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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
Peng-Robinson (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
m
pv RT ·
van der Waals
( )
c
m
m
a
p v b RT
v
]
+ − ·
]
]
Soave-Redlich-Kwong
( )
( )
( )
c
m
m m
a T
p v b RT
v v b
α ]
+ − ·
]
+
]
]
Peng-Robinson
( )
( ) ( )
( )
c
m
m m m
a T
p v b RT
v v b b v b
α ]
+ − ·
]
+ + −
]
]
The parameters
c
a , ( ) T α , 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 α 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.
Equations of State (MAM 04.Feb.2000) 1
We will focus on the two equations of most interest, the SRK and PR EOSs, first writing
the equations in the following common form.
( )
( ) ( )
( )
1 2
c
m
m m
a T
p v b RT
v f b v f b
α ]
+ − ·
]
+ +
]
]
Using the following substitutions
m
pv
z
RT
· (definition of gas deviation factor)
( )
2 2
c
a T p
A
R T
α
· (dimensionless)
bp
B
RT
· (dimensionless)
Equation can be algebraically rewritten in the following form:
3 2
2 1 0
0 z a z a z a − + − ·
where
( )
0
1 a B A wB B ] · + +
]
( )
1
a A B B u w u ] · − − +
]
( )
2
1 1 a B u · − −
SRK PR
1
f · 1
1 2 +
2
f · 0
1 2 −
1 2
u f f · + 1 2
1 2
w f f · 0 -1
2
4 u w σ · −
1
2 2
Note that even though Eq. is written in terms of z , Eq. can always be used to determine
the molar volume if desired.
Equations of State (MAM 04.Feb.2000) 2
The values of
c
a and b are determined by noting that at the critical point,
0
c
m
T
p
v

·

2
2
0
c
m
T
p
v

·

Since ( ) 1
c
T α · , evaluating these expressions at the critical point results in the following
expressions
2 2
c
c a
c
R T
a
p
· Ω
c
b
c
RT
b
p
· Ω
With the following values determined from the various EOSs.
SRK PR
a
Ω · 0.427480 0.457236
b
Ω · 0.086640 0.077796
c
z · 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
( )
( )
2
1 1
r
T m T α
]
· + −
]
where,
2
1 2 o
m m m m ω ω · + −
Equations of State (MAM 04.Feb.2000) 3
Values of the coefficients in Eq. can be obtained from the following table.
SRK PR
0
m · 0.480 0.37464
1
m · 1.574 1.54226
2
m · 0.176 0.26992
The parameter
ω
is called the Pitzer accentric factor and is empirically determined from
the actual vapor pressure curve for a substance according to the following relationship:
( )
0.7
log 1
r
vr
T
p ω
·
· − +
where,
( )
0.7
0.7
r
v c
vr
T
c
p T T
p
p
·
·
·
and
v
p is vapor pressure.
The values of
ω
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. 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 EOSs 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.
m
dG v dp ·
For an ideal gas, it can be shown that
Equations of State (MAM 04.Feb.2000) 4
( ) ln dG RT d p ·
For non-ideal fluids, a property called “fugacity” ( f )is defined having the following two
properties:
( ) ln dG RT d f ·
0
lim
p
f p

·
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,
ϕ
as
0
1
exp
p
f z
dp
p p
ϕ
]

· ·
]
]
]

results in the following expression
1
ln 1 ln
m
v
m
m
RT
z z p dv
RT v
ϕ

| `
· − − + −

. ,

The terms in Eq. can, of course, be evaluated using an EOS, resulting in the following:
( )
2
ln 1 ln ln
2
u
z B
A
z z B
u
B
z B
σ
ϕ
σ
σ
+ ]
+
]
· − − − −
]

