Fluid Phase Equilibria 228229 (2005) 223231

Calculation of critical points using a reduction method

Dan Vladimir Nichita
Programa de Yacimientos Naturalmente Fracturados, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas no. 152,
07730 Mexico, D.F., Mexico

Abstract

Efficient and accurate calculation of critical points is an important aspect of general phase equilibrium calculations. When calculating
critical points, the computationally expensive part is to solve the spinodal equation. For Heidemann and Khalil formulation the dimensionality
of the problem is equal to the number of components (nc). In this paper we describe a new procedure enabling the reduction of problem
dimensionality.
The reduction is effectively achieved by spectral decomposition of the matrix C with elements (1 Cij ), where Cij denotes the binary
interaction parameters (BIP). The dimensionality of the problem is given by the number of reduction parameters, M = m + 1, where m is the
number of nonzero (or non-negligible) eigenvalues of C. The spinodal equation consists in equating to zero a determinant of order M (for
naturally occurring hydrocarbon mixtures, M is much less than nc). The procedure suggested by Michelsen and Heidemann for zero BIP is a
particular case of our approach.
For the spectral decomposition of C, the method is particularly efficient for mixtures with many components and few nonzero BIP. The
proposed method proved its reliability when tested for several mixtures having various phase diagram shapes. Finally, we show that critical
points of mixtures with more than 50 components, with a detailed paraffin-naphthene-aromatic (PNA) distribution of the heavy fraction, can
be calculated by only performing linear algebra operations with a small dimensionality. Application of the reduction method leads to important
savings in computer time.
2004 Elsevier B.V. All rights reserved.

Keywords: Method of calculation; Equation of state; Critical point; Spinodal; Reduction method

1. Introduction An attempt to reduce the dimensionality of the problem

Development of accurate and efficient methods for direct
calculation of critical points is valuable for phase equilibrium
calculations to be performed in solving a variety of problems
in chemical and petroleum engineering.
Generally, for the critical point calculation methods, the
spinodal equation is given by setting to zero a determinant
of nc or nc 1 order, containing second-order derivatives of
thermodynamic potentials. The most widely used criteria for
critical point calculation were established by Heidemann and
Khalil [1].
Tel.: +52 55 9175 7042; fax: +52 55 5119 8423.
E-mail address: dnichita@imp.mx.
was made by Michelsen and Heidemann [2], but is restricted
to all BIP zero. In the elegant approach of Billingsley
and Lam [3], the spinodal equation consists in solving a
2 2 problem, with no restrictions on BIP; however, their
method is somewhat unattractive because it requires solving
two nc nc linear systems of equations at each iteration
level.
The reduction theorem [4] states that, under certain as-
sumptions, the flash, stability, and spinodal calculations can
be carried out by solving equivalent problems with reduced
dimensionalities. The reduction method proved to be useful
to solve a variety of phase equilibrium problems [59].
Recently [9], a critical point calculation method based on
the reduction theorem has been reported, in which the deter-
minant in the spinodal equation has a lower order, irrespec-

0378-3812/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.09.036
224 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231

tive to the number of components in the mixture. The order Suppose than only m < nc eigenvalues are nonzero,
of this determinant is M + 1, given by the number of reduc-

tion parameters, M = m + 1, where m is the number of nonzero i , i = 1, ..., m,
(or non-negligible) eigenvalues of the matrix with (1 Cij ) i = i = 1, nc (2)
0, i = m + 1, nc,
elements. This matrix is rank-deficient for many actual mix-
tures, giving m  nc. The determinant contains second-order is
then C
derivatives of the Helmholtz free energy with respect to the re-
duction parameters. The method proved to be robust and effi- = Q QT
C (1 )
cient, and very attractive for mixtures with many components.
In this work a critical point calculation method is pro- where = diag( i ) is the (m m) diagonal matrix contain-
posed, for which the dimensionality of the problem is further ing nonzero eigenvalues = ; = 1, m, and the eigen-
reduced by one, the order of the determinant being equal to M. vectors spanning the null-space of C has been removed,
The approach of Michelsen and Heidemann for all BIP zero thus Q R ncm
contains only the first m row vectors of
is found to be a particular case of the development presented Q Rncnc .
here. Eq. (1) reads
Even though a general form of cubic EOS which includes
the PR EOS [10] and the SRK EOS [11] is used here, the m

