J.

of Supercritical Fluids 55 (2010) 594602

Contents lists available at ScienceDirect
The Journal of Supercritical Fluids
j our nal homepage: www. el sevi er . com/ l ocat e/ supf l u
An isomorphic PengRobinson equation for phase-equilibria properties of
hydrocarbon mixtures in the critical region
Kh.S. Abdulkadirova
a
, C.J. Peters
b,c
, J.V. Sengers
a,c,
, M.A. Anisimov
a,c
a
Institute for Physical Science and Technology, University of Maryland, College Park, MD 20742, USA
b
Chemical Engineering Department, Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates
c
Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD 20742, USA
a r t i c l e i n f o
Article history:
Received 14 July 2010
Received in revised form
13 September 2010
Accepted 14 September 2010
Keywords:
Critical phenomena
Equation of state
Hydrocarbon mixtures
PengRobinson equation
Vaporliquid equilibria
a b s t r a c t
The principle of isomorphism of critical phenomena asserts that the equation of state of uid mixtures
in the critical region has the same form as that of the pure components, provided that the mixture is
not considered at a xed composition but at a xed value of a constant eld variable related to the
chemical potentials of the components of the mixtures. This principle has been successfully applied by
various investigators to formulate nonclassical equations of state for uid mixtures in the critical region.
In this paper we show how the same principle can be applied to simple classical equations of state using
the PengRobinson equation as a representative example. The isomorphic PengRobinson equation thus
obtained is applied to represent phase equilibria properties of some binary mixtures of methane, butane
and decane.
2010 Elsevier B.V. All rights reserved.
1. Introduction
After more than a century since van der Waals extended his
famous equation of state to the description of binary and ternary
uidmixtures [1,2], his ideas have remainedanimportant guidance
for modeling vaporliquidequilibria. Cubic andgeneralizedvander
Waals equations are still widely used in practice [37]. An example
of a popular cubic equationis the PengRobinsonequation[8] often
used in industry, especially for renery and reservoir simulations.
Fluidphase behavior inthe near-critical regionis of key importance
in many process technologies at high pressures, such as supercriti-
cal uid extraction, exploitation of rich gas condensate/volatile oil
reservoirs, and gas-injected enhanced oil recovery.
However, there are two problems with the application of classi-
cal equations of statetocharacterizethethermodynamic properties
of uids anduidmixtures near critical points. Therst well-known
problem is that classical equations neglect density uctuations
which become large near the critical point. A second and perhaps
even more conceptual problemis encountered when such classical
equations are used for mixtures near critical points. When a mix-
ture witha xedcompositionis representedby a classical equation,

Corresponding author at: Institute for Physical Science and Technology, Univer-
sity of Maryland, College Park, MD 20742, USA. Tel.: +1 301 405 4805; fax: +1 301
314 9404.
E-mail address: sengers@umd.edu (J.V. Sengers).
the critical point of the classical equation is located at the top of
the coexistence curve implied by the classical equation, while in
reality the critical point is no longer located at the top of the dew-
bubble curve. As a result, the critical point of the classical equation
no longer corresponds to a real critical point but becomes a pseu-
docritical point. It is the latter issue that will be addressed in the
present publication.
Van der Waals understood this problemand sawthe solution in
the proper application of the equilibrium and stability conditions
which need to be reformulated upon the increase of number of
thermodynamic variables [9]. In fact, the extension of the modern
theory of critical phenomena to mixtures is based on a principle
of isomorphism of critical phenomena [1013] which utilizes the
van der Waals formulation of stability conditions. This principle
asserts that the equation of state of a mixture in the critical region
is isomorphic to that of a one-component uid provided that the
mixture is not considered at a xed composition, but at a xed
value of a suitable chosen eld variable. For binary mixtures with a
simplephasediagraminwhichthecritical points of thetwocompo-
nents are connected by a continuous critical locus, an appropriate
eld variable is commonly taken to be a function of the chemical
potentials
1
and
2
of the two components [1416]:
=
1
1 +exp[(
1

