1.

Equations of State
When the effects of complex phase behavior cannot be accurately
calculated using simple approaches, it is often desirable to utilize
some sort of equation of state (EOS). An EOS approach is often
recommended when dealing with volatile oils and retrograde
condensate gases. The two most common equations of state
utilized in petroleum engineering applications are the PengRobinson (PR) and Soave-Redlich-Kwong (SRK) equations, which
historically were derived from van der Waals (vdW) equation.
These three equations are called cubic because they result in a
cubic representation for the molar volume. The basic equations are
the following:
Ideal Gas
pvm = RT

(1.1)
van der Waals

ac
p + 2 ( vm b ) = RT
vm

(1.2)

Soave-Redlich-Kwong

ac (T )
p+
( vm b ) = RT
vm ( vm + b )

(1.3)

Peng-Robinson

ac (T )
p+
( vm b ) = RT
vm ( vm + b ) + b ( vm b )

Equations of State (MAM 11.Dec.2000)

(1.4)

The parameters ac , (T ) , and b are empirically determined from

experimental data (for pure components, critical temperature and
pressure, and a specified point on the vapor pressure curve), (T )
being a function of temperature and having a value of one at the
critical temperature. Note that the parameters do not have the same
value in each equation.
We will focus on the two equations of most interest, the SRK and
PR EOSs, first writing the equations in the following common
form.

ac (T )
p+
( v b ) = RT
( vm + f1b )( vm + f 2b ) m

(1.5)

Using the following substitutions

z=

A=

B=

pvm
(definition of gas deviation factor)
RT
ac (T ) p
R 2T 2

(1.6)

(dimensionless)

bp
(dimensionless)
RT
Equation 1.5 can be algebraically rewritten in the following form:

z 3 a2 z 2 + a1 z a0 = 0

(1.7)

where
a0 = B A + wB ( B + 1)

a1 = A B B ( u w ) + u
a2 = 1 B ( u 1)

Equations of State (MAM 11.Dec.2000)

SRK

PR

1
0
1
0
1

1+ 2
1 2
2
-1

f1 =
f2 =
u = f1 + f 2
w = f1 f 2

= u 2 4w

2 2

Note that even though Eq. 1.7 is written in terms of z , Eq. 1.6 can
always be used to determine the molar volume if desired.
The values of ac and b are determined by noting that at the
critical point,

p
vm

=0

(1.8)

2 p
=0
vm2 T

(1.9)

Tc

Since (Tc ) = 1 , evaluating these expressions at the critical point

results in the following expressions

ac = a

b = b

R 2Tc2
pc

(1.10)

RTc
pc

(1.11)

with the following values determined from the various equations of

state.

Equations of State (MAM 11.Dec.2000)

SRK

PR

a =

0.427480

0.457236

b =

0.086640

0.077796

zc =

0.333333

0.307401

Note that the value of the z-factor at the critical point is also given.
The numbers above can be expressed analytically, as given at the
end of this document.
For both the SRK and PR equations, the temperature-dependent
parameter is expressed as

(T ) = 1 + m 1 Tr

(1.12)

where,
m = mo + m1 m2 2

(1.13)

Values of the coefficients in Eq. 1.13 can be obtained from the

following table.
SRK

PR

m0 =

0.480

0.37464

m1 =
m2 =

1.574
0.176

1.54226
0.26992

The parameter is called the Pitzer accentric factor and is

empirically determined from the actual vapor pressure curve for a
substance according to the following relationship:

= log pvr T =0.7 + 1

r

(1.14)

where,
pvr T =0.7 =

pv (T = 0.7Tc )

pc

(1.15)

and pv is vapor pressure.