] +
]
2 SOLUTIONS
In general an EOS can be solved for either one of the three parameters z (or
m
v ),
p
, or
T . First we’ll deal with what’s called a “flash” calculation, solving for z when pressure and
temperature are known.
Equations of State (MAM 04.Feb.2000) 5
Equation 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.
When there are three real roots, the largest root represents the z-factor 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 z-factor (and thus the
specific molar volume and/or density) is the following:
1. For a given pressure and temperature, determine the coefficients in Eq. .
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. .
Use the z-factor from the lowest fugacity.
4. Calculate densities,
pM
zRT
ρ · , and/or molar volumes,
m
zRT
v
p
·
, as desired.
Equations of State (MAM 04.Feb.2000) 6
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.
3 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
j
z
(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
j
x
and the
mole fractions of the gaseous phase
j
y
. By definition,
1
j j j
j j j
x y z · · ·
∑ ∑ ∑
.
Often compositions of the liquid and gaseous phases are expressed in terms of
equilibrium rations,
j
K
, defined by
j
j
j
y
K
x
·
Note that
j
K
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
j
K
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,
g
n%
. 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.
The
j
z
,
j
K
, and
g
n%
then fully define the composition of a two-phase mixture. Liquid
and gas compositions can be determined by molar balances using the following relationships.
Equations of State (MAM 04.Feb.2000) 7
( )
1 1
j
j
g j
z
x
n K
·
+ − %
( )
1 1
j j
j j j
g j
K z
y K x
n K
· ·
+ − %
Note that a bubble points,
j j
x z ·
, while at dew points,
j j
y z ·
.
Dealing with mixtures also requires that chemical potentials and fugacities must be
calculated for each component, defined by the following relationships.
( )
ln
j j
dG RT d f ·
0
lim
j j
p
f y p

·
Equation states that fugacities must approach partial pressures (ideal behavior) as
pressure approaches zero.
At equilibrium, each component’s fugacity must be the same in both phases, i.e.,
gj lj
f f ·

for all components. We can also define the fugacity coefficient for each component as
j
j
j
f
y p
ϕ ·
With these definitions, it then turns out that
lj
j
gj
K
ϕ
ϕ
·
To apply the EOSs for mixtures, effective mixture coefficients for Eq. must be
determined using some sort of “mixing rules”. For both the PR and SRK EOSs, the following
mixing rules are used to obtain the effective mixture values of b and
c
a α .
Equations of State (MAM 04.Feb.2000) 8
( )
1
c i ci i j cj j ij
i j
a y a y a α α α δ · −
∑ ∑
j j
j
b y b ·

Note that for a single component, these two equations will yield one components values
of
c
a α and b . Also, evn though these two equations are based on gas mixtures, they can also be
applied to liquid mixtures by substituting the
j
x
for the
j
y
. Equation is a double summation,
with both indexes i and j going over the entire number of components in the system.
The
ij
δ
are called “binary interaction coefficients” and are empirical measures of the
attractive and repulsive forces between molecules of unlike size. Note that
0
ii jj
δ δ · ·
and
0
ij ji
δ δ · ·
. 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.
EOS calculations of the fugacity coefficients for each phase are then made using the
following equation.
( ) ( ) ( )
2
ln 1 ln ln
2
j j j j
u
z B
A
z B z B A B
u
B
z B
σ
ϕ
σ
σ
+ ]
+
]
′ ′ ′ · − − − − −
]

] +
]
where,
( )
2 1
cj j i ci i ij
i
j
c
a y a
A
a
α α δ
α

′ ·

j
j
b
B
b
′ ·
Equations of State (MAM 04.Feb.2000) 9
Note that Eq. reverts to Eq. where there is only one component present.
For two-phase mixtures, Eq. 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 procedure for doing a flash calculation on a mixture the is the following.
1. Calculate the
cj j
a α
and
j
b
for each component. These are functions of pressure and
temperature, but not composition.
2. Guess values for the
j
K
. Various correlations are available for estimating these
values (e.g., McCain, 1990).
3. Find a value of
g
n%
which maintains molar balances, i.e., that ensures
1
j j
j j
x y · ·
∑ ∑
(more on this later).
4. Use the
j
x
in the mixing equations to find the coefficients and solve the EOS for the
liquid. Select the smallest root. Likewise use the
j
y
to solve the EOS for the gas
phase. Select the largest root.
5. Calculate fugacity coefficients for each component in each phase using Eq. . Use
these to determine the
j
K
from Eq. .
6. Repeat from Step 2, using the calculated
j
K
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.
( )
2
T C
j j
T C
j j
K K
Error
K K

