Fugacity: It is derived from Latin, expressed as fleetness or escaping tendency.

It is used
to study extensively phase and chemical reaction equilibrium.
We know that
SdT VdP dG = -(1)
For isothermal condition
VdP dG =
For ideal gases
P
RT
V =
}
= dP
P
RT
dG .
P RTd dG ln =
To find Gibbs free energy for an real gases. True pressure is related by effective
pressure. Which we call fugacity(f).
f RTd dG ln = -------(2)
Applicable for all gases (ideal or real)
On differentiation
+ = f RT G ln
Is an constant depends on temperature and nature of gas.
fugacity has same units as pressure for an ideal gas.
For ideal Gases
SdT VdP dG =
For Isothermal conditions
VdP dG =
from equation (2)
VdP f RTd = ln
dP
RT
V
f d = ln
p
dp
f d = ln
p d f d ln ln =
p f = Fugacity = Pressure for Ideal gases
Fugacity coefficient ) ( : Fugacity coefficient ids defined as the ratio of fugacity of a
component to its pressure.
P
f
=
Is the measure of non ideal behavior of the gas.
Standard State: Pure gases, solids and liquids at temperature of 298k at 1 atmosphere are
said to exist at standard condition. The property at this condition are known as standard
state property and is denoted by subscripto.
o
G = Standard Gibbs free energy
o
f = Standard fugacity
Estimation of fugacity for gases
I method
SdT VdP dG =
For Isothermal conditions
VdP dG =
from equation (2)
VdP f RTd = ln
dP
RT
V
f d = ln
Integrating the above equation with the limits 0 to f and pressure 1 to P
} }
=
P
dP
RT
V
f d
1
ln
Lower limit is taken as P =1 atm
At 1 atm assuming the gases expected to behave ideally
}
=
P
VdP
RT
f
1
1
ln
if PVT relations are known , we can find fugacity at any temperature and pressure
II method
Using compressibility factor
VdP dG =
VdP f RTd = ln --------------(2)
V in terms of compressibility terms it is given as
P
ZRT
V =
Substitute V in equation 2
dP
p
ZRT
f RTd = ln
p Zd f d ln ln =
subtracting both sides by dlnP
P d P Zd P d f d ln ln ln ln =
P d z
P
f
d ln ) 1 ( ln =
P d Z d ln ) 1 ( ln =
Integrating the equation from 1 to and 0 to P
} }
=
P
P d Z d
0 1
ln ) 1 ( ln

}
=
P
P
dP
Z
0
) 1 ( ln
Using generalized charts: using reduced properties a similar chart as compressibility chart
is predicted for fugacity.
r
r
dP
P
Z
P
f
}

=
1
ln
Fugacity is plotted against various reduced pressure at various reduced temperature
Using Residual Volume(o): The residual volume is the difference between actual
volume (V) and the volume occupied by one mole of gas under same temperature and
pressure
P
RT
V = ,
P
RT
V + =
f RTd dP
P
RT
dG ln = |
.
|

+ =
f RTd
P
dP
dP
RT
RT ln = |
.
|

|
.
|

=
P
f
d dP
RT
ln

}
= dP
RT P
f
ln
Problem
For isopropanol vapor at 200
o
C the following equation is available
Z=1- 9.86 x 10
-3
P-11.45 x 10
-5
P
2
Where P is in bars. Estimate the fugacity at 50 bars and 200
o
C
2 5 3
10 41 . 11 10 86 . 9 1 P P
RT
PV
Z

= =
) 10 41 . 11 10 86 . 9 1 (
2 5 3
P P
P
RT
p
ZRT
V

= =
}
=
P
VdP
RT
f
1
1
ln
}

=
P
dP P P
P
RT
RT
f
1
2 5 3
) 10 41 . 11 10 86 . 9 1 (
1
ln
} } }

=
50
1
50
1
5 3
50
1
10 41 . 11 10 86 . 9 ln PdP dP
p
dp
f
, )
2
) 1 50 (
10 41 . 11 1 50 10 86 . 9
1
50
ln ln
2 2
5 3


|
.
|

=

f
f=26.744 bar
5348 . 0
50
744 . 26
= = =
P
f

Fugacity for liquids and solids

General expression for fugacity is
}
=
P
VdP
RT
f
1
1
ln
For solids and liquids at constant temperature the specific volume does not change
appreciably with pressure, therefore the above equation is integrated by taking volume
constant. Integrating the above equation from condition 1 to 2
} }
=
2
1
2
1
ln
P
P
f
f
dP
RT
V
f
, )
1 2
1
2
ln P P
RT
V
f
f
=
Problem:
Liquid chlorine at 25
o
C has a vapour pressure of 0.77Mpa, fugacity 0.7Mpa and Molar
volume 5.1x 10
-2
m
3
/kg mole. What is the fugacity at 10 Mpa and 25
o
C
Pa P
Pa P
6
2
6
1
10 10
10 77 . 0
=
=
Pa f
6
1
10 7 . 0 = K T 298 =
Kgmole
J
R 8314 =
, )
1 2
1
2
ln P P
RT
V
f
f
=
f=0.846Mpa
Activity(a):
It is defined as the fugacity of the existing condition to the standard state fugacity
o
f
f
a =
Effect of pressure on activity
The change in Gibbs free energy for a process accompanying change of state from
standard state at given condition at constant temperature can be predicted as
f RT G ln =
o o
f RT G ln =
a RT
f
f
RT G G G
o
o
ln ln =
|
|
.
|

= = A
at constant temperature VdP dG =
} }
=
G
G
P
P
O o
dP V dG
) (
o
P P V G = A ) ( ln
o
P P V a RT =
) ( ln
o
P P
RT
V
a = This equation predicts the effect of pressure on activity
Effect of Temperature on Activity
a RT G G G
o
ln = = A
T
G
T
G
a R
o
= ln
Differentiating the above equation with T at constant P
P
o
P
P
T
T
G
T
T
G
dT
a d
R
|
|
|
|
|
.
|

c
|
|
.
|

|
|
|
|
.
|

c
|
.
|

c
= |
.
|

\
ln
2 2
ln
RT
H
RT
H
dT
a d
R
o
P
+ = |
.
|

2
ln
RT
H H
dT
a d
R
o
P

= |
.
|

This equation predicts the effect of temperature on activity.

Properties of solutions
The relationships for pure component are not applicable to solutions. Which needs
modification because of the change in thermodynamic properties of solution. The
pressure temperature and amount of various constituents determines an extensive state.
The pressure, temperature and composition determine intensive state of a system.
Partial Molar properties:
The properties of a solution are not additive properties, it means volume of solution is not
the sum of pure components volume. When a substance becomes a part of a solution it
looses its identity but it still contributes to the property of the solution.
The term partial molar property is used to designate the component property when it is
admixture with one or more component solution.
A mole of component i is a particular solution at specified temperature and pressure has
got a set of properties associated with it like etc S V
i P
, . These properties are partially
responsible for the properties of solution and it is known as partial molar property
It is defined as
, )
i j
n
nM
M
j
n P T
i
i
=
(
]
1

c
c
=
, ,
i
M = Partial molar property of component i.
M = Any thermodynamic property of the solution
n = Total number moles in a solution
n
i
=Number of moles of component I in the solution
This equation defines how the solution property is distributed among the components.
Thus the partial molar properties can be treated exactly as if they represented the molar
property of component in the solution.
The above expression is applicable only for an extensive property using
We can write