Equations of State (MAM 11.Dec.2000)

The values of are typically determined from published tables,

along with critical temperature and pressure.
It should be noted that these cubic forms of the equation of state
can apply to liquids as well as gases. Even though z has
traditionally been used for gases, there is nothing restricting this to
be the case, since all of the quantities in Eq. 1.6 are defined for
liquids as well as gases. Of course the values of z for liquids will
be smaller than those for gases since liquids are denser.
To address the more complex question of phase, the equations of
state must be extended to include the concept of chemical
potential, sometimes called the Gibbs molar free energy ( G ),
changes in which are defined by the following relationship.
dG = vm dp

(1.16)
For an ideal gas, it can be shown that

dG = RT d ( ln p )

(1.17)

For non-ideal fluids, a property called fugacity ( f ) is defined

having the following two properties.
dG = RT d ( ln f )

(1.18)

lim f = p

(1.19)

p 0

Note that the fugacity can be thought of as the potential for transfer
between phases. This means that molecules will tend to move
phase-wise, so as to minimize the fugacity.
Further defining a fugacity coefficient, as

Equations of State (MAM 11.Dec.2000)

p z 1
f
= exp
dp
p
0 p

(1.20)

results in the following expression

1
ln = z 1 ln z +
RT

vm

RT

p dvm

(1.21)

The terms in Eq. 1.21 can, of course, be evaluated using an EOS,

resulting in the following.
u +

z+B
A
2
ln = z 1 ln ( z B )
ln
B z + B u
2

(1.22)

1.1 Solutions
In general an EOS can be solved for either one of the three
parameters z (or vm ), p , or T . First well deal with whats called
a flash calculation, solving for z when pressure and temperature
are known.
Equation 1.7 is a cubic equation. In general the following
possibilities are possible for the roots (solutions) of this equation.
1. Three real roots, some or all possibly repeated.
2. One real root and two imaginary roots.
For pure components, away from the vapor pressure line, there is
generally one real root and two imaginary roots. The value of z
will be relatively large for gases and relatively small for liquids.
Near the vapor pressure line, however, there will be three real
roots. It is in this region that fugacities are needed to determine

phase.

Equations of State (MAM 11.Dec.2000)

When there are three real roots, the largest root represents the zfactor of the gaseous phase, while the smallest root represents the

z-factor of the liquid phase. The middle root is non-physical. A

determination of which phase is present can be made by comparing
the fugacities for both phases. The phase with the lowest fugacity
is the one present.
On the vapor pressure line, of course, there are two phases
simultaneously present. When two phases are present concurrently,
this means that their fugacities must be equal, since molecules can
be in either phase. In fact, the way vapor pressure is usually
determined at a given pressure is to iterate on the above equations,
seeking the pressure that results in equal liquid and gas fugacities.
For pure components, then, the procedure for determining the zfactor (and thus the specific molar volume and/or density) is the
following:
1. For a given pressure and temperature, determine the
coefficients in Eq. 1.7.
2. Solve this equation for the largest and smallest real
roots using a cubic root solver.
3. Calculate both liquid and gaseous fugacity coefficients
(if there are two) using Eq. 1.22. Use the z-factor from
the lowest fugacity.
4. Calculate densities, =

vm =

pM
, and/or molar volumes,
zRT

zRT
, as desired.
p

If it is desired to find a vapor pressure at a given temperature,

iterate on the above procedure, until a pressure is selected so that
the fugacities calculated in Step 3 are equal. The Excel Solver
works quite well for this.

Equations of State (MAM 11.Dec.2000)

1.2 Mixtures
For mixtures an additional consideration must be taken into
account, composition. With so-called flash calculations, the
composition of the total system (mixture) is usually taken as a
known. The mole fractions of each component are given the
symbols z j (not to be confused with the z-factor), where j is the
component index, spanning the total number of components in the
system. Likewise the mole fractions of the liquid phase are given
the symbols x j and the mole fractions of the gaseous phase y j . By
definition,

x =y =z
j

= 1.

Often compositions of the liquid and gaseous phases are expressed

in terms of equilibrium rations, K j , defined by

Kj =

yj

(1.23)

xj

Note that K j will be small (but never zero) for components that
prefer to be in the liquid phase, and much greater than one (but
never infinite) for components that prefer to be in the gaseous
phase. The values of K j can be determined from correlations, but
the more modern approach is to determine them through EOSs.
The final composition variable needed is the total mole fraction of
the mixture that is in the gaseous phase, n% g . This variable is, of
course, not defined outside the two-phase envelope, and has a
value ranging from zero (at a bubble point) to one (at a dew point)
inside the envelope.