·

Iterations should be stopped when the Eq. 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
g
n%
. The
following procedure is typically used.
Equations of State (MAM 04.Feb.2000) 10
When the
j
z
and
j
K
are known (as in Step 3 above), the correct value of
g
n%
is the one
that ensures molar balances. Although either the
j
x
or
j
y
equation may be used for this purpose,
here we will focus on the
j
x
equation, Eq. . Using Newton-Raphson iteration to solve this
equation results in the following.
( )
( )
1
1 1
j
g
j
g j
z
f n
n K
· −
+ −

%
%
( )
( )
( )
2
1
1 1
j j
g
j
g j
z K
f n
n K

′ ·
]
+ −
]

%
%
Recall that Newton-Raphson iterative involves successive guessing, with the “new” guess
calculated from the “old” one by
( )
( )
1
k
g
k k
g g
k
g
f n
n n
f n
+
· −

%
% %
%
One of the roots of Eq. is always
0
g
n · %
, so the initial guess should start well away from
this value. Outside the two-phase envelope, the value of
g
n%
is undefined and may take on non-
physical values. The following relationships define how to determine whether the calculation is
being done inside the two-phase envelope or not.
Liquid phase
1
j j
j
z K <

Gaseous phase
1
j
j j
z
K
<

Bubble point
1
j j
j
z K ·

Equations of State (MAM 04.Feb.2000) 11
Dew point
1
j
j j
z
K
·

Two-phase
1
j j
j
z K >

and
1
j
j j
z
K
>

The above procedure can also be used to calculate bubble and dew point pressures, by
simply iterating on pressure until the appropriate Eq. or is true. Again, the Excel Solver is a
good way to do this type of calculation.
4 EXACT VALUES OF EOS PARAMETERS
van der Waals
2 2 2 2
27
0.421875
64
c c
c
c c
R T R T
a
p p
· ·
1
0.125
8
c c
c c
RT RT
b
p p
· ·
3
0.375
8
c
z · ·
Soave-Redlich-Kwong
2 2 2 2 1 3 2 3
2
1 2 2
0.427480
9
c c
c
c c
R T R T
a
p p
| ` + +
· ·

. ,
1 3
2 1
0.086640
3
c c
c c
RT RT
b
p p
| ` −
· ·

. ,
1
0.333333
3
c
z · ·
Peng-Robinson
Equations of State (MAM 04.Feb.2000) 12
( ) ( )
( ) ( )
2 2 2 2
2 3 1 3
1 3 2 3
1715
112 80 2
16 2 13
1 2205 1134
0.457236
1536
16 2 13 16 2 13
162 16 2 13 45 16 2 13
c c
c
c c
R T R T
a
p p
]
− + − ]

]
]
· + + ·
]
] − −
]
]
− − + −
]
]
( )
( )
1 3
1 3
343
16 2 35
16 2 13
1
0.077796
1008
1536
144 16 2 13
16 2 13
c c
c c
RT RT
b
p p
]
− +
]

]
· ·
]
+ + −
]

]
]
( )
( )
1 3
1 3
1 7
11 16 2 13 0.307401
32
16 2 13
c
z
]
]
· − + − ·
]

]
]
5 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 04.Feb.2000) 13

We will focus on the two equations of most interest. is written in terms of z . Eq.Feb. Equations of State (MAM 04. the SRK and PR EOSs. can always be used to determine the molar volume if desired.   acα ( T ) p+  ( v − b ) = RT ( vm + f1b ) ( vm + f 2b )  m    Using the following substitutions z= pvm (definition of gas deviation factor) RT acα ( T ) p R 2T 2 A= (dimensionless) B= bp (dimensionless) RT Equation can be algebraically rewritten in the following form: z 3 − a2 z 2 + a1 z − a0 = 0 where a0 = B  A + wB ( B + 1)    a2 = 1 − B ( u − 1) f1 = f2 = u = f1 + f 2 w = f1 f 2 a1 = A − B  B ( u − w ) + u    SRK 1 0 1 0 1 PR 1+ 2 1− 2 2 -1 2 2 σ = u 2 − 4w Note that even though Eq. first writing the equations in the following common form.2000) 2 .