=
i i
M n nM
i
i
x
n
n
=

=
i i
M x M
x
i
=Mole fraction of component i in the solution.
Measuring of partial molar properties
To understand the meaning of physical molar properties consider a open beaker
containing huge volume of water in one mole of water is added to it, the volume increase
is 18x 10
-6
m
3
If the same amount of water is added to pure ethanol the volume increased
is approximately 14 x 10
-6
m
3
this is the partial molar volume of H
2
O in pure ethanol.
The difference in volume can explain the volume applied by water molecules depending
on water molecules surrounding to them. When water is added to large amount of
ethanol, ethanol molecules hence volume occupied surround all the water molecules will
be different in ethanol.
If same quantity of water is added to an equimolar mixture of H
2
O and ethanol, the
volume change will be different. Therefore Partial molar property change with
composition. The intermolecular forces also changes with change in thermodynamic
property.
Let
w
V = Partial molar volume of the water in ethanol water solution
w
V = Molar volume of pure water at same temperature and pressure
t
V =Total volume of solution when water added to ethanol water mixture and allowed
for sufficient time so that the temperature remains constant
w w
t
V n V A = A
w
t
w
n
V
V
A
A
=
In a process a finite quantity of water is added which causes finite change in composition.
w
V = property of solution for all infinitely small amount of water.
(
]
1

c
c
=
A
A
=

w
t
w
t
v w
n
V
n
V
V
0
lim
Temperature pressure an number of moles of ethanol remains constant during addition of
water.
E
n P T
w
t
w
n
V
V
, ,
(
]
1

c
c
= n
E-
no of moles of ethanol
The partial molar volume of component i
i n P T
i
t
i
j
n
V
V
=
(
]
1

c
c
=
, ,
Partial molar properties and properties of the solution
Consider any thermodynamic extensive property (V
i
, G
i etc)
for homogenous system can
be determined by knowing the temperature, pressure and various amount of constituents.
Let total property of the solution
nM M
t
=
+ + + =
3 2 1
n n n n
1,2,3 represents no of constituents
Thermodynamic property is a , )
j
n n n n P T f
3 2 1
, , , ,
For small change in the pressure and temperature and amount of various constituents can
be written as
+
(
]
1

c
c
+
(
]
1

c
c
+
(
]
1

c
c
+
(
]
1

c
c
=
=
i
i n T P
t
n n p T
t
n p
t
n T
t
t
dn
P
M
dn
P
M
dT
P
M
dP
P
M
dM
j
, ,
1
, , , , ,
3 2
At constant temperature and pressure dP and dT are equal to zero.
The above equation reduces to
dni
n
M
dM
i j
n T P
n i
i i
t
t
=

=
=
(
]
1

c
c
=
, .
1
dM
t
in terms of partial molar property
i
n
i
i
t
dn M dM

=
=
1
i
M is an extensive property depends on composition and relative amount of constituents.
All constituent properties at constant temperature and pressure are added to give the
property of the solution.
+ + + =
3 3 2 2 1 1
dn M dn M dn M dM
t
, )dn x M x M x M dM
t
+ + + =
3 3 2 2 1 1
, )
3 3 2 2 1 1 3 3 2 2 1 1
n M n M n M n x M x M x M M
t
+ + = + + + =

=
i i
t
M n M
Problem
A 30% mole by methanol water solution is to be prepared. How many m
3
of pure
methanol (molar volume =40.7x10
-3
m
3
/mol) and pure water (molar volume =
18.068x10
-6
m
3
/mol) are to be mixed to prepare 2m
3
of desired solution. The partial molar
volume of methanol and water in 30% solution are 38.36x10
-6
m
3
/mol and 17.765x10
-6
m
3
/mol respectively.
Methanol =0.3 mole fraction
Water=0.7 mole fraction
V
t
=0.3 x38.36x10
-6
+0.7x17.765x10
-6
=24.025x10
-6
m
3
/mol
For 2 m
3
soolution
mol
3
6
10 246 . 83
10 025 . 24
2
=

=

Number of moles of methanol in 2m
3
solution
=83.246x10
3
x0.3= 24.97x10
3
mol
Number of moles of water in 2m
3
solution
=83.246x10
3
x07= 58.272x10
3
mol
Volume of pure methanol to be taken
= 24.97x10
3
x 40.7x10
-3
=1.0717 m
3
Volume of pure water to be taken
= 58.272x10
3
x 18.068x10
-6
=1.0529 m
3
Estimation of Partial molar properties for a binary mixture :
Two methods for estimation
Analytical Method and Graphical Method(Tangent Intercept method)
Analytical Method: The general relation between partial molar property and molar
property of the solution is given by
k
n P T
K
k i
x
M
x M M
, ,

|
|
.
|

c
c
= i k = x
1
For binary mixture
2 , 1 = = k i
P T
x
M
x M M
,
2
2 1
|
|
.
|

c
c
= 1
1 2
= + x x ,
1 2
1 x x = ,
1 2
x x c = c
At constant Temperature and pressure
|
|
.
|

c
c
+ =
1
1 1
) 1 (
x
M
x M M ------(a)
|
|
.
|

c
c
=
1
2
1
x
M
x M M -----------(b)
The partial molar property (extensive property) for a binary mixture can be estimated
from the property of solution using above equations (a) and (b).
Tangent Intercept method:
This is the graphical method to estimate partial molar properties. If the partial molar
property (M) is plotted against the composition we get the curve as shown in the figure.
Suppose partial molar properties of components required at any composition, and then
draw a tangent to this point to the curve. The intercept of the tangent with two axis x
1
=1
and x
1
=0 are I
1
and I
2.
Slope of the tangent
1
2
1
x
I M
dx
dM
=
1
1 2
dx
dM
x I M =
1
1 2
dx
dM
x M I =
Comparing I
2
with equation (b)
2 2
M I =
and also (right hand side)
1
1
1
1 x
M I
dx
dM

=
1
1 1
1
dx
dM
x M I =
1
1 1
1
dx
dM
x M I + = Comparing with equation(a) 1
1
M I =
The intercept of the tangent gives the partial molar properties.
Limiting cases: For infinite dilution of component when at x
1
=0 a tangent is drawn at
x
1
=0 will give the partial molar property of component 1 at infinite dilution ) (
1

M and
tangent is drawn at x
2
=0 or x
1
=1 will give infinite dilution ) (
2

M of component 2
~
2
M
Problem
The Gibbs free energy of a binary solution is given by
mol
cal
x x x x x x G ) 10 ( 150 100
2 1 2 1 2 1
+ + + =
(a) Finnd the partial molar free energies of the components at x
2
=0.8 and also at infinite
dilution.
(b) Find the pure component properties
Sol:
mol
cal
x x x x x x G ) 10 ( 150 100
2 1 2 1 2 1
+ + + =
Substitute
1 2
1 x x = and simplifying
150 49 8 9
1
2
1
3
1
+ + = x x x G
|
|
.
|

c
c
+ =
1
1 1
) 1 (
x
G
x G G
49 16 27
1
2
1
1
=
c
c
x x
x
G
101 16 35 18
1
2
1
3
1 1
+ + = x x x G
|
|
.
|

c
c
=
1
1 2
x
G
x G G
150 8 18
2
1
3
1 2
+ = x x G
To find the partial molar properties of components 1 and 2
x
2
=0.8
,
x
1
=1-0.8 = 0.2
101 16 35 18
1
2
1
3
1 1
+ + = x x x G
mol
cal
G 944 . 102
1
=
150 8 18
2
1
3
1 2
+ = x x G
mol
cal
G 824 . 149
2
=
At infinite dilution
0
1 1 1
= =

atx G G
mol
cal
G 101
1
=

1
1 2 2
= =

atx G G or x
2=0
mol
cal
G 160
2
=

To find the pure component property

1
1 1 1
= = atx G G
mol
cal
G 100
1
=
0
1 2 2
= = atx G G
mol
cal
G 150
1
=
Chemical Potential:
It is widely used as a thermodynamic property. It is used as a index in chemical
equilibrium, same as pressure and temperature. The chemical potential
i
of component i
in a solution is same as its partial molar free energy in the solution
i
G
The chemical potential of component i
j
n P T
i
t
i
n
G
G i
, ,
(
]
1

c
c
= =
j =
2 1
, , , n n T P f G
t
_

1
]
1

o
o
+
1
]
1

o
o
+
1
]
1

o
o

n i
1 i
i
n , T
i
t
n , P
t
n , T
t
t
dn
n
G
dT
T
G
dP
P
G
dG
j

+
(
]
1

c
c
+
(
]
1

c
c
=
i i
n P
t
n T
t
t
dn dT
T
G
dP
P
G
dG
, ,
For closed system there will be no exchange of constituents (n is constant)
dT S dP V dG
t t t
=
at constant temperature
t
T
V
P
G
=
(
]
1

c
c
at constant pressure
t
P
S
T
G
=
(
]
1

c
c

+ =
i i
t t t
dn dT S dP V dG
At constant temperature and pressure
j

=
i i P T
t
dn dG
,
For binary solution
2 2 1 1
x x G + =
Effect of temperature and pressure on chemical potential
Effect of temperature:
We know that
j
n P T
i
t
i
n
G
G i
, ,
(
]
1

c
c
= = -------------------(1)
differentiating equation (1) with respect to T at constant P
i n P
i
Tdn
G
T c
c
=
(
]
1

c
c
2
,

---------------------(2)
SdT VdP dG = ---------(3)
differentiating equation (3) with respect to T at constant P
S
T
G
P
=
(
]
1

c
c
differentiating again w r t n
i
i
n P
i
t
i
S
n
S
n T
G
j
=
(
]
1

c
c
=
c c
c
,
2
i
S is partial molar entropy of component I
2
,
T
T
T
T
T
i
i
n P
i

|
.
|

c
c
=
(
(
(
(
]
1

c
|
.
|

c
2
T
S T
i i

=
TS H G =
In terms of partial molar properties
i i i
S T H G A =
i i i
i i i
S T H
S T H
A =
A =