proposed method is applicable to any EOS that observes the C
ij = qi qj (3)
restrictions of the reduction theorem. =1
The paper is structured as follows: first we present the
where qi are the elements of the eigenvectors q =
reduction method, we recall the Heidemann and Khalil criti-
(q1 , q2 , . . . , q nc )T ; = 1, m (row vectors of matrix Q)
cality criteria, then we present the proposed method, followed
corresponding to the eigenvalues .
by its application to several mixtures with many components,
Obviously, m equals r (the rank is equal to the number of
before drawing the conclusions of this work.
nonzero eigenvalues), and the relationship (3) is exact, since
only zero eigenvalues has been ignored. If a further reduction
of the dimensionality is desired, one can set m < r, and Eq.
2. The reduction method (3) is no more exact, but

m
In this work we use a general form of cubic EOS (see 
Appendix A), with van der Waals mixing rules. The idea ij
C = qi qj (3 )
of the reduction method is to express or approximate the =1
attractive parameter in the EOS by the sum of a small number
of scalar products [4,12]. This is done by using a suitable In this case some nonzero eigenvalues has been removed, then
decomposition of the matrix A = {aij }, for aij given by Eq. scaling is required to preserve the one diagonal condition for
the matrix C. Scaling of the remaining eigenvectors is done
(A.5).
Usually, for many actual mixtures, most of the BIP are by
zero. The BIP matrix is sparse, and often rank-deficient, and
its rank r  nc. A general form of cubic two-parameter EOS Q(s) = SQ (4)
is used in this work; however, the proposed method is not
restricted to the EOS used here. In the following, we will use and the elements of the diagonal scaling matrix S with respect
the spectral decomposition of the matrix C = E C, where to the eigensystem Q are
C is the BIP matrix, and the E matrix has all elements unity. 1
is symmetric and has all diagonal elements m
The matrix C
unity. S = 2
qk , , = 1, m (5)
k=1

It is clear that truncation in Eq. (3 ) for m < m without proper

2.1. The spectral decomposition
scaling is both formally and physically incorrect, since the
one-diagonal condition for the matrix C is violated.
can be expressed as
The symmetric matrix C
The rank of C is r = 2nNZ + 1 nE , where nNZ is the

number of components having nonzero BIP, and nE is the
= QQT
C (1) number of components having equal nonzero BIP with the
remaining components. This suggest that the application of
where Q Rncnc is the right-hand side eigensystem of C, the reduction method for phase equilibrium calculation is
and the diagonal matrix = diag(i ) contains the associated particularly efficient for mixtures with many components and
set of eigenvalues {i }i=1,nc . few nonzero BIP.
 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231 225

2.2. The reduction parameters where n = (n1 , n2 , . . . , nnc )T , and the normalization
condition nT n = 1 is imposed.
It is more convenient to express the decomposition of the The second criticality condition locates the critical

matrix A with elements aij , rather than that of the matrix C point(s) on the spinodal:
A = QQT nc nc nc  
(6) 3 A
C= ni nj nk = 0
where ni nj nk T,V,nl=i,j,k
k=1 j=1 i=1
(a) (14)
qi = qi ai , = 1, m, i = 1, nc (7)
(a) The original method of Heidemann and Khalil consists in
For convenience, we will refer to qi as qi in the rest of the nested iterations; in the outer loop Eq. (14) is solved for vol-
paper. ume, and in the inner loop Eq. (13) is solved for temperature.
The reduction parameters [4] are defined as The most expensive part of the critical point calculation

