University of Jordan

Chemical Engineering Department

Chemical Engineering Thermodynamics 905721

Dr. Ali Khalaf Al-Matar

aalmatar@ju.edu.jo

Exam I Solution
20/11/2003

Derivation of the fugacity coecient for the

Peng-Robinson EOS

The derivation is similar to the derivation given in class for the van der Waals
EOS. We need to get the equation of state in its mathematical form combined
with its associated mixing rules. One of the tricks in the question is that regardless of the complexity of the combining rules given, the derivation is done
once. This is a result of the combining rules being composition independent.
Consequently, we need only to derive the expression for the fugacity coecient
once (not three times for every case).
You can solve this problem using a simple or a hard approach. The simple
approach includes using the residual Helmholtz free energy and its relation to
fugacity. The hard approach involves the brute force calculation of the derivatives required within the volume integral for fugacity. I am solving using the
residual Helmholtz free energy approach.

1.1

Obtain the EOS

The Peng-Robinson EOS is given as

P =

RT
a
RT
a

v b v(v + b) + b(v b)
v b v2 + 2vb b2

(1)

The mixing rules to be used are

a =

b =

m X
m
X
i=1 j=1
m X
m
X

xi xj aij =
xi xj bij =

i=1 j=1

m m
1 XX
ni nj aij
n2T i=1 j=1

m m
1 XX
ni nj bij
n2T i=1 j=1

(2)

(3)

With the cross parameters given by the appropriate combining rule. Notice
that the formulation in the expressions for the a and b parameters is similar
which reduces the amount of derivatives to be evaluated.
1

1.2

Convert the EOS to Density and Compressibility Notation

The equation of state to be used (regardless of its complexity) needs to be converted to the density (specific volume) and compressibility factor. Consequently,
the Peng-Robinson EOS becomes
Z=

1.3

1
1
a

1 b RT 1 + 2b b2 2

(4)

Obtain an Expression for Helmholtz Free Energy

We have an equation of state that we can apply for a pure component to obtain
the residual Helmholtz free energy. At a constant temperature and volume we
can use
Z
Zb
(a aIG )
Z 1
Z 1
=
d =
d(b)
(5)
RT

b
0

From the Peng-Robinson EOS

Z 1 =
=

1
1 b
a
1

2
2
1 b RT 1 + 2b b
1 b
1
b
a

1 b RT 1 + 2b b2 2

(6)

Substitute this expression into the residual Helmholtz free energy

(a aIG )
=
RT

Zb
0

a
1
d(b) +
1 b
bRT

Zb
0

1
d(b)
1 + 2b b2 2

The first term to the right hand side of the equal sign is easy to integrate.
However, the second can be obtained from the tables of integration formulas as

Z
2a0 x + b0 b02 4a0 c0 1/2
1
1

dx =
ln
(7)
1/2
1/2
02
0
0
0
0
02
0
0

a0 x2 + b0 x + c0
(b 4a c )
2a x + b + (b 4a c )

This result applies when the discriminator is negative i.e.,

4a0 c0 b02 < 0
In our case we have
a0 = b2 , b0 = 2b, c0 = 1
Which upon substitution

1/2
02
= (8b2 )1/2 = 8b = 2 2b
b 4a0 c0
2

(8)

Substituting back and carrying out the first integral to get

"
#

a
(a aIG )
1 + (1 + 2)b

ln
= ln(1 b)
RT
8bRT
1 + (1 2)b

(9)

We can use the compressibility factor, and the A and B factors to reduce this
equation into dimensionless form. Notice that the A factor is not the Helmholtz
free energy to avoid confusion between symbols.
"
#

(a aIG )
Z + (1 + 2)B
A

ln
(10)
= Z 1 ln(Z B)
RT
8B
Z + (1 2)B

1.4

Obtain an Expression for the Fugacity Coecient

Using the relationship between fugacity coecient and residual Helmholtz free
energy we have

(A AIG )
ln i =
ln Z
(11)
ni
RT
T,V,nj
Consequently, we need to put the residual Helmholtz free energy into its extensive form by multiplying by the total number of moles

i
h

an2T
(A AIG )
ln 1 + (1 + 2)b ln 1 + (1 2)b
= nT ln(1b)
RT
8bRT nT
(12)
Carry out the dierentiation with respect to the number of moles of any arbitrary component