2
)/RT]
, (1)
where T is the temperature and R is the universal molar gas con-
stant. The advantage of the denition of the eld variable is that
0896-8446/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2010.09.021
Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602 595
Fig. 1. Vaporliquid phase boundaries for mixtures of methane and ethane in the
temperaturedensity plane as calculated from an equation of state formulated by
Povodyrev et al. [17,18]. The dashed curves represent vaporliquid coexistence
curves at various constant values of the eld variable , including the coexistence
curves of pure methane ( =0) and pure ethane ( =1). The solid curve represents
the dew-bubble curve of the equimolar mixture (x =0.5).
0 1, where the values =0 and =1 correspond to the pure
components.
To illustrate the principle of isomorphism of critical behavior
we show in Fig. 1 phase boundaries for mixtures of methane and
ethane in the critical region calculated from a scaled equation of
state developed by Povodyrev et al. [17,18]. The dashed curves rep-
resent vaporliquid phase boundaries of the mixtures at various
values of the eld variable . The curves with =0.0 and =1.0
represent the coexistence curves of pure methane ( =x =0) and
of pure ethane ( =x =1), where x represents the mole fraction of
ethane. The solid curve in Fig. 1 represents the phase boundary
of the equimolar mixture, (x =0.5), commonly referred to as dew-
bubble curve [16]. While the coexistence curves at constant are
all similar to the coexistence curves of the pure components ( =0
and =1), the dew-bubble curve is qualitatively different from the
coexistencecurves of thepurecomponents. Whiletheclassical one-
uid model, which assumes that the mixture at xed composition
can be described by an equation of state similar to that of a one-
component uid, breaks down in the critical region, the one-uid
model is valid when considered at constant .
Many investigators have applied the principle of isomorphism
of critical phenomena to characterize thermodynamic properties of
uid mixtures in the critical region in the context of nonanalytical
equations of state [16,1949]. However, the principle of isomor-
phism of critical behavior should also be applicable to classical
equations of state. Hence, it is of interest to investigate whether
application of the isomorphismprinciple to simple cubic equations
will lead to an improved capability of such equations for represent-
ing the thermodynamic properties of uid mixtures in the critical
region. We shall do this by adopting the classical PengRobinson
(PR) equation as an example. An earlier attempt towards a similar
goal was made by Fox and Storvick [5052].
We shall proceed as follows. In Section 2 we consider the clas-
sical PR equation and the corresponding Helmholtz energy for
one-component uids made dimensionless in a form suitable for
our analysis. We shall then formulate a corresponding isomorphic
Helmholtz energy for uid mixtures in Section 3. In Section 4 we
consider a so-called critical-line condition to simplify the relation-
ship between the isomorphic eld variable and the concentration
of the mixture. In Section 5 we then apply the isomorphic PR equa-
tion to some mixtures of alkanes in the critical region. Concluding
remarks are presented in Section 6.
2. PengRobinson equation for pure uids
The original PR equation for the pressure P has the following
form in terms of the molar density :
P =
RT
1 b

a(T)
2
1 +b +b(1 b)
. (2)
The system-dependent parameters a(T) and b are given by [8]:
a(T) =
0.45724 [1 +k(1 T
0.5
r
)]
2
R
2
T
2
c
P
c
, (3)
b =
0.0778RT
c
P
c
, (4)
k = 0.37464 +1.54226 0.26992
2
, (5)
where T
r
=T/T
c
is a reduced temperature, the acentric factor and
where T
c
and P
c
are the critical temperature and pressure, respec-
tively. Eq. (2) yields for the compression factor at the critical point:
Z
0
=
P
c
RT
c

0
= 0.30745. (6)
In the classical PR equation one conventionally adopts an incorrect
classical critical density
0
=P
c
/RT
c
Z
0
which differs from the actual
experimentally observed value of the critical density
c
.
Expressing the critical parameters through the coefcients
a =a(T
c
) and b one obtains:
T
c
= 0.17015
a
Rb
, P
c
= 0.01324
a
b
2
,
0
= 0.25305
1
b
. (7)
All thermodynamic properties and the system-dependent param-
eters can be made dimensionless with the aid of the critical
parameters [53]:
=

0
,

T =
T
c
T
,

P =
PT
c
P
c
T
, =

0
T
c

P
c
T
,

b = b
0
,
a =
a
0
RT
c
. (8)
In terms of dimensionless variables, the PR equation becomes:

P( ,

T) =
1
Z
0
_

1

a(

T)
2
1 +2

b
2
_
, (9)
where the temperature-dependent function a is:
a(

T) = Z
1

T
_
1 +k
_
1
_

T
_
0.5
__
2
(10)
with:
Z
1
=
0.45724
Z
0
= 1.4874, (11)
and:

b =
0.0778
Z
0
= 0.25308. (12)
An equation of state does not specify uniquely the temperature
dependence of caloric properties like the specic heat capacities.
In the theory of critical phenomena it is advantageous to consider
the Helmholtz-energy density, i.e., the molar Helmholtz energy A
dividedby the molar volume V[54]. The reducedHelmholtz-energy
density =AT
c
/TP
c
is relatedto the pressure, density andchemical
potential by:

A =

P + , (13)
596 Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602
and it satises a differential relation of the form:
d

A =

Ud

T + d , (14)
where

U=UP
c
is the reduced energy density [55,56]. Since:

_


_

T
=
_


_

T
, (15)
it follows that the chemical potential can be obtained by inte-
grating the equation of state for

P( ,

T):
=
_
1

_

P

_

T
d . (16)
We thus obtain for the Helmholtz-energy density associated with
the PR equation:

A( ,

T) =

Z
0
_
ln
_

1

b
_
+
a

2
arctanh
_
1

2
__
+
0
(

T).
(17)
The function
0
(

T) in Eq. (17) arises from the integration constant

in Eq. (16). It is not specied by the PR equation, but it does yield a
temperature-dependent contributiontothe specic heat capacities
independent of the density. In practice, one represents
0
(

T) by a
truncated Taylor series expansion around the critical temperature
in terms of

T = (T T
c
)/T:

0
(

T) =
0
0
+
0
1

T + . (18)
The rst two coefcients,
0
0
and
0
1
, in this expansion determine
the zero points of entropy and energy. Hence, they do not affect the
calculation of any of the thermodynamic properties and they can
be given arbitrary values for one-component uids.
It is convenient to separate the Helmholtz-energy density into
a critical contribution

A and a regular background contribution

A
reg
[55]:

A =

A +

A
reg
(19)
with:

A
reg
=

P
0
(

T) +
0
(

T), (20)
where

P
0
(

T) and
0
(

T) represent the pressure

P and the chemical
potential at the critical density =
0
. The contribution

A is
dened so as to satisfy the following two conditions: rst,

A =
0 at the critical point and, second,
1
= (
2

A/
2
)

T
, since is
the physical quantity directly related to the strength of the critical
uctuations [54]. From Eqs. (9), (16) and (17) we nd:

P
0
(

T) =
1
Z
0
_
1
1

a(

T)
1 +2

b
2
_
, (21)
and:

0
(

T) =
0
(

T) +
0
(

T) (22)
with:

0
(

T) =

P
0
(

T) +
1
Z
0
_
ln(1

b) +
a(

T)
_
2

b
arctanh
_
1

2
_
_
.(23)
We note that

P( ,

T),

P
0
(

T) and
0
(

T) only depend on temper-

ature through a(

T). If we expand

P
0
(

T) and
0
(

T) around the
critical temperature in terms of

T we obtain:

P
0
(

T) =

P
00
+

P
01

T, (24)

0
(

T) =
00
+
01

T, (25)
with:

P
00
= 1, (26)

P
01
=
Z
1
(1 +k)
Z
0
(1 +2b b
2
)
, (27)

00
= 1 +
1
Z
0
_
ln(1

b) +
Z
1
_
2

b
arctanh
_
1

2
_
_
, (28)

01
=

P
01

Z
1
(1 +k)
Z
0
_
2

b
arctanh
_
1

2
_
. (29)
The resulting expression for the critical part

A of the
PengRobinson equation is then readily obtained as:

A( ,

T) =

A( ,

T)
0
(

T) +

P
0
(

T) (30)
as afunctionof = 1and

T =

T +1.