2
,
T
H
T
i
n P
i

=
(
]
1

c
c
This equation represents the effect of temperature on chemical potential.
Effect of Pressure:
We know that
j
n P T
i
t
i
n
G
G i
, ,
(
]
1

c
c
= = -------------------(4)
differentiating equation (4) with respect to T at constant P
i n T
i
Pdn
G
P c
c
=
(
]
1

c
c
2
,

---------------------(5)
SdT VdP dG = ---------(3)
differentiating equation (3) with respect to P at constant T
V
P
G
T
=
(
]
1

c
c
differentiating again w r t n
i
i
n T
i i
V
n
V
n P
G
j
=
(
]
1

c
c
=
c c
c
,
2
,
i
n T
i
V
P
=
(
]
1

c
c
,

This equation represents the effect of pressure on chemical potential

Fugacity in solutions
For pure fluids fugacity is explained as
f RTd dG ln =
1 lim
0
=

P
f
P
The fugacity of the component i in the solution is defined as analogously by
i i
f RTd d ln =
1
P
f
lim
i
i
0 P

i
is Chemical potential
i
f is partial molar fugacity
For ideal gases
T i i
P y P =
P
T
Total pressure.
Fugacity in Gaseous solutions
We know that
j
n P T
i
t
i
n
G
G i
, ,
(
]
1

c
c
= = ------(1)
differentiating equation (1) with respect to T at constant P
i n T
i
Pdn
G
P c
c
=
(
]
1

c
c
2
,

-----(2)
SdT VdP dG = -----(3)
differentiating equation (3) with respect to P at constant T
V
P
G
T
=
(
]
1

c
c
differentiating again w r t n
i
i
n T
i i
V
n
V
n P
G
j
=
(
]
1

c
c
=
c c
c
,
2
,
i
n T
i
V
P
=
(
]
1

c
c
,

P V
i i
c = c
dP V f RTd
i i
= ln
Subtracting both sides by
i
P d ln
i i
y d P d P d ln ln ln + =
Composition is constant dln y
i
=0
The above equation can be written as
P
dP
P d P d
i
= = ln ln
dP
RT
V
f d
i
i
= ln
i
i
i
i
P d dP
RT
V
P d f d ln ln ln =
i
i
i
i
P d dP
RT
V
P
f
d ln ln =
(
]
1

Modifying equation (a)

i
- Represents fugacity of the component i in the solution.
Ideal solutions
An ideal mixture is one, which there is no change in volume due to mixing. In other
words for an ideal gaseous mixture partial molar volume of each component will be equal
to its pure component volume at same temperature and pressure.
i i
V V = and

= =
i i i i
V x x V V --- Raoults law
Ideal solutins are formed when similar components or adjacent groups of group are
mixed
i i
V V =
Eg: Benzene-Toluene
Methanol- Ethanol
Hexane- Heptane
Solutin undergo change in volume due to mixing are known as non ideal solutions
i i
V V =
Eg: Methanol-Water
Ethanol-water.
Ideal solutions formed when the intermolecular force between like molecules and unlike
molecules are of the same magnitude.
Non-ideal solutions are formed when intermolecular forces between like molecules and
unlike molecules of different magnitude.
For ideal solutions
i i
t
V n V

= -------------------(1)
Vi is the molar volume of pure component I
i j
i
t
i
V n , P , T
n
V
V
1
]
1

o
o

-----------------
(2)
The residual volume for the pure component is
p
RT
V
i
=
Therefore we know from reduced properties
}
|
.
|

=
P
i
i
dP
P
RT
V
RT P
f
0
1
ln ----(3)
For component i in terms of partial molar properties
j dP
P
RT
V
RT
d i
i
|
.
|

=
1
ln
}
|
.
|

=
P
i
i
i
dP
P
RT
V
RT P
f
0
1
ln ----(4)
Subtracting equation (3) from (4)
, )
}
=
P
i
i
i i
i
dP V V
RT P f
P f
0
1
ln ----(5)
we know that P y P
i i
=
equation (5) reduces to
, )
}
=
P
i
i
i i
i
dP V V
RT y f
f
0
1
ln
comparing equation (2)
1 =
i i
i
y f
f
i i i
y f f = --Lewis Randal rule
Lewis Randal rule is applicable for evaluating fugacity of components in gas mixture.
Lewis Randal rule is valid for
1. At low pressure when gas behaves ideally.
2. When Physical properties are nearly same.
3. At any pressure if component present in exess.
Henrys Law
This law is applicable for small concentration ranges. For ideal solution Henrys law is
given as
i i i
k x f =
i i i
k x P =
k
i
- Henrys Constant,
i
f -Partial molar fugacity,
i
P -Partial pressure of component i.
Non Ideal solutions
For ideal solutions
i i i
k x f = ------------(a)
For non ideal solutions
i i i i
k x f = ----------(b)
Where
i
is an activity coefficient of component i.
Comparing equation (a) and (b)
= =
i
i
i
f
f
Non ideal solution / Ideal solution
For both ideal and Non ideal solutions the fugacity of solution is given by
equation

=
i
i
i
x
f
x f ln ln

=
i i
x ln ln
Problem:
A terinary gas mixture contains 20mole% A 35mole% B and 45mole% C at 60 atm and
75
o
C. The fugacity coefficients of A,B and C in this mixture are 0.7,, 0.6 and 0.9.
Calculate the fugacity of the mixture.
Solution:
c c B B A A
x x x ln ln ln ln + + =
) 9 . 0 ln( 45 . 0 ) 6 . 0 ln( 35 . 0 ) 7 . 0 ln( 2 . 0 ln + + =
2975 . 0 ln =
7426 . 0 =
P
f
= , f =44.558atm
Gibbs Duhem Equation
Consider a multi component solution having ni moles of component I the property of
solution be M in terms of partial molar properties
i
t
M n nM M
_
-----------------------(1).
Where n is the total no of moles of solution
Differentiating eq (1) we get
i i i i
dn M M d n nm d + = ) ( ----------------------------(2)
We know that
j =
2 1
, , , n n P T f nM
+
(
]
1

c
c
+
(
]
1

c
c
+
(
]
1

c
c
+
(
]
1

c
c
= c


2
, , ,
2
1
, ,
1 , , , ,
3 1 3 . 2 1
2 1 2 1
) ( ) ( ) ( ) (
) ( dn
n
nM
dn
n
nM
dP
P
nM
dT
T
nM
nM
n n P T n n P T
n n T n n P
(
]
1

c
c
+
(
]
1

c
c
+
(
]
1

c
c
= c

i
n P T
i n n T n n P
dn
n
nM
dP
P
M n
dT
T
M n
nM
j
, ,
, , , ,
) ( ) ( ) (
) (
2 1 2 1
From the definition of partial molar properties

+
(
]
1

c
c
+
(
]
1

c
c
= c

i i
n n T n n P
dn M dP
P
M n
dT
T
M n
nM
2 1 2 1
, , , ,
) ( ) (
) (
----------(3)
Subtracting equation (2) from equation (3)

=
(
]
1

c
c
+
(
]
1

c
c

0
) ( ) (
2 1 2 1
, , , ,
i i
n n T n n P
M d n dP
P
M n
dT
T
M n
------------------(4)
Equatin (4) is the fundamental form of Gibbs Duhem equation
Special Case
At constant temperature and pressure dT and dP are equal to zero. The equation becomes