(A AIG )/RT
n
(b)
= ln(1 b) +
(13)
ni
(1 b)
ni
T,V,nj

(b)
(b)
2
2)
2) ni
(1
+
(1

ni
anT

8bRT nT
1 + (1 + 2)b
1 + (1 2)b

# (an2T )
"
(nT b)

2
ni
ni
an
1 + (1 + 2)b

T
ln
2
(n
1 + (1 2)b
8bRT nT
8RT
T b)
This contribution can be evaluated if the derivatives with respect to the
number of moles are obtain. The next section derives general expressions for
the quadratic mixing rules.

1.5

Obtain Derivatives of the Mixing Rules

The following derivatives are required to be obtained from the mixing rules
#
#
"
"
m
m P
m
m
P
P
P
ni nj aij
ni
nj aij

i=1 j=1
i=1 j=1
(n2T a)
=

ni
ni
ni

nj

(n2T a)
ni

nj

= 2

nj

m
X

nj

nk aik .

(14)

k=1

Also,

(nT b)
ni

"

nj

(nT b)
ni

nT

nj

m P
m
P

ni nj bij

ni

i=1 j=1

"

k=1

ni nj bij

ni

i=1 j=1

"

m
X

m
m P
P

nT

= 2
nj

1
nT

m m
1 XX
ni nj bij
n2T i=1 j=1

nj

m
P

i=1

m
P

ni

nj bij

ni

j=1

nj

xk bik b.

(15)

For a single summation:

(nT b)
ni

nj

m
P

ni bi )

i=1

ni

nj

= bi

(16)

1.6

Plug into the Fugacity Coecient Expression

The derivatives are ready to be plugged into the fugacity coecient expressions
as follows

m
P
xk bik b
2
k=1
ln i = ln Z ln(1 b) +
(1 b)

m
P
#

xk bik b "
a 2
(1 2)
(1 + 2)
k=1

8bRT
1 + (1 + 2)b 1 + (1 2)b

m
P
m
P
#
"

2
xk aik
xk bik b
2

a
1 + (1 + 2)b
k=1
k=1

ln

b
1 + (1 2)b
8bRT
8bRT
Simplifying this equation further by taking a common factor in the last term to
obtain

m
P
xk bik b
2
k=1
ln i = ln Z ln(1 b) +
(1 b)

m
P
#

xk bik b "
a 2
(1 + 2)
(1 2)
k=1

8bRT
1 + (1 + 2)b 1 + (1 2)b

m
m
P
"
# 2 P xk aik

xk bik b
2

a
1 + (1 + 2)b
k=1

k=1

ln

a
b
8bRT
1 + (1 2)b
To simplify the notation further define
m
!
X
bi =
2
xk bik b

(17)

k=1

ai

m
X

xk aik

k=1

From which
ln i

bi
= ln Z ln(1 b) +
(1 b)
"
#

abi
(1 + 2)
(1 2)

8bRT 1 + (1 + 2)b 1 + (1 2)b

"
#

a
1 + (1 + 2)b
2ai
bi

ln

a
b
8bRT
1 + (1 2)b
5

(18)

There is another simplification that can be carried out

"
#

(1 2)
abi
bi
(1 + 2)

(1 b)
8bRT 1 + (1 + 2)b 1 + (1 2)b

bi
1
bi
b
ab
=
= (Z 1)

b (1 b)
b
8bRT 1 + 2b b2 2
Consequently,
ln i

bi
bi
= ln Z ln(1 b) +
+ (Z 1)
(1 b)
b
"
#

1 + (1 + 2)b
2ai
bi
a

ln

a
b
8bRT
1 + (1 2)b

(19)

To have a more compact notation, define the variables in terms of the reducing
variables A, B, and Z as follows
b =

B
;
Z

a
A
= ;
bRT
B

ai
Ai
=
;
a
A

bi
Bi
=
.
b
B

Applying these transformations, we end up with the desired expression for the
fugacity coecient using the Peng-Robinson equation of state. This expression is
derived for quadratic mixing rules for the co-volume and the energy parameters.
It simplifies a little computationally if we use arithmetic averages for the covolume.
"
#