Ais thecritical contri-

bution to the Helmholtz-energy density. It is this part which needs
to be renormalized if one wants to incorporate the effects of the
critical uctuations [55,57]. In the classical approximation adopted
herethecompact expression(17) for

Aandthedecomposedexpres-
sion (19) for

A remain equivalent.
3. Isomorphic PengRobinson equation for uid mixtures
For mixtures the critical parameters P
c
, T
c
and
c
depend on the
composition. To deal with this additional complication we nd it
convenient to adopt for mixtures a modied set of thermodynamic
variables [14,19]:

T =
1
RT
,

P =
P
RT
,
1
=

1
RT
,
2
=

2
RT
,

A =
A
RT
,

U = U.
(31)
The choice of
1
and
2
as the eld variables is not convenient
in practice, since
1
or
2
diverge in the pure component limits.
Instead one denes two elds, h and , that are related to the activ-
ities e

1
and e

2
by:
h = ln(e

+e

2
), =
1
1 +e
(
1

2
)
, (32)
so that:

1
= h +ln(1 ),
2
= h +ln. (33)
The pressure

P considered as a function of

T, h, and satises the
differential relation:
d

P =

Ud

T +dh +wd (34)

with:
w =
(x )
(1 )
, (35)
where x is the mole fractionof component 2, so that x is the partial
densityof component 2(solute). Amodiedisomorphic Helmholtz-
energy density , dened as:

A
iso
(

T, , ) = h

P, (36)
which satises the differential relation:
d

A
iso
=

Ud

T +hd wd (37)
is more useful, since it has a measurable property (overall molar
density ) as a canonical variable. On comparing Eq. (37) with Eq.
(14) we see that for the mixture h is the ordering eld, like for the
one-component uid, whichis conjugate to the density as the order
parameter. Theisomorphic eldvariable is oftencalledthehidden
eld (i.e., irrelevant eld) and w is the density variable conjugate
to . The mole fraction x of the solute is related to by:
x =
(1 )

A
iso

T,
. (38)
Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602 597
To implement the principle of isomorphism of critical behavior we
consider

A
iso
as a function of:

T =
_
T T
c
()
T
_
, =
[
0
()]

0
()
. (39)
The isomorphism principle states that for a mixture at constant
,
iso
has the same dependence on

T and as

A of a one-
component uid. Since in the one-component limit

A
iso


A =
(P/RT
c
)

A, we may write:

A
iso
(

T, , ) =
P
c
RT
c
()

A(

T, , ), (40)
where is again given by the PengRobinson Eq. (17). First of
all,
iso
depends on through the critical parameters P
c
(), T
c
()
and
c
(). Furthermore,

A(

T, , ) depends on through the

system-dependent parameter k() in the denition (10) of a(

T) for
which we adopt a quadratic mixing rule:
k() = k
1
(1 ) +k
2
+k
mix
(1 ). (41)
In Eq. (41) k
1
and k
2
represent the values of k for the two pure
components through the values
1
and
2
of the two components
in Eq. (5), while k
mix
will be treated as an adjustable coefcient
for the mixtures. With Eq. (10) the dependence of the critical
parameters and of the coefcients in the expansion (18) for the
background contribution a(

T), as well as that of the coefcients

P
01
and
01
in Eqs. (24) and (25), is now completely specied. A
procedure for handling the dependence of the critical parameters
and of the coefcients in the expansion (18) for the background
contribution
0
(

T) to the chemical potential will be presented in

the subsequent section. The variable varies from 0 to 1 when the
mole fractionx varies from0to1. However, unlike the mole fraction
x, the eld variable will have the same value in the two coexisting
phases.
The isomorphic Helmholtz-energy density
iso
, as denedby Eq.
(40), satises the differential relation:
d

A
iso
=

Ud

T +h
c
()d wd (42)
with:
w =
_

A
iso

T,
. (43)
We note that (

A
iso
/)

T,
in Eq. (38) and (

A
iso
/)

T,
in Eq. (43)
are related by:
_

A
iso

T,
=
_

A
iso

T,

1
T
dT
c
()
d
_

A
iso

T
_
,

2
0
()
d
c
d
_

A
iso

T,
. (44)
4. Relationship between mole fraction x and eld variable
The isomorphic PengRobinson equation, dened by Eq. (40),
yields the thermodynamic properties of mixtures as a function
of

T, , and. In order to represent experimentally measured

thermodynamic-property data, we need to evaluate the relation-
ship between the mole fraction x and the eld variable . Eq. (32)
does not specify this relationship uniquely, since it depends on the
choices made for the zero points of energy and entropy through the
values of the coefcients
0
0
and
0
1
in Eq. (18) for the two compo-
nents [14]. It is convenient to specify this transformation so that
equals x on the critical locus:
P
c
() = P
c
(x), T
c
() = T
c
(x),
0
() =
0
(x). (45)
Condition (45) is commonly referred to as critical line condi-
tion (CLC) [1517,5860]. From Eq. (38) we conclude that the CLC
requires that at the critical locus:
_