= 0
i i
M d x
For binary solution at constant temperature and pressure the equation becomes
0
2 2 1 1
= + M d x M d x
0 ) 1 (
2 1 1 1
= + M d x M d x ------------(5)
dividing equation(5) by dx
1
0 ) 1 (
1
2
1
1
1
1
= +
dx
M d
x
dx
M d
x
The above equation is Gibbs Duhem equation for binary solution at constant temperature
and pressure in terms of Partial molar properties.
Any Data or equation on Partial molar properties must satisfy Gibbs Duhem
equation.
Problem:
Find weather the equation given below is thermodynamically consistent
) 10 ( 150 100
2 1 2 1 2 1
x x x x x x G + + + =
1
1 1
) 1 (
x
G
x G G
c
c
+ =
1
1 2
x
G
x G G
c
c
=
101 16 35 18
1
2
1
3
1 1
+ + + = x x x G
150 8 18
2
1
3
1 2
+ = x x G
16 70 54
1
2
1
1
1
+ = x x
dx
G d
1
2
1
1
2
16 54 x x
dx
G d
=
G D equation
0 ) 1 (
1
2
1
1
1
1
= +
dx
M d
x
dx
M d
x
0 ) x 16 x 54 )( x 1 ( ) 16 x 70 x 54 ( x
1
2
1 1 1
2
1 1
+ +
It satisfies the GD equation, the above equation is consistent.
Phase Equilibrium
Criteria for phase equilibrium: If a system says to be in thermodynamic equilibrium,
Temperature, pressure must be constant and there should not be any mass transfer.
The different criteria for phase equilibrium are
At Constant U and V: An isolated system do not exchange mass or heat or work with
surroundings. Therefore dQ=0, dW=0 hence dU=0. A perfectly insulated vessel at
constant volume dU=0 and dV=0.
0
,
>
V U
dS
At Constant T and V: Helmoltz free energy is given by the expression
TS U A =
TS A U + =
on differentiating
SdT TdS dA dU + + =
we know that
PdV TdS dU =
SdT TdS dA PdV TdS + + =
SdT PdV dA =
Under the restriction of constant temperature and volume the equation simplifies to
0
,
s
V T
dA
At Constant P and T
The equation defines Gibbs free energy
TS H G =
TS PV U G + =
SdT TdS VdP PdV dU dG + + =
SdT TdS VdP PdV dG dU + + =
TdS PdV dG dG dU + =
Under the restriction of constant Pressure and Temperature the equation simplifies to
0
,
s
P T
dG
This means the Gibbs free energy decreases or remains un altered depending on the
reversibility and the irreversibility of the process. It implies that for a system at
equilibrium at given temperature and pressure the free energy must be minimum.
Phase Equilibrium in single component system
Consider a thermodynamic equilibrium system consisting of two or more phases of a
single substance. Though the individual phases can exchange mass with each other.
Consider equilibrium between vapor and liquid phases for a single substance at constant
temperature and pressure. Appling the criteria of equilibrium
0 = dG
0 = +
b a
dG dG
a
dG and
b
dG are chane in free energies of the phases a and b respectively.
We know that
i i
dn G SdT VdP dG

+ =
For phase a
a a a a a a a
dn G dT S dP V dG + =
For phase b
b b b b b b b
dn G dT S dP V dG + =
At constant temperature and pressure
a a a
dn G dG = ,
b b b
dn G dG =
For a whole system to be at equilibrium
b a
b a
dn dn
or
dn dn
=
= + 0
j 0 =
a b a
dn G G
b a
G G =
When two phases are in equilibrium at constant temperature and pressure, Gibbs free
energies must be same in each phase for equilibrium.
C f RT C f RT
b a
+ = + ln ln
b a
f f =
Clapeyron Clausius Equation
Clapeyron Clausius Equation are developed two phases when they are in equilibrium
(a) Solid- liquid
(b) Liquid-Vapor
(c) Solid Vapor
Consider any two phases are in equilibrium with each other at given temperature and
pressure. It is possible to transfer some amount of substance from one phase to other
in a thermodynamically reversible manner(infinitely slow).The equal amount of
substance will have same free energies at equilibrium .
Consider G
A
is Gibbs free energy in phase A and G
B
is Gibbs free energy in phase B
at equilibrium.
G
A
=G
B
------(1)
AG = G
A
-G
B
=0 ------(2)
At new temperature and pressure the free energy / mole of substance in phase A is
A A
dG G + for Phase B
B B
dG G +
From basic equation
SdT VdP dG -----(3)
dT S dP V dG
A A A

dT S dP V dG
B B B

dT S dP V dT S dP V
B B A A

j [ j [
A B A B
S S dT V V dP
V
S
dT
dP

V represents the change in volume when one mole of substance pases from
phase A to Phase B
T
Q
S
V T
Q
dT
dP

j [
A B
V V T
Q
dT
dP

----(4)
This is a basic equation of Clapeyorn Clasius equation.
BVapor state A- Liquid state
Q=molar heat of vaporization =
V
H
V
B
is molar volume in vapor state, V
A
is molar volume in liquid state,
j [
l g
V V T
Q
dT
dP

V
g
>>>V
l
(Gas volume is very high when compared to liquid volume)
g
V
TV
H
dT
dP

V
H (Latent heat of vaporization),
P
RT
V
g

TRT
P
dT
dP

2
T
dT
R P
dP

Integrating the above equation from T

1
to T
2
and pressure from P
1
to P
2
.
1
]
1

1
]
1

2 1 1
2
T
1
T
1
R P
P
ln

This equation is used to calculate the vapor pressure at any desired temperature.
Problem:
The vapor pressure of water at 100
o
C is 760mmHg. What will be the vapor pressure
at 95
o
C. The latent heat of vaporization of water at this temperature range is
41.27KJ/mole.

2
1
P
mmHg 760 P
K 368 273 95 T
K 373 273 100 T
2
1
+
+
l l

2
1
2
1
T
T
P
P
T
dT
R P
dP
1
]
1

1
]
1

2 1 1
2
T
1
T
1
R P
P
ln

1
]
1

1
]
1

368
1
373
1
314 . 8
10 27 . 41
760
P
ln
3
2
mmHg 3 . 634 P
2

Phase Equilibrium in Multi component system
An heterogeneous system contains two or more phases and each phase contains two or
more components in different proportions. Therefore it is necessary to develop phase
equilibrium for multi component system in terms of chemical potential.
The partial molar free energy or chemical potential is given as
j
n P T
i
i i
n
G
G
, ,
(
]
1

c
c
= =
For a system to be in equilibrium with respect to mass transfer the driving force for
mass transfer( Chemical potential) must have uniform values for each component in
all phases.
Consider a heterogeneous system consists of phase , , and
containing various components 1,2,3-------C , that constitutes the system.
The symbol
k
i
represents chemical potential of component iin phase k.
At constant temperature and pressure, for the criterion for equilibrium is
dG=0 ----(1)
Free energy for multi component system given by the expression

+ =
i i
dn SdT VdP dG ------(2)
At constant Temperature and pressure
i i
dn dG ----(3)
Comparing equation 1 and 3

=
i i
dn 0
For multi component system

= =
=
C
i k
k
i
k
i
dn
1
0

Expanding the above equation

0
2 2 2 2 2 2 2 2
1 1 1 1 1 1 1 1
= + + +

+ + + +
+ + + +






c c c c c c c c
dn dn dn dn
dn dn dn dn
dn dn dn dn
-----(4)
Since the whole system is closed it should satisfy the mass conservation equation
0
2 2 2
1 1 1
= + +

+ + +
+ + +



C C C
dn dn dn
dn dn dn
dn dn dn
----(5)
The variation in number of moles dn
i
is independent of each other. However the sum of
change in mole in all the phases must be zero. For the criterion of equilibrium is that the
chemical potential of each component must be equal in all phases.






C C C
= =

= =
= =
2 2 2
1 1 1
At constant temperature and pressure the general criterion for thermodynamic
equilibrium in closed system for heterogeneous multi component system
At constant T and P


i i i
= =
for i=1,2,3--------C
Since + = =
i i i
f RT G ln
The above equation is also satisfied in terms of fugacity