Bi
Z + (1 + 2)B
2Ai
A
Bi

ln i = ln(ZB)+ (Z1)
ln

. (20)
B
A
B
8B
Z + (1 2)B
where
B

Bi

bP
;
RT

m
P
xk bik b P
2
k=1

RT
RTc
b = 0.07780
Pc
aP
A =
;
(RT )2

m
P
xk aik P
k=1
Ai =
;
(RT )2
(RTc )2
(T );
a(T ) = 0.45724
Pc
6

(21)

(22)
(23)
(24)

(25)
(26)


r !
p
T
(T ) = 1 + 1
;
Tc

(27)

= 0.37464 + 1.5422 0.26992 2 .

(28)

Algorithm for using the Fugacity Expression

The expression for the fugacity coecient and its associated variables and equations needs to be solved to obtain a value for the fugacity. This is not hard
computationally. However, one of the main points encountered frequently is the
solution for the roots of a cubic equation. The provided notes are implemented
in the Excel worksheet to obtain the roots of the cubic at any given temperature
and pressure.

Mixing Rules

Three mixing rules were used to solve the exam statement.

Lorentz-Berthelot

1
(bii + bjj ),
2

(29)

aij = (aii ajj )1/2 .

(30)

bij =

Waldman-Hagler
bij =

b2ii + b2jj
2

1/2

aij = (aii ajj )

MADAR-1

2
1X
bij =
3

!1/2
bii bjj
b2ij

,
!

0.25 (bii + bjj )2

L/3 L/3

(31)

1
! 22L/3

bii bjj

!
bii bjj
1/2
aij = (aii ajj )
.
b2ij
L=0

(32)

(33)

(34)

Isobutane and Carbon Dioxide System

The exam asked to generate plots for the fugacity as a function of composition
and pressure for the system: isobutane and carbon dioxide. The required input
information are given below for the two components.
The fugacity coecient as obtained from the Peng-Robinson equation of
state was evaluated as a function of pressure and composition using Microsoft
7

Table 1: Critical parameters, and the acentric factors of

i-butane.
Component
Tc (K) Pc (MPa) (-)
Carbon dioxide 304.14
7.375 0.239
Isobutane
407.8
3.604 0.183

carbon dioxide and

Zc (-)
0.274145
0.275296

Excel. The Excel worksheet is obtained and modified from the textbook of
Elliot and Lira.
Figures 1 through 3 present the final plots of fugacity for isobutane and
carbon dioxide respectively as a function of composition and pressure. Figure
1 is plotted using the Lorentz-Berthelot set of mixing rules, Figure 2 is plotted
using the Waldman-Hagler, while Figure 3 is plotted using the MADAR-1 set
of mixing rules. Additionally, Figure 4 is plotted to show the eect of mixing
rules on the same graph at pressures of 1, 2, and 4 MPa.

4.1

Pure Component Limit

From the first three figures, it is evident that at the pure component limit, the
fugacity of CO2 approaches the pressure of the system. This is to be expected
since CO2 is supercritical at the temperature of the system. However, for the
isobutane it seems that the fugacity is almost an order of magnitude lower than
the system pressure. Isobutane being a liquid at the given temperature explains
the low fugacity of at the pure component limit. Furthermore, there is a linear
composition dependence at any given pressure as the pure component limit is
approached.

4.2

Influence of System Pressure

The pressure aects the fugacity of both components appreciably. However, the
influence of the pressure may be divided into two main regions:
At pressures below approximately 1 MPa, the fugacity is a linear function
of the composition in all the composition range.
At pressures above approximately 1 MPa, the fugacity begins to show some
sort of going through a maximum, rising again, going through a minimum,
then it begins to increase again. This is due to the mixture being a
vapor approaching its dew pressure at compositions rich in CO2 that is
being enriched with isobutane tending to lower the fugacity. Consequently,
condensing the mixture to a liquid phase at isobutane rich areas.
At very low pressures, the ideal gas mixture limit is approached. This leads
to the fugacity of any component being equal to its partial pressure. This
happens at a pressure of 0.001 MPa which is suciently low to guarantee the
application of the ideal gas mixture limit. This pressure was given to check

the results obtained from the Excel sheet. The ideal gas mixture and pure
component limits are useful safeguards for checking and debugging the codes
used.