A
iso

T,
=
_

A
reg

T,
= 0, (46)
where:

A
reg
=
P
c
()
RT
c
()

A
reg
(47)
with
reg
given by Eq. (20). On the critical locus

A and its rst

derivatives are zero, so that only the regular background contri-
bution to the Helmholtz-energy density appears in the condition
given by Eq. (46). We note again that the coefcients in the expan-
sions (18), (24), and (25) for

P
0
(

T) and
0
(

T) in Eq. (20) depend on

k and, hence, on , except for

P
00
and
00
. To formulate the CLC
explicitly, we need to substitute the -dependent expression (20)
for

A
reg
into Eqs. (47) and (46) and use Eq. (44). As earlier shown by
Povodyrev et al. [19], condition (46) is satised if we demand that:
d
0
0
d
=
1
T
c
()
dT
c
d
[

P
01
() +
01
() +
0
1
()] +
RT
c
()
P
c
()
d
d
_
P
c
RT
c
_
(48)
The dependenceof

P
01
() and
01
() is speciedthroughEqs. (27),
(29) and (41). In addition we try to specify
0
0
() and
0
1
() so as to
satisfyEq. (48). As mentionedinSection2, thecoefcients
0
0
() and

0
1
() can be assigned arbitrary values for =0 and =1; however,
for intermediate values
0
0
() and
0
1
() are no longer arbitrary,
since they affect such quantities as the enthalpy of mixing [58,60].
There are a number of ways to implement the CLC. The simplest
way is to select
0
0
() and
0
1
() such that:

0
1
() =

P
01
()
01
() (49)
and:
d
0
0
()
d
=
RT
c
()
P
c
()
d
d
_
P
c
()
RT
c
()
_
. (50)
We refer to Eqs. (49) and (50) as CLC1, which is equivalent to the
assumptionthat theinternal energyUcanbetakentobezeroevery-
where on the critical locus [58]. CLC1 has the advantage that the
isomorphic PengRobinson equation of state (IPREOS) will contain
only one (adjustable) mixing parameter, namely k
mix
in Eq. (41).
This simple one-parameter version of the IPREOS turns out to give
a realistic representation of dew-bubble curves in a PT diagram
as shown in the Appendix. However, to retain more exibility, in
particular to represent vaporliquid curves in a Px diagram, we
retain the complete Eq. (48) and satisfy it for d
0
0
()/d by adopting
a quadratic interpolating formula for
0
1
():