i i i
f f f = =
for i=1,2,3--------C
Phase Diagram for Binary solution
Constant pressure equilibrium
Consider a Binary system made up of component A and B. Where it is assumed to be
more volatile than B where vapour pressure A is more than B. When the pressure is
fixed at the liquid composition can be changed the properities such as temperature and
vapour compositions get quickly determined VLE at constant pressure is represented on
T-xy diagram.
Boiling point diagrams
When temperature is plotted against liquid(x) and vapour(y) phase composition. The
upper curve gives and lower curve gives. The lower curve is called as bubble point
curve and upper curve is called as Dew point curve. The mixture below bubble point is
sub cooled liquid and above the Dew point is super heated vapour. The region between
bubble point and Dew point is called mixture of liquid and vapour phase.
Consider a liquid mixture whose composition and temperature is represented by
point A. When the mixture is heated slowly temperature rises and reach to point B,
where the liquid starts boiling, temperature at that point is called boiling point of whether
heating mixture reaches to point G when all liquids converts to vapour the temperature
at that point is called as Dew point. Further heating results in super heated vapour. The
number of tic lies connects between vapour and liquid phase. For a solution the term
boiling point has no meaning because temperature varies from boiling point to Dew point
at constant pressure.
Effect of pressure on VLE
The boiling point diagram is drawn from composition x=0 to x=1, boiling point of pure
substances increases with increase in pressure. The variation of boiling point diagrams
with pressure is as shown in diagram. The high pressure diagrams are above low
pressure.
Equilibrium diagram
Vapor composition is drawn against liquid comp at constant pressure. Vapour is always
rich in more volatile component the curve lies above the diagonal line.
Constant temperature Equilibrium
VLE diagram is drawn against composition at constant temperature. The upper curve is
and lower curve is drawn at vapour comp(y). Consider a liquid at known pressure and
composition at point A as the pressure is decreases and reaches to point B where it
starts boiling further decreases in pressure reaches to point C when all the liquid
converts to vapour, further decreases in pressure leads to formation of super heated
vapour. In between B to C both liquid and vapour exists together
Non ideal solution
An ideal solution obeys Raoults law and p-x line will be straight. Non ideal solution do
not obey Raoults law. The total pressure for non ideal solutions may be greater or lower
than that for ideal solution. When total pressure is greater than pressure given by Raoults
law, the system shows positive deviation from Raoults law.
Eg: Ethanol-toluene
When the total pressure at equilibrium is less than the pressure given by Roults law the
system shows negative deviation from Raoults law.
Eg: Tetrahydrofuron-ccl
4
Azeotropes
Azeotropes are constant boiling mixtures. When the deviation from Raoults law is very
large p-x and p-y curve meets at this point y
1
=x
1
and y
2
=x
2
A mixture of this composition is known as Azeotrope. Azeotrope is a vapour liquid
equilibrium mixture having the same composition in both the phases.
Types of Azeotropes
Azeotropes are classified into two types
1. Maximum curve pressure, minimum boiling azeotropes
2. Minimum pressure maximum boiling azeotrope
The azeotrope formed when negative deviation is very large will exhibit minimum
pressure or maximum boiling point, this is known as minimum pressure Azeotrope.
Eg : Ethanol water, benzene-ethanol
The azeotrope formed when ue deviation is very large will exhibit minimum pressure or
maximum boiling point, this is known as minimum pressure azeotrope.
Phase diagram for both types of Azeotropes
Minimum Temperature azeotropes
Maximum Tem Min pressure Azeotropes
Calculation of VLE for ideal solution
Ideal solution: Ideal solution is one which obeys Raoults law. Raoults law states that the
partial pressure is equal to product of vapor pressure and mole fraction in liquid phase.
A VA A
x P P =
P
A
- Partial pressure
P
VA
- Vapor pressure
x
A
- Mole fraction of component A
For binary solution (For component A and B)
We know that
B A T
P P P + = -------(1)
A VA A
x P P = ,
B VB B
x P P =
Substitute P
A
and P
B
in equation 1
B VB A VA T
x P x P P + =
B A
x x + = 1 ,
B A
x x = 1
) 1 (
A VB A VA T
x P x P P + =
, )
VB A VB VA T
P x P P P + = --------(2)
VB VA
VB T
A
P P
P P
x

=
Assuming the vapor phase is also ideal
T
A VA
T
A
A
P
x P
P
P
y = =
Substituting P
T
from equation (2)
, )
VB A VB VA
A VA
A
P x P P
x P
y
+
=
Dividing numerator and denominator by P
VB
1 1 +
|
|
.
|

=
A
VB
VA
A
VB
VA
A
x
P
P
x
P
P
y
, ) 1 1 +
=
A
A
A
x
x
y

The above equation relates x and y

o is known as relative volatility of component A with respect to component B
Problem: The binary system acetone and acetone nitrile form an ideal solution. Using the
following data prepare
- P-x-y diagram at 50
o
C
- T-x-y diagram at 400mm Hg
- x-y diagram at 400 mm Hg
T P
V1
P
V2
38.45 400 159.4
42 458.3 184.6
46 532 216.8
50 615 253.5
54 707.9 295.2
58 811.8 342.3
62.3 937.4 400
Solution: , )
2 1 2 1 V V V T
P x P P P + = ,
T
V
A
P
x P
y
1 1
= , P
V1
= 615, P
V2
= 253.5
x
1
P
T
y
1
0.0 253.5 0.0
0.2 325.8 0.377
0.4 398.1 0.6179
0.6 470.4 0.784
0.8 542.7 0.906
1.0 615 1
T-x-y diagram at 400 mm Hg , P
T
=400mmHg
2 1
2
1
V V
V T
P P
P P
x

= ,
T
V
A
P
x P
y
1 1
=
T P
V1
P
V2
x
1
y
1
38.45 400 159.4 1 1
42 458.3 184.6 0.7869 0.9015
46 532 216.8 0.5812 0.7729
50 615 253.5 0.405 0.6226
54 707.9 295.2 0.2539 0.449
58 811.8 342.3 0.122 0.2475
62.3 937.4 400 0 0
Calculation of VLE for non Ideal solution
For non ideal solution
Partial pressure is given by
Vi i i i
P x P =
i
- Activity coefficient
x
i
- Mole fraction
P
Vi
vapor pressure
For binary mixture
1 1 1 1 V
P x P =
2 2 2 2 V
P x P =
2 1
P P P
T
+ =
2 2 2 1 1 1 V V T
P x P x P + =
1 1 1
2 2 2
2 2 2 1 1 1
1 1 1 1
1
1
1
V
V
V V
V
T
P x
P x
P x P x
P x
P
P
y

+
=
+
= =
The above equation relates x and y for non ideal solution
Activity coefficients are functions of liquid composition x, many equations are available
to estimate them. The important equations are
Vanlaar equation
Wilson equation
Margules Equation
Vanlaar Equation:
Estimation of activity coefficient
2
2 1
2
2
1
ln
(
]
1

+
=
x x
B
A
Ax

2
2 1
2
1
2
ln
(
]
1

+
=
x
A
B
x
Bx

Where A and b are known as vanlaar constants, if the constants are known the
activity coefficients can be estimated.
Estimation of Vanlaar constants
1
st
Method: If the activity coefficients are known at any one composition, then vanlaar
constants A and B can be estimated by rearranging the equation
2
1 1
2 2
1
ln
ln
1 ln
(
]
1

+ =

x
x
A
2
2 2
1 1
2
ln
ln
1 ln
(
]
1

+ =

x
x
B
2
nd
Method
For a systems forming azeotrope, if the temperature and pressure s are known at
azeotropic composition then activity coefficients can be calculated as shown below.
1 1 1 1 V
P x P =
1 1 1 1 V T
P x y P =
At azeotrpic composition x
1
=y
1
1
1
=
V
T
P
P
,
2
2
=
V
T
P
P
Van laar constants A and B can calculated using the above equations.
Problem: The azeotope of ethanol and benzene has composition of 44.8mol% C
2
H
5
OH at
68
o
C and 760mmHg.At 68
o
C the vapor pressure of benzene and ethanol are 517 and 506
mmHg.
Calculate
- Vanlaar constants
- Prepare the graph of activity coefficients Vs composition
- Assuming the ratio of vapor pressure remains constant, prepare equilibrium
diagram at 760mmHg.
Solution:
At azeotropic composition x
1
=y
1
=0.448, x
2
=y
2
=0.552, P
V1
=506mmHg,
P
V2
=517mmHg
1
1
=
V
T
P
P
,
2
2
=
V
T
P
P
501 . 1
506
760
1
= = , 47 . 1
517
760
2
= =
2
1 1
2 2
1
ln
ln
1 ln
(
]
1

+ =

x
x
A
2
) 501 . 1 ln( ) 448 . 0 (
) 47 . 1 ln( ) 552 . 0 (
1 ) 501 . 1 ln(
(
]
1

+ = A
A=0.829
2
2 2
1 1
2
ln
ln
1 ln
(
]
1

+ =

x
x
B
2
) 47 . 1 ln( ) 552 . 0 (
) 501 . 1 ln( ) 448 . 0 (
1 ) 47 . 1 ln(
(
]
1

+ = B
B=0.576
Make use of the equations given below for plotting graph of activity coefficients Vs
composition.
2
2 1
2
2
1
ln
(
]
1

+
=
x x
B
A
Ax
,
2
2 1
2
1
2
ln
(
]
1

+
=
x
A
B
x
Bx

1 1 1
2 2 2
2 2 2 1 1 1
1 1 1 1
1
1
1
V
V
V V
V
T
P x
P x
P x P x
P x
P
P
y

+
=
+
= =
x
1
x
2
1

y
1
0 1 6.745 1 0
0.2 0.8 2.4 1.095 0.384
0.4 0.6 1.644 1.374 0.4384
0.6 0.4 1.21 1.721 0.5077
0.8 0.2 1.0112 2.618 0.609
1.0 0 1 3.723 1
Margules equation
Eetimation of activity coefficients
j j
1
2
2 1
2 ln x A B A x + =
j j
2
2
1 2
2 ln x B A B x + =
The constant A in the above equation is terminal value of ln
1
at x
1
=0 and constant B is
the terminal value of ln
2
at x
2
=0
When A=B
2
2 1
ln Ax = ,
2
1 2
ln Ax =
The above equations are known as Margules suffix equation.
Wilson Equation:
Wilson proposed the following equation for activity coefficients in binary solution
j
(
]
1