4.3

Eect of Dierent Mixing Rules

The figures provided; indicate that there is an eect of the mixing rules used.
There are minor dierences between the Waldman-Hagler and MADAR-1 rules.
However, both rules feature some major dierences with the Lorentz-Berthelot
rules. These dierences increase close to regions where there is a liquid phase.
The Lorentz-Berthelot rules provides lower values of the fugacity compared to
the Waldman-Hagler and MADAR-1 rules. This may be explained by the overestimation of repulsive forces using the Lorentz-Berthelot rules.
The dierences between the Lorentz-Berthelot rules and the two other rules
is quantitative and qualitative. The trends predicted and locations of phase
changes are contradictory among these rules. These dierences increase with
the pressure i.e., increase when the Lorentz-Berthelot rules results are not as
good as the gas limits. The dierence in the values of fugacity amounts to
threefold dierence. Consider P = 4 MPa, the maximum fugacity of isobutane
predicted by the Lorentz-Berthelot rules is about 0.2 MPa at x = 0.15, while
that predicted by Waldman-Hagler and MADAR-1 rules is 0.57 MPa at x =
0.37! Additionally, the Lorentz-Berthelot rules show an almost constant value of
carbon dioxide fugacity over the region where minimum and maximum fugacities
in isobutane fugacity occurs. This is some sort of an inconsistency compared to
the inverted trends predicted by the Waldman-Hagler and MADAR-1 rules.

0.8

0.001 MPa
0.100 MPa
1.000 MP
2.000 MPa
4.000 MPa

Fugacity of isobutane (MPa)

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Mole fraction of isobuatne

Fugacity of carbon dioxide (MPa)

3.5

0.001 MPa
0.100 MPa
1.000 MP
2.000 MPa
4.000 MPa

3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Mole fraction of isobutane

Figure 1: Fugacities of isobuatne and carbon dioxide as a function of composition

and pressure using the Lorentz-Berthelot mixing rules.

10

0.8

0.001 MPa
0.100 MPa
1.000 MP
2.000 MPa
4.000 MPa

Fugacity of isobutane (MPa)

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.7

0.8

0.9

1.0

Mole fraction of isobuatne

Fugacity of carbon dioxide (MPa)

0.001 MPa
0.100 MPa
1.000 MP
2.000 MPa
4.000 MPa

0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

Mole fraction of isobutane

Figure 2: Fugacities of isobuatne and carbon dioxide as a function of composition

and pressure using the Waldman-Hagler mixing rules.

11

0.8

0.001 MPa
0.100 MPa
1.000 MP
2.000 MPa
4.000 MPa

Fugacity of isobutane (MPa)

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.7

0.8

0.9

1.0

Mole fraction of isobuatne

Fugacity of carbon dioxide (MPa)

0.001 MPa
0.100 MPa
1.000 MP
2.000 MPa
4.000 MPa

0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

Mole fraction of isobutane

Figure 3: Fugacities of isobuatne and carbon dioxide as a function of composition

and pressure using the MADAR-1 mixing rules.

12

0.8

L-B, 1 MPa
L-B, 2 MPa
L-B, 4 MPa
W-H, 1 MPa
W-H, 2 MPa
W-H, 4 MPa
MADAR-1, 1 MPa
MADAR-1, 2 MPa
MADAR-1, 4 MPa

Fugacity of isobutane (MPa)

0.6

0.4

0.2

0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.7

0.8

0.9

1.0

Mole fraction of isobutane

Fugacity of carbon dioxide (MPa)

L-B, 1 MPa
L-B, 2 MPa
L-B, 4 MPa
W-H, 1 MPa
W-H, 2 MPa
W-H, 4 MPa
MADAR-1, 1 MPa
MADAR-1, 2 MPa
MADAR-1, 4 MPa

0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

Mole fraction of isobutane

Figure 4: The eect of dierent mixing rules on the fugacity of isobutane and
carbon dioxide at pressures of 1, 2, and 4 MPa.

13