0
1
() =
0
1,1
(1 ) +
0
1,2
+
0
1,mix
(1 ), (51)
using
0
1,1
,
0
1,2
and
0
1,mix
as adjustable coefcients for the mix-
ture in addition to k
mix
. We refer to this more exible version of the
CLC as CLC2. We remark that for the calculation of pressure, spe-
cic heat capacities and speed of sound, one does not need
0
(),
but only its rst and second derivatives with respect to which
can be readily calculated from Eq. (48). However, if we were to
calculate excess enthalpies we would need
0
() to be obtained
by integrating Eq. (48) [19,40]. Having satised the CLC, we can
replace dP
c
()/d, dT
c
()/d, and d
0
()/d, by dP
c
(x)/dx, dT
c
(x)/dx,
and d
0
(x)/dx, respectively.
598 Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602
Table 1
System-dependent parameters (critical temperature, Tc; critical pressure, Pc; critical
density, c; molecular weight, M; acentric factor, ) for the pure uids.
Methane
a
Butane
b
Decane
c
Tc (K) 190.564 425.20 617.6594
Pc (MPa) 4.5992 3.796 2.120
c (kg/m
3
) 162.66 227.85 235.9635
M (g/mol) 16.0428 58.125 142.489
0.008 0.193 0.489
a
Refs. [6163].
b
Refs. [63,64].
c
Ref. [65].
Table 2
Coefcients T
j
and P
j
in Eqs. (52) and (53) for the critical parameters of
methane +butane.
T
j
(K) P
j
(MPa mol/kJ)
T
1
=320.211 P
1
=0.04449
T
2
=296.156 P
2
=0.18963
T
3
=847.537 P
3
=0.36798
T
4
=1388.105 P
4
=0.34442
T5 =722.760 P5 =0.12188
5. Applications
As anillustrationweapplytheisomorphic PengRobinsonequa-
tion of state (IPREOS) to represent experimental vaporliquid PT
and Px data for mixtures of methane, butane, and decane. In the
previous sectionwe consideredtwo versions of anIPREOS, depend-
ing on the actual implementation of the critical line condition to
assure that equals x on the critical locus: one simple version of
the IPREOS with CLC1, given by Eqs. (49) and (50), containing only
one adjustable parameter k
mix
and a more general version with the
less restrictive CLC2, given by Eqs. (48) and (51) containing three
additional adjustable parameters throughEq. (51). We prefer to use
the IPREOS with CLC2, since it yields a better representation of the
experimental data over a wider range of temperatures. The results
obtained by adopting the simple IPREOS with CLC1 are presented
in the Appendix.
To implement the IPREOS in practice, we need equations for
the critical temperature T
c
(x) and the critical pressure P
c
(x) as a
function of the composition. Like in the case of one-component
uids, the critical density is then taken as
0
(x) = Z
1
0
P
c
(x)/RT
c
(x).
The information needed to specify the PengRobinson equation for
the pure uids is presented in Table 1.
5.1. Methane +butane
In practice we represent the critical temperature and pressure
of this mixture by polynomials of the form [17,19]:
T
c
(x) = T
c1
(1 x) +T
c2
x +(T
1
+T
2
x +T
3
x
2
+T
4
x
3
+T
5
x
4
)x(1 x),
(52)
P
c
(x)
RT
c
(x)
=
P
c1
RT
c1
(1 x) +
P
c2
RT
c2
x +(P
1
+P
2
x +P
3
x
2
+P
4
x
3
+P
5
x
4
)x(1 x), (53)
where x is the mole fraction of butane and where T
ci
and P
ci
are the
critical temperatures andpressures of methane (i =1) andof butane
(i =2). We have determined the coefcients T
j
and P
j
(j =15) from
a t of Eqs. (52) and (53) to experimental data for the critical tem-
peratures and pressures for the mixture [66,67]. The values thus
obtainedare presentedinTable 2. Acomparisonof the values calcu-
0.0 0.2 0.4 0.6 0.8 1.0
0.001
0.002
0.003
0.004
0.005
0.006
0.0 0.2 0.4 0.6 0.8 1.0
200
250
300
350
400
450
a
b
P
c

/

(
R
T
c
)
,

M
P
a

m
o
l

/

k
J
x, mol.fr. n-butane
T
c

,

K
Fig. 2. Tc(x) and Pc(x)/RTc(x) for mixtures of methane +butane as a function of the
mole fraction x of butane. The curves represent the values calculated from Eqs. (52)
and (53). The symbols indicate experimental data obtained by Sage et al. [66].
latedfromEqs. (52) and(53) withthe experimental values reported
by Sage et al. [66] is shown in Fig. 2.
In applying the IPREOS with CLC2 to mixtures of methane (C
1
)
andbutane(C
4
) weadoptedthefollowingvalues for thecoefcients
in Eqs. (41) and (51):
k
mix
= 1.7,
0
1,1
= 14.30,
0
1,2
= 12.828,
mix
= 5.045,
(54)
deduced from a t to experimental Px data measured by Sage et
al. [66]. In Fig. 3 we show Px curves at the temperatures corre-
sponding to the experimental data of Sage et al. In Fig. 4 we show
PT curves for three selected mole fractions x of butane. Note that,
in order to make a comparison of the PT curves with experimental
values, we had to extract such data fromthe experimental Px data.
We conclude that the IPREOS yields a reasonable representation of
the phase-equilibria data except for a range corresponding to small
P and small x.
5.2. Methane +decane
The system methane +decane exhibits a phase diagram desig-
nated as Type V in the classication of Scott and Van Konynenburg
[68,69], so that the vaporliquid critical locus does not exist for all
values of the mole fraction x of decane. The vaporliquid critical
locus corresponds to [67,70] (Fig. 5).
x x
min
= 0.095, (55)
so our calculations are also limited to this concentration range.
For a description of the critical temperature and pressure we have
adopted the following equations:
T
c
(x) =
(T
min
T
c2
x
min
)(1 x)
(1 x
min
)
+T
c2
x +T
1
(1 x)(1 +t
4
x)
exp
_

t
2
(x x
min
)
t
3
_
(56)
P
c
(x)
RT
c
(x)
=
_
P
min
(x)
RT
min
(x)