+ A
A

A +
A
+ A + =
2 1 21
21
2 12 1
12
2 2 12 1 1
ln ln
x x x x
x x x
j
(
]
1

+ A
A

A +
A
A + =
2 1 21
21
2 12 1
12
1 1 21 2 2
ln ln
x x x x
x x x
Wilson equation have two adjustable parameters
12
A and
21
A . These are related to pure
component molar volumes.
(
]
1

=
(
]
1

= A
RT
a
V
V
RT V
V
12
1
2 11 12
1
2
12
exp exp

1
]
1

1
]
1

RT
a
exp
V
V
RT
exp
V
V
21
2
1 22 12
2
1
21

V
1
and V
2
molar volumes of pure liquids
- Energies of interaction between molecule
Wilson equation suffers main disadvantages which is not suitable for maxima or minima
on ln versus x curves.
Consistency of VLE data
Gibbs duhem equation in terms of thermal consistency
0
ln
) 1 (
ln
1
2
1
1
1
1
= +
dx
d
x
dx
d
x

Plot of logarithmic activity coefficients Vs x
1
of component in binary solution
According to Gibbs Duhem equation both slopes must have oppsite sign then only the
data is consistent, otherwise it is inconsistent.
For the data to be consistent it has satisfy the following condition.
1. If one of ln curves has maximum at certain concentration and the other curve
should be minimum at same composition.
2. If there is no maximum or minimum point both must have + ue or ue on entire
range.
Co-existence equation
The general form of Gibbs duhem equation at constant temperature and pressure

= 0
i i
M d x ---(1)
In terms of partial molar free energies

= 0
i i
G d x ------(2)
dividing equation (2) by dx
1

= 0
1
dx
G d
x
i
i
-----(3)
+ =
i i
f RT G ln
at constant temperature
1 1
ln
dx
f RT
dx
G d
i i
= ----(4)
substituting equation (4) in equation (3)
0
ln
1
=

dx
f RT
x
i
i
0
ln
1
=

dx
f d
x
i
i
------(5)
For binary system
0
ln ln
1
2
2
1
1
1
= +
dx
f d
x
dx
f d
x ----(6)
0 ln ln
2 2 1 1
= + f d x f d x -----(7)
Equation (5) (6) and (7) are Gibbs Duhem equation in terms of fugacites and thus
applicable for both liquid and vapor phase
For liquids
i i i i
f x f =
i i i i
f x f ln ln ln ln + + =
differentiating with respect to x
1
1 1 1 1
ln ln ln ln
dx
f d
dx
x d
dx
d
dx
f d
i i i i
+ + =

-------(8)
f
i
is a pure component ffugacity it does not vary with x
1
Substituting equation (8) in equation (5)
0
ln ln
1 1
= +

dx
x d
x
dx
d
x
i
i
i
i

=0
=0
0
ln
1
=

dx
d
x
i
i

----------------(9)
For binary system
0
ln ln
1
2
2
1
1
1
= +
dx
d
x
dx
d
x

---------(10)
0 ln ln
2 2 1 1
= + d x d x -----------(11)
Equation (9) (10) and (11) are Gibbs Duhem equation in terms of activity coefficients
For ideal vapor
i i
P f =
From equation 5
0
ln
1
=

dx
P d
x
i
i
------------(13)
For binary system
0
ln ln
1
2
2
1
1
1
= +
dx
P d
x
dx
P d
x ----------(14)
0 ln ln
2 2 1 1
= + P d x P d x ---------------(15)
Equation (13) (14) and (15) are Gibbs Duhem equation in terms Partial pressure.
For ideal vapor
T
P y P
1 1
= ,
T
P y P
2 2
=
0 ) ln( ) ln(
2 2 1 1
= +
T T
P y d x P y d x
0 ln ) ( ln ln
2 1 2 1 1 1
= + + +
T
P d x x y d x y d x
1
2 1
= + x x
0 ln ln ln
2 1 1 1
= + +
T
P d y d x y d x
2 2 1 1
ln ln y d x y d x
P
dP
=
2
2
2
1
1
1
y
dy
x
y
dy
x
P
dP
=
0
1 2
= + y y ,
1 2
dy dy =
on simplification
(
]
1

=
) 1 (
) 1 (
1
1
1
1
1
y
x
y
x
dy
P
dP
Further simplification
(
]
1

=
) 1 (
1
1 1
1
y y
x y
P
dy
dP
This is known as coexistence equation. It relates P,x,y for binary VLE system. This
equation is used to rest consistency of VLE data.
Consistency test for VLE data
0 ln ln
2 2 1 1
= + d x d x
2
1 1
2
ln
ln
x
d x
d

=
) 1 (
ln
ln
1
1 1
2
x
d x
d

}

=
) 1 (
ln
ln
1
1 1
2
x
d x
d

Redlich Kister Test

The excess free energy of mixing for a solution is given as
Nonideal ideal
e
G G G =

=
i i
e
x RT G ln
For binary system
j
2 2 1 1
ln ln x x RT G
e
+ =
differentiating with respect to x
1
(
]
1

+ + + =
1
2
2
1
2
2 1
1
1
1
1
ln
ln
ln
ln
dx
dx
dx
d
x
dx
d
x RT
dx
dG
e

From Gibbs Duhem Equation

0
ln ln
1
2
2
1
1
1
= +
dx
d
x
dx
d
x

(
]
1

+ =
1
2
2 1
1
ln ln
dx
dx
RT
dx
dG
e

1 2
dx dx =
j
2 1
1
ln ln = RT
dx
dG
e
(
]
1

=
2
1
1
ln

RT
dx
dG
e
} }
=
=
=
=
(
]
1

=
1
0
1
2
1
1
0
1
1
1
1
ln
x
x
x
x
e
dx RT dG

The two limits indicates pure component for which 0 =

e
G , where LHS is zero for both
limits.
We can write
}
=
=
(
]
1

=
1
0
1
2
1
1
1
ln 0
x
x
dx

This can be checked graphically. Net area should be equal to zero for
consistency(Area=0).
Problem
Verify whether the following data is consistent
X
1
1

2
0 0.576 1.00
0.2 0.655 0.985
0.4 0.748 0.930
0.6 0.856 0.814
0.8 0.950 0.626
1.0 1.00 0.379
Solution:
We know that the Redlich kister test is
}
=
=
(
]
1

=
1
0
1
2
1
1
1
ln 0
x
x
dx

2
1

2
1
ln

0.576 -0.552
0.665 -0.408
0.804 -0.218
1.052 0.051
1.518 0.417
2.639 0.97
Plot
2
1
ln

Vs x
1
Area under the curve is zero. Data is consistent.
CHEMICAL REACTION EQUILIBRIUM
Energy change accompanies all chemical reactions. Because of this energy
change the temperature of the products may increase or decrease depending on the
exothermic or endothermic nature of the reaction. The energy change may be
expressed in terms of heat of reaction, heat of combustion and heat of formation.
Heat of reaction is the change in enthalpy of a reaction under pressure of 1.0
atmosphere, starting & ending with all materials at a constant temperature T
Heat of combustion is the heat of reaction of a combustion reaction.
Heat of formation is the heat of reaction of a formation reaction. A formation
reaction is one which results in the formation of one mole of a compound from the
elements.
Eq. H
2
+ O
2
H
2
O
C +O
2
CO
2
C + H
2
+ 1/2 Cl
2
CHCl
3
The standard heat of reaction, standard heat of formation, and standard heat of
formation are respectively the heat of reaction, heat of combustion and heat of formation
under 1 atmosphere starting and ending with all materials at constant temperature of
25
0
C.
In chemical industries, processes are carried out under isothermal conditions
and this requires the addition or removal of heat from the reactor. Heat of reaction
values will give the amount of heat to be removed or added. Knowing of this heat
value helps to design the heat exchange equipment.
Standard heat of reaction
Calculation of H
298
form heats of formation data:
The standard heat of reaction accompanying any chemical change is equal to
the algebraic sum of the standard heats of formation of products minus the
algebraic sum of the standard heat of formation of reactants.
H
r
= H
f 298 products
- H
f 298 reactants
Heat of formation of any clement is zero
Heat effects of chemical Reaction:
For the reaction, aA + bB cC + dD
Let heat capacity be C
p
= + T + T
2
then we have C
pA
=
A
+
A
T +
A
T
2
C
pB
=
B
+
B
T +
B
T
2
C
pC
=
C
+
C
T +
C
T
2
C
pD
=
D
+
D
T +
D
T
2
And H
0
298
be standard heat of reaction at 298 K and standard heat of reaction at any
other temperature can be found by Kirchoffs rule
, )
o
p
d H
C
dT
A
= A where
= [c(
C
+
C
T +
C
T
2
) + d(
D
+
D
T +
D
T
2
) ] - [a (
A
+
A
T +
A
T
2
) + b (
B
+
B
T +