Equations of State (MAM 11.Dec.2000)

The z j , K j , and n% g then fully define the composition of a twophase mixture. Liquid and gas compositions can be determined by
molar balances using the following relationships.

xj =

zj

1 + n% g ( K j 1)

yj = K j xj =

Kjzj

1 + n% g ( K j 1)

(1.24)

(1.25)

Note that a bubble points, x j = z j , while at dew points, y j = z j .

Dealing with mixtures also requires that chemical potentials and
fugacities must be calculated for each component, defined by the
following relationships.

dG j = RT d ( ln f j )

(1.26)

lim f j = y j p

(1.27)

p 0

Equation 1.27 states that fugacities must approach partial pressures

(ideal behavior) as pressure approaches zero.
At equilibrium, each components fugacity must be the same in
both phases, i.e., f gj = flj for all components. We can also define
the fugacity coefficient for each component as

j =

fj

(1.28)

yj p

With these definitions, it then turns out that

Equations of State (MAM 11.Dec.2000)

lj
gj

Kj =

(1.29)

To apply the equations of state for mixtures, effective mixture

coefficients for Eq. 1.7 must be determined using some sort of
mixing rules. For both the PR and SRK equations of state, the
following mixing rules are used to obtain the effective mixture
values of b and ac .
ac = y j acj j yi aci i (1 ij )

(1.30)

b = y jbj

(1.31)

Note that for a single component, these two equations will yield
one components values of ac and b . Also, even though these
two equations are based on gas mixtures, they can also be applied
to liquid mixtures by substituting the x j for the y j . Equation 1.30
is a double summation, with both indexes i and j going over the
entire number of components in the system.
The ij are called binary interaction coefficients and are
empirical measures of the attractive and repulsive forces between
molecules of unlike size. Note that ii = jj = 0 and ij = ji = 0 .
There are many ways that binary interaction coefficients are
characterized (Ahmed, 1989), but in general they increase as the
relative difference between molecular weights increase. When no
data is available, values of zero are sometimes use. Often binary
interaction coefficients are used to history match EOS
calculations against actual PVT experiments.

Equations of State (MAM 11.Dec.2000)

10

EOS calculations of the fugacity coefficients for each phase are

then made using the following equation.
u +

z+B 2
A
ln j = ( z 1) Bj ln ( z B )
( Aj Bj ) ln
u
B
z+B
2

(1.32)

where,

Aj =

Bj =

2 acj j yi aci i (1 ij )
i

(1.33)

ac

bj

(1.34)

Note that Eq. 1.32 reverts to Eq. 1.22 where there is only one
component present.
For two-phase mixtures, Eq. 1.7 must be solved twice, once for the
liquid phase and once for the gas phase. When two phases exist,
both EOS calculations will yield three real roots. The smallest root
of the liquid equation should be taken as the z-factor for the liquid
phase, and the largest root of the gas equation should be taken as
the gas z-factor.
The above equations can be simplified using the following
definitions.
fbj =

Tcj

(1.35)

pcj

f aj (T ) =

Tcj
1 + mo + m1 j m2 2j
pcj

Equations of State (MAM 11.Dec.2000)

) 1

T
Tcj

(1.36)

11

Then,
A = a

B = b

Aj = 2

p
T2

y f y f (1 )
j

i ai

(1.37)

ij

p
y j fbj
T j

(1.38)

f aj yi f ai (1 ij )
i

(1.39)

y j f aj yi f ai (1 ij )
j

Bj =

aj

f bj

(1.40)

j bj

The procedure for doing a flash calculation on a mixture then is the

following.
1. Calculate the acj j and b j for each component. These
are functions of pressure and temperature, but not
composition.
2. Guess values for the K j . Various correlations are
available for estimating these values (e.g., McCain,
1990).
3. Find a value of n% g which maintains molar balances,
i.e., that ensures

x =y
j

= 1 (more on this later).