SRK 0.077796 0. evaluating these expressions at the critical point results in the following expressions ac = Ω a R 2Tc2 pc b = Ωb RTc pc With the following values determined from the various EOSs.086640 0. as given at the end of this document. m = mo + m1ω − m2ω 2 Equations of State (MAM 04.The values of ac and b are determined by noting that at the critical point. For both the SRK and PR equations. The numbers above can be expressed analytically.307401 Ωa = Ωb = zc = Note that the value of the z-factor at the critical point is also given.457236 0. the temperature-dependent parameter is expressed as α ( T ) = 1 + m 1 − Tr    where. ∂p ∂vm =0 Tc ∂2 p =0 2 ∂vm T c Since α ( Tc ) = 1 .2000) ( ) 2 3 .333333 PR 0.427480 0.Feb.

Of course the values of z for liquids will be smaller than those for gases since liquids are denser. sometimes called the Gibbs molar free energy ( G ). The values of ω are typically determined from published tables.26992 m0 = m1 = m2 = The parameter ω is called the Pitzer accentric factor and is empirically determined from the actual vapor pressure curve for a substance according to the following relationship: ω = − log pvr T =0. pvr T =0. changes in which are defined by the following relationship.480 1. are defined for liquids as well as gases.574 0.7Tc ) pc and pv is vapor pressure. since all of the quantities in Eq.2000) 4 . dG = vm dp For an ideal gas.54226 0. it can be shown that Equations of State (MAM 04. It should be noted that these cubic forms of the equation of state can apply to liquids as well as gases. along with critical temperature and pressure.7 + 1 r ( ) where.7 = r pv ( T = 0.176 PR 0. there is nothing restricting this to be the case. Even though z has traditionally been used for gases. SRK 0.37464 1.Values of the coefficients in Eq. the EOSs must be extended to include the concept of chemical potential. can be obtained from the following table.Feb. To address the more complex question of “phase”.

can. solving for z when pressure and temperature are known. of course. a property called “fugacity” ( f )is defined having the following two properties: dG = RT d ( ln f ) lim f = p p →0 Note that the fugacity can be thought of as the potential for transfer between phases. First we’ll deal with what’s called a “flash” calculation. resulting in the following: u +σ  z+B A  2 ln ϕ = z − 1 − ln ( z − B ) − ln  u −σ Bσ  z + B  2      2 SOLUTIONS In general an EOS can be solved for either one of the three parameters z (or vm ). or T . p . ϕ as  p z −1  f ϕ = = exp  ∫ dp  p 0 p    results in the following expression 1 ln ϕ = z − 1 − ln z + RT vm  RT  − p  dvm  ∫ v  ∞ m The terms in Eq.dG = RT d ( ln p ) For non-ideal fluids.2000) 5 . be evaluated using an EOS. This means that molecules will tend to move phase-wise. so as to minimize the fugacity. Equations of State (MAM 04. Further defining a fugacity coefficient.Feb.

For pure components. When there are three real roots. Solve this equation for the largest and smallest real roots using a cubic root solver. . A determination of which phase is present can be made by comparing the fugacities for both phases.Feb. then. Use the z-factor from the lowest fugacity. The phase with the lowest fugacity is the one present. The value of z will be relatively large for gases and relatively small for liquids. Three real roots. while the smallest root represents the z-factor of the liquid phase. there are two phases simultaneously present. there will be three real roots. there is generally one real root and two imaginary roots. seeking the pressure that results in equal liquid and gas fugacities. 4. and/or molar volumes. Calculate densities. 2. On the vapor pressure line. 3. The middle root is nonphysical. 2. away from the vapor pressure line. vm = .2000) 6 . In general the following possibilities are possible for the roots (solutions) of this equation: 1. the procedure for determining the z-factor (and thus the specific molar volume and/or density) is the following: 1. Near the vapor pressure line. since molecules can be in either phase. this means that their fugacities must be equal. some or all possibly repeated. determine the coefficients in Eq. . the largest root represents the z-factor of the gaseous phase. For a given pressure and temperature. the way vapor pressure is usually determined at a given pressure is to iterate on the above equations. as desired. When two phases are present concurrently. ρ = zRT pM . In fact. of course. One real root and two imaginary roots.Equation is a cubic equation. however. Calculate both liquid and gaseous fugacity coefficients (if there are two) using Eq. It is in this region that fugacities are needed to determine phase. For pure components. p zRT Equations of State (MAM 04.