B
T
2
)]
= [(c
C
+d
D
) (a
A
+ b
B
) ]+ [ (c
C
+ d
D
T) (a
A
+ b
B
)]T + [ c
C
+ d
D
)
(a
A
+ b
B
)] T
2
or
, ) , )
Pr Re tan
Pr Re tan
Pr Re tan
oducts ac ts
C D A B
oducts ac ts
oducts ac ts
cC dC aC bC

A =
A = + +
A =
A =



Substituting in Kirchoffs rule
, , ,
pC pD pA pB
C C and C C
C
p
= + T +T
2
tan
substituting the values of
p p p
products reac ts
p pC pD pA pB
C C C
C cC dC aC bC then
A =
1 1 A = + +
] ]

, )
0
298
0 2
0 2
298
2 3
2 3
H T
H
o
H T T T
d
H T T
dT
H T T T I

A
A
A = A + A + A
A = A + A + A
A A
A = A + + +
} }
OR in general
, )
0 2
2 3
=
2 3
P
H C dT T T dT
T T T I

A = A = A + A + A
A A
A + + +
} }
A chemical reaction proceeds in the direction of decreasing free energy.The sum of the
free energies of the reactants should be more than the sum of energies of products. For a
reaction to take place
Re Re
or 0
action action
products reaction
G G G G A = A <

Therefore G should be less than zero for a reaction to occur. When equilibrium is
reached free energies of the reactants equal free energies of products,. Therefore the
criterion for reaction equilibrium is G = 0
G
Reaction
Calculation: Consider the reaction aA + bB cC + dD
Let , , ,
A B C D
G G G and G be the partial molar free energies of A,B,C, and D in the
reaction mixture.
0 A A
0 0
0
0
0
0
f f
ln but the activity of A
ln
ln
ln
ln
A A A
A A
A A A
B B B
C C C
D D D
G G RT a
f f
G G RT a
G G RT a
G G RT a
G G RT a
= =
= +
= +
= +
= +
2 3
2 3
o
H T T T I

A A
A = A + + +
, ) , )
, ) , )
, ) , )
, )
Re
Re tan
0 0
0 0
= c ln ln
ln ln
action
products ac ts
D B
C A
C C D D
A A B B
C D A B
G G G
cG dG aG bG
G RT a d G RT a
a G RT a b G RT a
cG dG aG bG
A =
= + +
1
+ + +
]
1
+ + +
]
= +

, )
0
Re
ln ln ln ln
ln
C
C D A B
c d
D
action
a b
A B
RT a a a a
a a
G G RT
a a
+ +
1
(
A = A +
(
]
At equilibrium G = 0 and
C
c d
D
a b
A B
a a
K
a a
1
(
=
(
]
K is equilibrium constant of the reaction
j
0 0
0 ln ln
C
c d
D
a b
A B
a a
G RT G RT K
a a
1
(
= A + = A +
(
]
at equilibrium
EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT K
Gibbs - Helmoholtz equation at constant pressure is given
, )
, )
2
2 2
2
but ln K
ln K
ln K
T
or
ln K
Van't Hoff equation.
This may be integrated to find the effect of temperature on K
When is
o
o
G
d
T
H
G RT
dT T
RT
d
d R
H H
dT dT T T
d
H
dT RT
H
| A
|
A
\ .
= A =
|
|

A A
\ .
= =
A
=
A
2 2
1 1
K
2
K
2
1 2 1
1 1
contant d lnK
K 1 1
ln
K
if K at T,t
T
T
H
dT
RT
H
R T T
is known
A
=
1 A
=
(
]
} }
, )
, )
2 2
0
2
2
hen K can be calculated at other T
ln K
When H varies with T
ln K
2 3
d
H
dT RT
T I
d dT
RT R R RT

A
A =
A A A |
= + + +
|
\ .
2
ln T
ln K =
2 6
T T I
M
R R R RT
A A A
+ + +
Where M is a consatnt of integration
0
2
0
2 3
0
ln
ln T
2 6
ln T
2 6

A =
| A A A
A = + + +
|
\ .
A A
A = A +
G RT K
T T I
G RT M
R R R RT
T T
G T I MRT
For the reasction C
2
H
4
+ O
2
C
2
H
4
O, develop equations for H
0
, K, and G
0
, find
G
0
at 550 K
C
p
(Cal / mol K) Data: C
2
H
4
= 3.68 + 0.0224 T
O
2
= 6.39 + 0.0021 T
C
2
H
4
O = 1.59 + .00332 T
Standard heat of reaction H
0
298
C
2
H
4
O = - 12 190 and C
2
H
4
= - 12 500, Cal / mol
And G
0
298
= -19070 Cal / mol
= 1(-12190) 1( -12500) = 310 Cal / mol
, )
p
Pr Re tan
In this problem C
1
= 1.59 3.68 6.39 5.285
2
oducts ac ts
T

= +
|
A = + =
|
\ .

, )
Pr Re tan
1
= 0.0332 0.0224 0.0021 0.00975
2
oducts ac ts

|
A = + =
|
\ .

Then the variation of standard heat of reaction with temperature is
Re 298
Pr Re tan
action
oducts ac ts
H H H A =

, )
, )
2 3 2
0 2
298
2 0
298
0.00975
5.285
2 3 2
0.00975
Given =310 = 5.285 then I = 1452
2
0.00975
5.285 1452 This is variation of with temparature
2
lnK =
o
o
H T T T I T T I
H T T I
H T T H

A A
A = A + + + = + +
A + +
A = + + A
A
2
0
0 298
298 298 298
5.285 0.00975 1452
ln = ln
2 6 2 2(2) 2
G 19070
G ln or lnK 32
2(298)
5.285 0.00975 1452
32 = ln298 298 therefore M= 48.76
2 2(2) 2(298)
I
T T T M T T M
R R R RT T
but RT K
RT
M
A A
+ + + + +
A
A = = = =

+ +
0
0 3 2
0 3 2
550
3
5.285 0.00975 1452
lnK = ln 48.763
2 4 2
G ln 2 ln
5.285 0.00975 1452
2 ln 2 ln 48.763
2 4 2
G 5.285 ln 4.875(10 )( ) 1452 97.526( )
G 5.285(550)ln550 4.875(10 )(550) 1452 97
T T
T
RT K T K
T K T T T
T
T T T T

+ +
A = =
1
= + +
(
]
A = + +
A = + +
0
550
.526(550)
G 35320.62 / Cal mol A =
50 mol% each of SO
2
and O
2
is fed to a converter to form SO
3
.
Show the variation of i) Standard heat of reaction with T ii) Equilibrium constant
with T. The H
f
and G
f
at 298 K are
Component
H
f
k Cal / k
mol
G
f
k Cal / k
mol
SO
2
-70960 -71680
O
2
0 0
SO
3
-94450 -88590
Feed contains 50 mole% SO
2
and O
2
.This means for every one mole SO
2
there will be
one mole O
2
in the reactant side and mole O
2
in the product side, according to SO
2
+
O
2
SO
3
Reactants: 1 mol SO
2
+ 1 mol O
2
Products: 1 mol SO
3
+ mol O
2
(excess)
j
Pr tan
-3 3 -3 -3 -3
Pr tan
0 2 3
1
= 6.0377 + 6.148 7.116 6.148 - 4.152
2
1
= 23.53(10 ) + 3.102(10 ) - 9.512 (10 ) + 3.102 (10 ) =12.474 x10
2
2 3
=
oducts reac ts
oducts reac ts
H T T T I

A = +
1 A =
]
A A
A = A + + +


j
-3
2
0 0 0 0
298
Re tan
-3 2
0
12.474x10
-4.152T+
2
298 is given by 94450 70960 23490 k Cal / k mol
-23490=-4.152 (298 ) + 6.237 x 10 (298)
I = -22818.19
4.152 6.237 1
products ac ts
T I
But H at H H H
I
H T x
+
A A = A A = =
+