nc algorithm is to solve Eq. (13), i.e. an nc order problem. The
Q = qi xi , = 1, M (8a) idea is to reduce the dimensionality of this problem.
i=1 In this work we are using the reduction method to reduce
with M = m + 1, and the order of the determinant in the spinodal equation, and then
information from spinodal calculation is used to evaluate the

nc
cubic form C. For many actual mixtures, such as hydrocar-
QM b = bi xi (8b)
bon reservoir fluids, spectacular computer time savings are
i=1
expected to be obtained by using the reduction method.
where qi are the elements of the reduction matrix [4],
with qMi bi , i = 1, nc.
Combining Eqs. (8a) and (A.3), the attractive parameter 4. The proposed method
a of the cubic EOS can be written as a sum of m < nc scalar
products, The elements of the matrix QS are [2]
m

 ij a
a= Q2 (9) nQSij = RT + (i + j )F1 + i j F1 +
2
xi b
=1  
aij
instead of the quadratic form (A.3). i j F3 F5 + (i j i j j i )F6 (15)
a
Finally, the set of M + 1 reduction parameters is
Eq. (13) can be written as
Q = (Q1 , Q2 , . . . , Qm , b)T = (Q1 , Q2 , . . . , Qm , QM )T

nc
(10) Si QSij nj = 0 (16)
j=1
Our goal is now to reduce the dimensionality of the criti-
cal point problem by expressing the Heidemann and Khalil Introducing Eq. (15) in Eq. (16), one obtains for Si
criticality criteria in terms of the reduction parameters Q.

ni 1 )F1 + a
Si = RT + (i n + + i F
xi b
3. The Heidemann and Khalil criticality criteria nc 
j=1 aij nj
i F3
F5 + (i i
i )F6
This brief section reviews the well-known Heidemann and a
Khalil criteria for critical point calculation. The first critical- (17)
ity condition is the equation for the intrinsic limit of thermo-
dynamic stability (spinodal): Michelsen and Heidemann [2] define from Eq. (16) the sum-
mations
det(QS ) = 0 (11)

nc
with Sx x i Si = 0 (18a)
    i=1
2 A ln fi
QSij = = , 
nc
ni nj T,V,nk=i,j nj T,V,nk=i,j Sx x i i Si = 0 (18b)
i, j = 1, nc (12) i=1

or, equivalently 
nc
Sx x i i Si = 0 (18c)
QS n = 0 (13) i=1
226 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231

Using the above equations for all BIP zero, Michelsen and and
Heidemann reduce to two the dimension of the problem. m

nc 
nc 
The aim of this work is to reduce the dimensionality for
xi qi aij nj = Q
Sqq , = 1, m (28)
nonzero BIP. The key of our method (and the departure from i=1 j=1 =1
Michelsen and Heidemann approach for all BIP zero) is to
replace Eq. (18c) by with the notation


nc 
nc

Sxq xi qi Si = 0, = 1, m (19) Sqq xi qi qi , , = 1, m (29)
i=1 i=1

This will allow us to obtain a spinodal determinant of reduced Eq. (19) takes the form
dimensions, as shown in the following section. m

D Q
+ DM = 0, = 1, m (30)
4.1. The spinodal equation =1

Let us first express n = nc i=1 ni . This is done by intro-
with
ducing Si in Eq. (18a), and gives after rearrangement a
D = RT + [Q Sq (F5 + F7 ) F5 Sqq ],
a b
n = F1 (F7 + F8 )
(20)
bRT , = 1, m (31)
We can express and
1 
nc nc m
 a
xi i aij nj = Sq Q
(21) DM = RTF1 Q +
a b
i=1 j=1 =1
m

and can be written as Sq F8 + F6 Sq Q Sqq ,
m
 =1
= Q Q
(22) = 1, m (32)
=1

By introducing n in Eq. (17), and then Si in Eq. (18b), and Eqs. (30) and (23) reads in matrix form
taking into account Eqs. (21) and (22), after some algebra,
Eq. (18b) has finally the form
m