of course. ng . The values of K j can be determined from correlations. until a pressure is selected so that the fugacities calculated in Step 3 are equal.2000) 7 . where j is the component index. and has a value ranging from zero (at a bubble point) to one (at a dew point) inside the envelope. Likewise the mole fractions of the liquid phase are given the symbols x j and the mole fractions of the gaseous phase y j . the composition of the total system (mixture) is usually taken as a “known”. By definition. and ng then fully define the composition of a two-phase mixture. 3 MIXTURES For mixtures an additional consideration must be taken into account. The final composition variable needed is the total mole fraction of the mixture that is in % the gaseous phase. composition. With so-called flash calculations. % The z j . Equations of State (MAM 04. The Excel Solver works quite well for this. defined by yj xj Kj = Note that K j will be small (but never zero) for components that prefer to be in the liquid phase. not defined outside the two-phase envelope. and much greater than one (but never infinite) for components that prefer to be in the gaseous phase. K j . ∑x =∑y =∑z j j j j j j = 1. spanning the total number of components in the system.If it is desired to find a vapor pressure at a given temperature. K j . The mole fractions of each component are given the symbols z j (not to be confused with the z-factor). but the more modern approach is to determine them through EOSs. This variable is. Often compositions of the liquid and gaseous phases are expressed in terms of equilibrium rations.Feb. iterate on the above procedure. Liquid and gas compositions can be determined by molar balances using the following relationships.

it then turns out that Kj = ϕlj ϕ gj To apply the EOSs for mixtures. i. f gj = f lj for all components. dG j = RT d ( ln f j ) lim f j = y j p p →0 Equation states that fugacities must approach partial pressures (ideal behavior) as pressure approaches zero. y j = z j . For both the PR and SRK EOSs.. while at dew points. We can also define the fugacity coefficient for each component as ϕj = fj yj p With these definitions. x j = z j . each component’s fugacity must be the same in both phases. Dealing with mixtures also requires that chemical potentials and fugacities must be calculated for each component.xj = % 1 + ng ( K j − 1) K jzj zj yj = K jxj = % 1 + ng ( K j − 1) Note that a bubble points.Feb. effective mixture coefficients for Eq. must be determined using some sort of “mixing rules”. At equilibrium. Equations of State (MAM 04. the following mixing rules are used to obtain the effective mixture values of b and acα .e.2000) 8 . defined by the following relationships.

they can also be applied to liquid mixtures by substituting the x j for the y j . When no data is available. 1989). There are many ways that binary interaction coefficients are characterized (Ahmed. 2 acjα j ∑ yi aciα i ( 1 − δ ij ) i      A′j = acα B′j = bj b 9 Equations of State (MAM 04. The δ ij are called “binary interaction coefficients” and are empirical measures of the attractive and repulsive forces between molecules of unlike size. Equation is a double summation. Often binary interaction coefficients are used to “history match” EOS calculations against actual PVT experiments. but in general they increase as the relative difference between molecular weights increase. EOS calculations of the fugacity coefficients for each phase are then made using the following equation. these two equations will yield one components values of acα and b . with both indexes i and j going over the entire number of components in the system. Note that δ ii = δ jj = 0 and δ ij = δ ji = 0 .acα = ∑ yi aciα i ∑ y j acjα j ( 1 − δ ij ) i j b = ∑ y jbj j Note that for a single component.2000) .Feb. evn though these two equations are based on gas mixtures. values of zero are sometimes use. Also. u +σ  z+B 2 A ln ϕ j = ( z − 1) B′j − ln ( z − B ) − ( A′j − B′j ) ln  u −σ Bσ z+B  2 where.

