and d = d0.
The differences, b, c, and d, are determined by using
Eqs. (3a)(3c), at the critical point. In this case, Eqs.
(3a)(3c), are linear equations of those small
differences, and the numerical solution is easily
computed. Thus, b, c, and d, are calculated with
equations, (9a)(9c).
3.2.2. Triple point
The experimental data of the temperature and the
pressure at the triple point of the substance under study
are used to determine
the parameters c, , f, and e. Examples of these triple
point data
in reduced form are included in Table 3 for some
substances. The
parameters c, , f, and e, must fulll with the
following equations

vl

P(T, v) dv = Psl

vs

(vl1 vs);

(11a)

substance, and the above condition is reached only if

the parame- ters c, , f, and e, fulll with Eqs. (11d)
and (11e). In this way, all parameters are determined.
The parameters c, and , are initialized with the
parameters of the cubic EOS (see Section 3.1). On the
other hand, the S-loop for the solidliquid phase
transition must exist at the limit of high temperature, and therefore, the parameters must fulll
the following equation
1

lim
T

0.

(12)

With this equation the minimum and maximum of the

S-loop for the solidliquid transition are located. Thus,
vmin/b 1.02, and vmax/b 1.04, which are proposed in
this work, are the molar vol- ume of the minimum, and
maximum, respectively. With this in mind, the
parameters f, and e, are initialized with

vv

P(T, v) dv = Plv

0.871

vmax
= vmin

(vv vl2 );

(13a)

b;

(11b)
vl

(11d)

(exp)

R(vmin e)
f =
1.995

2
10
10(vmin b)

trp

11

Psl = P lv;
(11c)
lv

Rb ,

(13b)

(exp)

where is dened according to

T Ttrp

(11e)
In Fig. 2, a schematic isotherm curve is illustrated for
a temper- ature above but close to the triple point
temperature constructed
with Eq. (1). In this case, Maxwell construction is applied
to both S-loops. Thus, Eqs. (11a) and (11b), correspond
to solidliquid, and liquidvapor phase transitions,
respectively. In Fig. 2, the upper, and lower dashed lines,
correspond to the common pressure Psl , and
P lv, respectively. In general, for a temperature above the
triple point
temperature from Eq. (1), the common pressure of the
solidliquid phase transition is always greater than the
common pressure of the liquidvapor phase transition,
i.e. Psl > Plv . The triple point of Eq.
(1) is determined with Eq. (11c), and in this case,
molar volume
value of the liquid phase must be the same for the solid
liquid, and
liquidvapor phase transitions, i.e. vl1 = vl2 . Thus, the
triple point of
Eq. (1) is determined for a given set of the
parameters {c, , f, e}.

vmin

.2/11

0.881.

(14)

vmax
b

3.3. Results
In this section, experimental reduced pressure vs
temperature along the three phase transitions (solid
liquid, solidvapor and liquidvapor, including the triple
point and the liquidvapor crit- ical point) for CO 2, and
Ar, are used to carry out the calculations described in
previous sections. The results are used to illustrate the
capabilities of Eq. (1). The parameters for CO2, and Ar,
are given
in Table 4. The triple point, which is
predicted, is also given in Table 4. In particular, the
temperature deviation at the triple point

(exp |) is 0.0%, and 0.14%, for CO , and

2
(6T 100 |(T )/T )
(exp)
Ar,
T
respectively. In the same way, the pressure deviation at
the triple

Table 4
Parameters obtained with Eq. (1) for CO2 and Ar together with the triple
point reduced properties.
Ar

Parameters
c
/RTc
aPc /R2 Tc

0.842154
0.332809
1.512547

0.804155
0.245437
1.869365

b/vc

0.426015

0.340589

c/vc

0.398453

0.276294

1.460831
0.378544
8.244160

0.983887
0.296685
4.854443

d/vc
e/vc
11
fTc 10 /P cvc 10
Triple point
Tt /Tc
Pt /Pc
vsol /vc
vliq /vc
vvap /vc

0.71
20
0.07
02
0.43
14
0.45
95
33.8
91

0.5562
0.0141
0.3439
0.3793
129.23

10

P/Pc

CO2

100

Argon
This work Wenzel Yokoseki

0.1

0.01
(exp)

(exp)

point (6P 100 |(P P

)/P
|) is 0.0%, and
2.17%, for CO2, and Ar, respectively. In both cases, the
pressure and the temper- ature of the triple point, which
are predicted by using Eq. (1), are in agreement with
the experimental data for each substance.
The reduced pressuretemperature phase diagram for
CO2 is shown in Fig. 3. The results obtained with Eq. (1)
and other equations from the literature are also included in Fig. 3. In
general, the results obtained by using Eq. (1) are in
agreement with experimen- tal data. In particular, the
melting line prediction with Eq. (1) is much better than
the other results, and furthermore, the melting line,
which was obtained with Eq. (5) by Yokozeki [24], has a
higher deviation. At least for this substance, Eq. (1)
predicts quite well the pressuretemperature diagram
on the temperature range of Fig. 3.