DM Q
+ DMM = 0 (23)
=1 or
with =0
DQ (34)
a
DM = [Q S (F5 + F7 ) F5 Sq ], = 1, m (24) where Q = (Q 1, Q M )T , with Q
2, . . . , Q M = .

b
What we have effectively obtained is the reduction of the
and dimensionality of the problem from nc nc in Eq. (13), to
a M M in Eq. (34).
DMM = RT (1 + F1 ) + [S (F8 + F6 ) S F6 ] (25)
b The spinodal criterion is
where
det(D) = 0 (35)

nc 
nc
S = xi i2 , S = xi i i , Note that now an M M determinant is to be calculated.
i=1 i=1 For all BIP equal to zero, m = 1, then Eq. (33) becomes

nc     
Sq =
xi i qi , = 1, m (26) D11 D12 0
= (33 )
i=1 D21 D22 0
Similarly, by introducing Si in Eq. (19), and using the rela- and we have found that the Michelsen and Heidemann spin-
tionships odal equation is as a particular case of ours. One can easily

nc m
 check that in this case from Eqs. (24), (25), (31) and (32)

xi qi i = Q Sqq , = 1, m (27) Michelsen and Heidemanns expressions for the elements of
i=1 =1 the matrix D are recovered (Eqs. (32)(35) in Ref. [2]).
 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231 227

4.2. The cubic form 4.3. Calculation procedure

For evaluating the second criticality condition, we need Nested iterations are performed to calculate the critical
the elements of the Q vector. These are obtained by back point, similar to the Heidemann and Khalil method. In the
substitution from Eq. (34); the condition = 1 was found to outer loop we iterate on the dimensionless volume for solving
be a suitable normalization. Eq. (14), while in the inner loop iterations are performed on
The cubic form from Eq. (14) can be expressed in a closed temperature to solve Eq. (35). We use NewtonRaphson (NR)
form as [2] iterations with numerical derivatives.

nc  Starting from (0) = 3.5, Eq. (35) is solved for temperature
 (ni )3
n C RT
2
+ 3n(F 1 )2 + 2(F
1 )3 with the NR method with T (0) = 1.5Tpc (for heavy mixtures,
i=1
x 2
i higher initial estimates may be required for temperature), then
 Q is obtained by back substitution, with = 1. Values of
a 2 and a are calculated from Eqs. (22) and (37), respectively,
+ [3 (2 )(F3 + F6 ) 2 F4 3aF6 ] = 0
3
b then ni is recovered from Eq. (40), and the cubic form is
(36) evaluated from Eq. (36). The dimensionless volume is up-
dated with the NR method, until the convergence criterion is
Another key factor in our approach is to express ni and all met.
other quantities from Eq. (36), namely ,
,
a , and n in terms
of Q available from the spinodal calculation; = f (Q)
from
Eq. (22), = 1, n = f (,
) from Eq. (20), thus we need to
5. Applications
relate a and ni to Q.

Taking into account Eq. (6), a is expressed as The proposed method has been thoroughly tested for a
m
 large number of mixtures having various phase diagram
a = Q
2 (37) shapes, and it has proved its reliability. Next, the results
=1 for some selected mixtures are presented. No attempts were
made to fit experimental data. Table 1 gives the results of
From Eqs. (17) and (20)
critical point calculations for the selected mixtures, together
F5 
nc with a comparison of determinants order between the Hei-
ni
RT + aij nj demann and Khalil method (nc), and the proposed method
xi b
j=1 (M = m + 1), and the number of iterations required for con-
 a  a vergence in the outer loop. Usually four to six iterations
= RTF1 + [i F8 + (i i )F ] + (F5 + F7 )i are required in the inner loop calculations, and convergence
b b
(38) in the outer loop is obtained in three to five iterations. The
PengRobinson EOS is used for all calculations.
By defining
 m
  5.1. Synthetic mixtures