P
c2
(x)
RT
c2
(x)
x
min
_
(1 x)
(1 x
min
)
+
P
c2
(x)
RT
c2
(x)
x
+P
1
(1 x)(1 +p
4
x) exp
_
p
2
(x x
min
)
p
3
_
, (57)
Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602 599
0.0 0.2 0.4 0.6 0.8 1.0
0
2
4
6
8
10
12
14
394.26 K
360.93 K
327.59 K
P
,

M
P
a
x, mol. fr. n-butane
Fig. 3. Vaporliquid phase boundaries in terms of P versus x at constant T for mix-
tures of methane and butane. The curves represent values calculated from the
IPREOS (with CLC2). The symbols indicate experimental data obtained by Sage et
al. [66].
where T
c2
and P
c2
are the critical temperature and pressure of
decane, while T
min
=277.6K and P
min
=36.13MP are the critical
temperature and pressure corresponding to the cutoff composition
x =x
min
=0.095. The experimental values reported by Reamer et al.
[70] correspondtomole fractions belowx =0.3. Toobtainadditional
values for the critical parameters we also extrapolated near-critical
experimental data reported by Lin et al. [71]. The values obtained
300 350 400
0
2
4
6
8
10
12
14
0.9 C
4
0.5 C
4
0.2 C
4
P
,

M
P
a
T, K
Fig. 4. Pressure temperature dew-bubble curves for mixtures of methane and
butane. The curves represent values calculated from the IPREOS (with CLC2) at
various values of the mole fraction x of butane (C
4
). The symbols indicate values
extracted from the experimental Px data obtained by Sage et al. [66].
Table 3
Values of the coefcients in Eqs. (56) and (57) for the critical parameters of
methane +butane.
T
1
=825.89 (K)
P
1
=0.03905 (MPa mol/kJ)
t
2
=p
2
=0.70
t
3
=p
3
=0.30
t
4
=p
4
=0.27313
0.0 0.2 0.4 0.6 0.8 1.0
0.000
0.005
0.010
0.015
0.020
0.0 0.2 0.4 0.6 0.8 1.0
300
400
500
600
700
P
c

/

(
R
T
c
)
,


M
P
a


m
o
l

/

k
J
x, mol.fr. n-decane
Reamer et al.
Lin et al.
T
c

,

K
Fig. 5. Tc(x) and Pc(x)/RTc(x) for mixtures of methane and decane as a function of
the mole fraction x of decane. The curves represent values calculated from Eqs. (56)
and (57). The symbols indicate experimental values [70,71].
for the coefcients in Eqs. (56) and (57) for T
c
(x) and P
c
(x)/RT
c
(x)
are presented in Table 3. The actual values of T
c
(x) and P
c
(x)/RT
c
(x)
are shown in Fig. 5.
It turns out that the experimental PT data reported by Reamer
et al. [70] and by Lin et al. [71] are not consistent with each other.
Specically, the mole fractions of methane obtained by Lin et al. in
the liquid phase differ by about 4% from those obtained by Reamer
et al. [70]. From a comparison of the two data sets we have con-
cluded that the bubble pressures reported by Lin et al. [71] are too
low compared to those reported by Reamer et al. [70]. Neverthe-
less we are able to predict the phase-equilibria data for mixtures of
methane and decane, at least qualitatively, in terms of one mixing
parameter k
mix
=0.97 as shown in the Appendix. Here we show
in Fig. 6 Px curves calculated fromthe IPREOS with CLC2 adopting
the following values for the coefcients in Eqs. (41) and (51):
k
mix
=0.96,
1,1
= 45.08,
1,2
=17.96,
mix
= 17.91,
(58)
It should be noted that the values for the critical parameters of
this mixture are not very accurate, which affects the predictive
capability of the IPREOS.
6. Discussion
The principle of isomorphic thermodynamic behavior of mix-
tures asserts that mixtures including the critical region can be
describedby a one-uidmodel providedthat the one-uidmodel is
taken at constant chemical potentials and not at constant composi-
tions. Inthis paper we have shownhowone canapply this principle
in terms of the PengRobinson equation of state. For an accurate
representation of the thermodynamic properties of the mixture
600 Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602
0.0 0.2 0.4 0.6 0.8 1.0
0
5
10
15
20
25
542 K
511 K
477 K
P
,