100

10

1E-3
0.4

0.6

0.8

1.0

1.2

1.4

T/Tc

Fig. 4. Phase diagram in reduced pressuretemperature coordinates.

Dots are experimental data for argon [37,38]. Solid curve is obtained
with Eq. (1); long-dashed curve obtained with Eq. (3) in Ref. [29] by
Wenzel and Schmidt; short-dashed curve obtained with Eq. (5) in Ref.
[24] by Yokozeki.

The reduced pressuretemperature phase diagram for

argon is used as the second example to show the
capabilities of Eq. (1), and the corresponding results and
comparisons are presented in Fig. 4. In this case, Eq. (3)
(in Ref. [29] by Wenzel and Schmidt) describes better
the melting curve, along the temperature range they
covered. On the other hand, Eq. (1) describes quite well
the melting curve for a temperature close to that of the
triple point, but the results for the melting curve have a
marked deviation for
a temperature beyond the
temperature of the liquidvapor critical point. Finally, the
results for the melting curve, which are obtained with
Yokozekis equation [24], have a similar deviation with
respect to our results with Eq. (1), and therefore, both
equations are almost equivalent in this case.

P/Pc

4. Conclusions

0.1

CO2
This work Wenzel
Yokoseki

0.01

1E-3 0.5

1.0

T/Tc

A unied EOS is proposed, and is given by Eqs. (1)

and (2). The EOS is basically a cubic equation plus the
10
term fT/(v e) . The above term (where f > 0 and e
are the adjustable parameters) corresponds to the attractive contribution of the solid
phase, has a molar volume short-range, and allows the
representation of the triple point, the melting curve,
and the sublimation curve. More- over, the prediction
for the solid phase denes a curve which never connects
its corresponding liquid phase at the solidliquid phase
coexistence, i.e. a critical point for the solidliquid phase
transition does not occur under the considerations
described in this work. This feature is in agreement with
the experimental evidence known up to date. In this
point, Yokozekis equation (see Eq. (5) in Ref. [24]) also
fullls this feature, but violates some physical
restrictions [26]. The complete set of the adjustable
parameters of the EOS is

b,
c,
d,
e, f,

Fig.
3.
Phase
diagram
in
reduced
pressuretemperature
coordinates. Dots
are
experimental data for carbon dioxide [44,45]; solid curve is obtained
with Eq. (1); long-dashed curve obtained with Eq. (3) in Ref. [29] by
Wenzel and Schmidt; short- dashed curve obtained with Eq. (5) in
Ref. [24] by Yokozeki.

}. The method to determine the parameters is fully

described in Section 3. In this method, the
parameters are determined by using the critical point data at the liquid
vapor region,
the acentric factor, (which is calculated by using the
reduced pressure, P/Pc, at the reduced temperature T/Tc
= 0.7), and the triple point data of the substance. The
resulting parameters are exclusive

for each substance. The melting curve, the sublimation

curve, and the vaporization curve are predictions of our
EOS, which are compared with experimental data in
Figs. 3 and 4. However, and in fact, the negative slope
of the melting curve, which is observed for water, is not
reproduced with our EOS. In this case, a special
treatment (which is suggested by Wenzel [21])
is
required
for
the water. In other cases, the
polymorphism is taken into account through the acentric
factor of the substance, and it must be considered as a
rst approach. The present model cannot handle
substances exhibiting solid polymorphism or having
melting pres- sure curves with negative slopes. These
issues will be addressed in another publication.
On the other hand, the vaporization curve can be
approached with the results of the cubic equation itself
because the attractive contribution of the solid phase is
negligible in this region. How- ever, the melting curve,
the sublimation curve, and the triple point emerge
because the attractive contribution of the solid phase
takes an important role in those cases. In this work, the
complete phase diagram of carbon dioxide and argon
are used to exhibit the main features of Eq. (1). In both
cases, the predictions for the three phase transition
lines of the phase diagram are in agreement with experimental data. In particular, the resulting phase diagram
for carbon dioxide ts the experimental data in a much
better way than other predictions from other equation
from the literature. For the case of argon, Eq. (1)
predicts a melting curve with a marked deviation, but
ts very well the remaining experimental data, i.e. the
vaporization curve, the sublimation curve, and the triple
point. In the worst case, our results in the melting region
are very similar to other results obtained by using
Yokozekis equation.
The EOS, together with the methodology described,
can be used to represent the complete pressure
temperature phase diagram for other systems, which
have not been included in this work, consid- ering the
availability of the experimental information in order to
obtain their corresponding parameters. Finally, the
implementa- tion of the use of our EOS to mixtures will
be developed in the near future.
Acknowledgements
The authors thank to IMP the support through the
research project D.00406 to carry out this work. FJGR
also thanks to CONA- CYT and IMP the support through
project Y.00116.

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