nc 
nc 
ui = aij nj = qi qj nj
j=1 j=1 =1 We present the results for two synthetic hydrocarbon mix-
tures, containing normal-alkanes: the 6-component mixture
m
 
nc m
 Y8 [13], and the 10-component mixture denoted MY10 [14].
= qi qj nj = qi Q
, i = 1, nc
For the Y8 mixture all BIP are set to zero, therefore there
=1 j=1 =1
(39) is only one nonzero eigenvalue, 1 = nc = 6. For MY10,
nonzero BIP of methane are assigned, giving three nonzero
we finally obtain for ni eigenvalues. Phase boundaries, the spinodal curve, and the
 a critical points are depicted in Fig. 1 (Y8) and Fig. 2 (MY10).
ni = xi [ui F5 + i F
6 i ((F5 + F7 )
bRT
 5.2. Natural hydrocarbon mixtures with many
+ (F6 + F8 ))]
F 1 (40) components

Because, ,
n , a , and ni (through ui ) are functions of Q,
the
cubic form C can be viewed as a function of only Q and Q at
given temperature and dimensionless molar volume = v/b,
that is C = C(T, , Q, Q).
This means that information obtained in the spinodal cal-
culation with Eq. (34) by evaluating lower order determi-
nants, Eq. (35), is sufficient for evaluating the cubic form.
Compositions for samples A (gas condensate, nc = 34), B
(heavy oil, nc = 24), and C (heavy gas condensate, nc = 24) are
taken from Pedersen et al. [15]. Nonzero BIP are for methane,
carbon dioxide, and nitrogen, leading for all three mixtures
to five nonzero eigenvalues. The properties of heavy com-
ponents (critical temperature, critical pressure, and acentric
factor) are assigned using Riazi and Al-Sahhaf [16,17] cor-
228 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231

Table 1
Critical point calculation for selected mixtures
Mixture nc nNZ m Order of det(D) Tc (K) Pc (bar) = v/b Number of iterations on
Y8 6 0 1 2 293.65 210.95 1.9603 4
MY10 10 1 3 4 572.28 79.95 3.3787 3
Sample A 34 3 5 6 336.79 243.36 1.9135 4
Sample B 24 3 5 6 716.12 125.27 3.0703 3
Sample C 24 3 5 6 345.20 323.21 1.8495 4
Sample C 52 3 5 6 321.94 341.42 1.6754 4

Fig. 3. Critical point and spinodal for sample A.

Fig. 1. Critical point, spinodal and phase boundaries for the Y8 mixture.

relations. BIP of methane with hydrocarbon components are
calculated according to Katz and Firoozabadi [18].
Fig. 3 (sample A), Fig. 4 (sample B), and Fig. 5 (sample
C) depict spinodal curves (including for negative pressures
and LL instability) and critical points.
For sample C we use also the detailed PNA distribution
of the heavy fractions given in Ref. [15]; in this case sample
C has 52 components, and results are also plotted in Fig. 5.
Although there are important differences between the two
characterizations of sample C, this aspect is no further in-
vestigated. The goal is to prove the ability of the proposed
method to solve large problems by only performing linear
algebra operations with a small dimensionality.