M
P
a
x, mol. fr. n-decane
Fig. 6. Vaporliquid phase boundaries in terms of P versus x at constant T for
mixtures of methane and decane (x >x
min
=0.095). The curves represent values
calculated from the IPREOS (with CLC2). The symbols indicate experimental data
obtained by Reamer et al. [70] at T =477Kand T =511Kand Linet al. [71] at T =542K.
near the critical point, one would need an additional transforma-
tion so as to incorporate asymptotic scaling laws with nonclassical
critical exponents [36,57,7275]. However, even by applying the
principle of isomorphic thermodynamic behavior based on a one-
uid model eld to a classical equation of state, one is able to get
already a reasonable description of phase-equilibria properties, as
illustrated for mixtures of methane, butane, and decane.
Acknowledgments
The research of Khapissat S. Abdulkadirova was performed
while she was a postdoctoral fellow at the Laboratory of Applied
Thermodynamics and Phase Equilibria of the Technical University
Delft in The Netherlands.
Appendix A. A simpler version of the isomorphic
PengRobinson equation
As was shown in Section 4, a simple version of the isomorphic
PengRobinson equation of state is obtained by adopting CLC1, as
given by Eqs. (49) and (50). The advantage of this simple version
of the IPREOS is that it species an equation for mixtures in terms
of only one mixing parameter, namely k
mix
in Eq. (41). In practice
we have used a more general IPREOS by adopting CLC2, as given by
Eqs. (48) and (51). This more general IPREOS contains three addi-
tional adjustableparameters, namely
0
1,1
,
0
1,2
and
mix
inEq. (51),
in part to compensate for incorrect values of the critical density

0
(x) implied by the PengRobinson equation and its effect upon
the calculation of phase boundaries in a Px diagram. However,
one may not have sufcient experimental data to determine four
adjustable coefcients for the mixtures. In that case one may want
to use the simpler version of the IPREOS. Hence, it is interesting to
alsoconsider results obtainedwiththis simple IPREOS, inparticular
for dew-bubble curves in a PT diagram.
180 210 240 270 300 330 360 390 420 450
0
2
4
6
8
10
12
14
0.2 C
4
0.5 C
4
0.8 C
4
P
,

M
P
a
T, K
Fig. A1. Pressuretemperature dew-bubble curves for mixtures of methane and
butane. The solid curves represent values calculated from the simple version of
the IPREOS with k
mix
=1.7 for various values of the mole fraction of butane (C
4
).
The dashed curve shows the critical locus. The symbols indicate experimental data
obtained by Sage et al. [66].
In Fig. A1 we present a comparison between the dew-bubble
curves for mixtures of methane and butane, calculated from the
simple version of the IPREOS with k
mix
=1.7, and the experimen-
tal data obtained by Sage et al. [66]. For comparison we also show
the dew-bubble curves calculated from the simple version of the
IPREOS without using any mixing parameter i.e., k
mix
=0. In Fig. A2
we present a comparison between the dew bubble curves calcu-
lated from the simplied version of the IPREOS with k
mix
=0.97
and experimental data obtained by Reamer et al. [70] and Lin et al.
[71]. We conclude that the simplied IPREOS gives a realistic esti-
mate of the pressuretemperature dew-bubble curves. However,
for a calculation of the vaporliquid phase boundaries in the Px
diagram, we prefer to use the more general version of the IPREOS
adopted in this paper.
450
500
550
600
650
0 5 10 15 20 25 30
0.9 C
10
0.8 C
10
0.5 C
10
0.2 C
10
P, MPa
T
,

K
Fig. A2. Pressuretemperature dew-bubble curves for mixtures of methane and
decane. Thecurves represent values calculatedfromthesimpleversionof theIPREOS
with k
mix
=0.97 for various values of the mole fraction of decane (C
10
). The dashed
curve shows the critical locus. The symbols indicate experimental data obtained by
Reamer et al. [70].
Kh.S. Abdulkadirova et al. / J. of Supercritical Fluids 55 (2010) 594602 601
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