4. Use the x j in the mixing equations to find the

coefficients and solve the EOS for the liquid. Select the
smallest root. Likewise use the y j to solve the EOS for
the gas phase. Select the largest root.
5. Calculate fugacity coefficients for each component in
each phase using Eq. 1.32. Use these to determine the
K j from Eq. 1.29.

Equations of State (MAM 11.Dec.2000)

12

6. Repeat from Step 2, using the calculated K j as the new

trial values. Stop when the calculated values are near
the trial values. McCain (1990) suggests the following
possible error calculation to determine convergence.
Error =

(K

T
j

K Cj

(1.41)

K Tj K Cj

7. Iterations should be stopped when the Eq. 1.41 results

in a value less than some specified tolerance.
Step 3 is usually done with a Newton-Raphson type iteration to
find the value of n% g . The following procedure is typically used.
When the z j and K j are known (as in Step 3 above), the correct
value of n% g is the one that ensures molar balances. Although either
the x j or y j equation may be used for this purpose, here we will
focus on the x j equation, Eq. 1.24. Using Newton-Raphson
iteration to solve this equation results in the following.
f ( n% g ) = 1
j

f ( n% g ) =
j

zj

1 + n% g ( K j 1)
z j ( K j 1)

1 + n% g ( K j 1)

(1.42)

(1.43)

Recall that Newton-Raphson iteration involves successive

guessing, with the new guess calculated from the old one by

n%

k +1
g

= n%
k
g

( )
f ( n% )
f n% gk

k
g

(1.44)

One of the roots of Eq. 1.42 is always n% g = 0 , so the initial guess

should start well away from this value. Outside the two-phase

Equations of State (MAM 11.Dec.2000)

13

envelope, the value of n% g is undefined and may take on nonphysical values. The following relationships define how to
determine whether the calculation is being done inside the twophase envelope or not.
Liquid phase

z K
j

<1

(1.45)

Gaseous phase
j

Bubble point

zj
Kj

z K
j

<1

(1.46)

=1

(1.47)

Dew point

zj

K
j

Two-phase

=1

(1.48)

z K
j

> 1 and

zj

K
j

>1

(1.49)

The above procedure can also be used to calculate bubble and dew
point pressures, by simply iterating on pressure until the
appropriate Eq. 1.47 or 1.48 is true. Again, the Excel Solver is a
good way to do this type of calculation.

1.3 Exact Values of EOS Parameters

van der Waals

ac =

b=

R 2Tc2
27 R 2Tc2
= 0.421875
pc
64 pc

1 RTc
RT
= 0.125 c
pc
8 pc

Equations of State (MAM 11.Dec.2000)

14

zc =

3
= 0.375
8

Soave-Redlich-Kwong
1 + 21 3 + 22 3 R 2Tc2
R 2Tc2
ac =
= 0.427480 2

9
pc

pc
21 3 1 RTc
RT
b=
= 0.086640 c

pc
3 pc

zc =

1
= 0.333333
3

Peng-Robinson

1715
112 + 80 2
16 2 13

1
2205
1134
ac =
+
+
23
13
1536 16 2 13
16 2 13

13

162 16 2 13 + 45 16 2 13

343

16 2 35 + 16 2 13
1
b=
1008
1536 +
+ 144 16 2 13
13

16
2
13

1
7
zc =
11
32
16 2 13

13

+ 16 2 13

13

R 2Tc2
R 2Tc2
= 0.457236

pc
pc

23

RTc = 0.077796 RTc

13
p
pc
c

= 0.307401

1.4 References
Ahmed, T.: Hydrocarbon Phase Behavior, Gulf Publishing Co., Houston (1989).
McCain, W.D., Jr.: The Properties of Petroleum Fluids, PennWell Publishing Co., Tulsa (1990).

Equations of State (MAM 11.Dec.2000)

15