Fig. 2. Critical point, spinodal and phase boundaries for the MY10 mixture. Fig. 4. Critical point and spinodal for sample B.
 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231 229

List of symbols
a attractive
 parameter
nc in the EOS
a (1/a) nc i=1 j=1 n i nj aij
ai component parameter in EOS
aij component EOS coefficient
A Helmholtz free energy
A matrix with elements aij
b covolume in the EOS
bi component EOS coefficient
C cubic form
C BIP matrix
C matrix with elements 1 Cij
Cij binary interaction coefficients between components
i and j
D matrix in spinodal equation
D elements of matrix D
fi fugacity of component i
F1 1/( 1)
Fig. 5. Critical point and spinodal for sample C. F2 2[1 /( + 1 ) 2 /( + 2 )]/
F3 {[1 /( + 1 )]2 [2 /( + 2 )]2 }/
Table 2
Critical point calculation for sample C (52 components)
F4 {[1 /( + 1 )]3 [2 /( + 2 )]3 }/
F5 2 ln[( + 1 )/( + 2 )]/
Iteration Temperature (K) Pressure (bar) Dimensionless Cubic form
volume
F6 F2 F 5
F7 F2 /(1 + F1 )
0 483.2673 239.6186 3.5 4.42
1 413.2421 351.6411 2.184092 9.41E01
F8 F3 /(1 + F1 )
2 332.1315 349.115 1.715533 6.94E02 m number of nonzero eigenvalues
3 322.0032 341.4699 1.675633 3.86E04 M number of reduction parameters
4 321.9442 341.4205 1.675408 9.43E08 n total
nc number of moles
n i=1 ni
ni mole number of component i
Table 2 shows the evolution of several parameters (tem-
nc number of components
perature, pressure, dimensionless volume, and cubic form)
nE number of components having equal nonzero BIP
during the iterative process for sample C with extended com-
with the remaining components
position. Only four iterations on dimensionless volume are
nNZ number of components having nonzero BIP
required for convergence.
p pressure
For all the situations considered, the dimensionality of the
q eigenvectors
problem is reduced; however, this reduction is spectacular for
qi elements
of the eigenvectors
mixtures with many components. The larger the number of
qi qi / a
components, the more efficient the proposed method is.
Q vector of reduction parameters
QS matrix of partial derivatives
6. Conclusions Q reduction
nc parameters
Q
i=1qi ni
An efficient procedure has been developed for critical Q Q / a
points calculation using the Heidemann and Khalil criticality r rank of matrix C
criteria. The proposed method is based on a reduction method R universal gas constant
that allows nonzero BIP in the EOS, and it requires low order S scaling matrix
determinants evaluation in the spinodal equation. The cubic Si see Eq. (16)
form can be evaluated using the information obtained from T temperature
spinodal calculation. v molar volume
For the computationally most expensive part of the algo- V total volume
rithm, the dimensionality can be significantly reduced using xi mole fraction, component i
the proposed method. The method is particularly efficient
for mixtures with many components and few nonzero BIP, Greek letters 
i (1/a) nc x a
such as naturally occurring hydrocarbon mixtures. Spectac- nc j=1 j ij
ular computer time savings can be expected for such calcu- i=1 i ni
lations. i bi /b
230 D.V. Nichita / Fluid Phase Equilibria 228229 (2005) 223231

nc
i=1 i ni
RTci
bi = b (A.7)
Kroneker delta pci
1 ,2 constants in EOS
1 2 in which Trj = T/Tcj and prj = p/pcj are the reduced temperature
dimensionless volume and pressure of component j (with critical temperature Tcj and
eigenvalues pressure pcj ) and the kij is the BIP between components i and
acentric factor j. The values of 1 , 2 , a and b and the expression of m as
a , b coefficients in the EOS a function of the acentric factor for the PR and SRK EOS
are as follows:
For the PREOS (1 = 1 + 2, 2 = 1 2), a =
Subscripts
0.45724 and b = 0.0778, and
c critical

i,j,k component index 0.37464 + 1.54226 0.269922 , < 0.489
pc pseudocritical m() = 0.379642 + 1.48503 0.1644232 (A.8)
r reduced
+0.016667 ,3 0.489
, reduction parameter index
For the SRK EOS (1 = 1, 2 = 0), a = 0.42748 and
Superscripts b = 0.08664, and
s scaled
T transposed m() = 0.48508 + 1.55171 0.156132 (A.9)
0 initial

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