4. results in a value less than some specified tolerance.Feb. that ensures ∑x =∑y j j j j = 1 (more on this later). both EOS calculations will yield three real roots. 1990). Use these to determine the K j from Eq. Calculate fugacity coefficients for each component in each phase using Eq.Note that Eq. These are functions of pressure and temperature. Find a value of ng which maintains molar balances. The following procedure is typically used. Select the smallest root. but not composition. reverts to Eq. Error = ∑ (K T j − KC ) j 2 KT KC j j Iterations should be stopped when the Eq. using the calculated K j as the new trial values. Various correlations are available for estimating these values (e. and the largest root of the gas equation should be taken as the gas z-factor. . Guess values for the K j . 1. must be solved twice. Select the largest root. i.2000) 10 . The smallest root of the liquid equation should be taken as the z-factor for the liquid phase. The procedure for doing a flash calculation on a mixture the is the following. once for the liquid phase and once for the gas phase. Use the x j in the mixing equations to find the coefficients and solve the EOS for the liquid. where there is only one component present. When two phases exist. McCain (1990) suggests the following possible error calculation to determine convergence.. 5. % Step 3 is usually done with a Newton-Raphson type iteration to find the value of ng . Stop when the calculated values are near the trial values.. % 3. . McCain. Eq. Likewise use the y j to solve the EOS for the gas phase.e.g. Equations of State (MAM 04. 6. 2. Repeat from Step 2. Calculate the acjα j and b j for each component. For two-phase mixtures.

2000) 11 .% When the z j and K j are known (as in Step 3 above). % f ( ng ) = 1 − ∑ j % 1 + ng ( K j − 1) z j ( K j − 1) zj % f ′ ( ng ) = ∑ j 1 + ng ( K j − 1)  %   2 Recall that Newton-Raphson iterative involves successive guessing. The following relationships define how to determine whether the calculation is being done inside the two-phase envelope or not. Although either the x j or y j equation may be used for this purpose. with the “new” guess calculated from the “old” one by k % f ( ng ) % % n =n − k g k +1 g k % f ′ ( ng ) % One of the roots of Eq. the value of ng is undefined and may take on nonphysical values. Using Newton-Raphson iteration to solve this equation results in the following. the correct value of ng is the one that ensures molar balances. Eq. Liquid phase ∑z K j j j <1 Gaseous phase ∑K j j j zj j <1 Bubble point ∑z K j =1 Equations of State (MAM 04. so the initial guess should start well away from % this value. here we will focus on the x j equation. is always ng = 0 .Feb. Outside the two-phase envelope. .

086640 c  pc  3  pc zc = 1 = 0.375 8 zc = Soave-Redlich-Kwong  1 + 21 3 + 22 3  R 2Tc2 R 2T 2 ac =  = 0.333333 3 Peng-Robinson Equations of State (MAM 04. 4 EXACT VALUES OF EOS PARAMETERS van der Waals ac = b= 27 R 2Tc2 R 2Tc2 = 0.427480 2c  9 pc   pc  21 3 − 1  RTc RT b= = 0. the Excel Solver is a good way to do this type of calculation.Dew point ∑K j j zj j =1 Two-phase ∑z K j j > 1 and ∑K j zj j >1 The above procedure can also be used to calculate bubble and dew point pressures.Feb. by simply iterating on pressure until the appropriate Eq.125 c 8 pc pc 3 = 0. or is true. Again.2000) 12 .421875 64 pc pc 1 RTc RT = 0.

Houston (1989). Jr.2000) 13 . W. Tulsa (1990)..077796 RTc 13  p pc  c    1  7 zc = 11 − 32  16 2 − 13   ( ) 13 + 16 2 − 13 ( ) 13   = 0. PennWell Publishing Co.307401    5 REFERENCES Ahmed.457236  pc  pc  23    343  16 2 − 35 + 16 2 − 13 1  b= 1008 1536  + + 144 16 2 − 13 13  16 2 − 13   ( ) ( )    RTc = 0. Equations of State (MAM 04.: The Properties of Petroleum Fluids.D.: Hydrocarbon Phase Behavior. T... Gulf Publishing Co. McCain.Feb. 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   ( ) ( ) ( ) ( )     R 2Tc2 R 2Tc2 = 0.