A = +

3 2
2
3
0 22818.19
for K we have
lnK= ln
R 2 6
4.152 12.474 10 22818.19
lnK= ln
2 2 2
T
Next
I
T T T M
R R RT
x
T T M
xR T

A A A
+ + +

+ + +
C
P
data:
Component a b(10
3
)
SO
2
7.116 9.512
O
2
6.148 3.102
SO
3
6.0377 23.537
0
0 298
298 298 298
0
298
Products Reactants
298
3
G
We have G = -RTln or lnK =
2(298)
G = G - G = - 88590 - (- 71680) = - 16910 k Cal / k mol
16910
lnK = 28.372
2(298)
4.152 12474 10
28.372 ln298
2 2
K
x

A
A
A A A

= +

3
22818.19
298
2 2 298
0.9842
11409.09
ln 2.076ln 3.1185 10 0.9842
M
x x
M
K T x T
T

+ +
=
= + + +
Derive the general equation for the standard free energy formation for N
2
+ 3/2
H
2
NH
3
The absolute entropies in ideal gas state at 298 K and 1.0 atm are
NH
3
= 46.01 g Cal / g mol K
N
2
= 45.77
H
2
= 31.21
H
0
298
(g Cal / g mol) = - 11040
Heat capacity Data is given by C
p
= a + bT + cT
2
the values are
Component a bx10
2
cx10
5
NH
3
6.505 0.613 0.236
N
2
6.903 - 0.038 0.193
H
2
6.952 - 0.46 0.096
Compute the free energy change at 1500K. Is reaction feasible?
0 0
298
Pr Re tan
0
298
We have G and
1 3
=46.01 (45.77) + (31.21) = 23.69 g Cal / g mol K
2 2
G 11040 298( 23.69) 39
o
oducts ac ts
H S S S S A = A A A = A A
1

(
]
A = =

Pr Re tan
2 2
Pr Re tan
80.38 g Cal / g mol K
1 3
6.505 (6.903) 6.952 7.3745
2 2
1 3
0.613 10 ( 0.038 10 ) ( 0.046 10
2 2
oducts ac ts
oducts ac ts
a a a
b b b x x x

1
A = = + =
(
]
A = = +


2 3
5 5 5 6
Pr Re tan
0 2 3
298
3 6
2
) 7.01 10
1 3
0.236 10 (0.193 10 ) (0.096 10 ) 0.045 10
2 2
2 3
7.01 10 0.045 10
11040 ( 7.3745)298 298 (
2 3
oducts ac ts
x
c c c x x x x
b c
H aT T T I
X X



1
=
(
]
1
A = = + =
(
]
A A
A = A + + +

= + +

3
2
298) OR I = -9153.26
ln ln and R =2 gCal / g mol K
2 6
I
a b c I
K T T T M
R R R RT
+
A A A
= + + +
0
298 298 298
3 6
2
-3980.38
ln or ln K = = 6.6784
-(2x298)
7.3745 7.01 10 0.045 10 9153.26
6.6784 ln298 298 (298)
2 2 2 6 2 2 298
11.798
G RT K
x x
M
x x x
M

A =

= + + + +
=
0
3 6
0 2
3 6
0 2
1500
7
var with T is given by, = - RT lnK
-7.3745 7.01 10 0.045 10 9153.26
= -2T ln 11.7987
2 2 2 6x2 2T
-7.3745 7.01 10 0.045 10
= -2x1500 ln1500 1500 1500
2 2 2 6x2
The iation of G G
x x
G T T T
x
x x
G
x


A A

A + + + +
`
' )

A + + +
0
1500
Pr Re tan
9153.26
11.7987
2x1500
g Cal
28488.81
g mol
oducts ac ts
G G G

+
`
' )
A = A A =

The reaction is not feasible G is highly +ve: For feasibility it should equal to zero
The hydration of Ethylene to alcohol is given by C
2
H
2
+ H
2
O C
2
H
5
OH
The heat capacity data for the component can be
represented by C
p
= a + bT where T is in kelvin
and C
p
is in cal / g mol
0
C
Develop general expression for the equilibrium constant and standard Gibbs free
energy change as function of temperature.
Pr Re tan
3 3 3 3
Pr Re tan
2
3
= 6.99 (2.83 7.3) 3.14
39.741 10 (28.6 10 2.46 10 ) 8.68 10
lnK = ln
R 2 6
3.14 8.68 10
lnK = ln
2 2 2 2
At 418 K
oducts ac ts
oducts ac ts
a a a
b b b x x x x
a b c I
T T T M
R R RT
x I
T T M
x T

A = + =
A = = + =
A A A
+ + +

+ +


3
-2
3
-3
3
3.14 8.68 10
, ln 6.8x10 = ln418 418
2 2 2 2 418
, I = -9655.807 & M = -5.667
3.14 8.68 10
593 K, ln 1.9x10 ln593 593
2 2 2 2 593
3.14 8.68 10 -9655.80
lnK = ln
2 2 2
x I
M
x x
Solving
x I
At M
x x
x
T T
x

+ +

= + +

+
3
-3 2
7
-5.667
2
3.14 8.68 10 -9655.807
But G = -2T ln -5.667
2 2 2 2
G = 3.14T ln T - 4.34x10 9655.807 11.334
T
x
T T
x T
T T

+

A + +
`
' )
A +
Temperature
0
C 145 6.8 x 10
-2
Equilibrium Constant 320 1.9 x 10
-3
Component a bx10
3
C
2
H
4
2.83 28.601
H
2
O 7.3 2.46
C
2
H
5
OH
6.99 39.741
THERMODYNAMIC FEASIBILITY OF REACTIONS
The equilibrium constant K is a measure of the concentration of the products
formed at equilibrium. It is related by the equation G
0
= - RT ln K. The more the value
of K, more will be the equilibrium conversion of products. When the value of G < 0,
means the value of K should be very large. Hence G is the measure of feasibility of a
chemical reaction.
i) If G
0
< 0, there can be appreciable conversion of reactants in to products.
The more the ve value, more will be the feasibility of the reaction
ii) If G
0
is +ve but less than 10 000 k Cal / mol, the reaction is not feasible,
at atmosphere , may be feasible at any other pressure
iii) If G
0
is greater than 10 000 kCal / mol the reaction is not at all feasible
under any condition.
Equilibrium Calculations ( Homogeneous gas Phase reactions):
aA (g) + bB (g) cC (g) + dD (g)
We have
C
c d
D
a b
A B
a a
K
a a
1
(
=
(
]
for gases,
j
0
0
c c c c c c c c
D D D D
A A A A
B B B B
c c c
as = p = 1 atmosphere: a = f
f = y but a p = y p
a y p
a y p
a y p
y p
K =
c
c
f
Activity a E f
f
f x




=
=
=
=
=
j
j
j
j
j
j
j
j
j
j
j
j
j
j
j
j
j
j
j
D D D c D c D c D
A A A B B B A B A B A B
c + d - (a + b) n
y p y y p p
x x
y p y p y y p p
( )( )( )(P ) =( )( )( )(P ) where = activity co efficient for gas phase
d c d c d c d c d
a b a b a b a b a b
y y
x
K k k k k k k

A
=
=
y = mole fraction
= Fugacity Co efficient for gas phase
P = Total pressure
Effect of variables on equilibrium :
Effect of temperature:
0
298 298
ln G RT K A = since G depends only on temperature as the
pressure is fixed at 1.0 atmosphere, K value varies with temperature. It is not affected by
Pressure, Concentration, etc,. Variation of K with T is given by
, )
2
ln K
Van't Hoff equation.
d
H
dT RT
A
=
For endothermic reactions H
0
is + ve as T increases K also increases. This
means that the equilibrium conversion is more at higher pressure.
For exothermic reactions H
0
is ve. Therefore K increases with T. Hence the
equilibrium conversion decreases as T increases. Eg. SO
2
+ 1/2 O
2
SO
3
Effect of pressure: Consider a reaction of ideal gases, then K = K
y
P
n
or K
y
= K / P
n
- When n >0. An increase in pressure decreases K
y
. Hence equilibrium product
yield is less at high pressures
- When n<0. An increase in pressure increases Ky and equilibrium product
yield
C
2
H
4
+ H
2
O C
2
H
5
OH n = 1 (1+1) = -1, n < 0
N
2
+ 3H
2
2NH
3
n = 2 4 = 2 n < 0 Here high
pressure is required
- When n =0 Here pressure has no effect on reaction. For ideal gases the effect
of pressure depends on the variation of and with pressure
Effect of Inert: Presence of inert has the opposite effect of increase of pressure.
Therefore when n > 0, addition of inert increases K
y
and equilibrium
conversion
And n < 0, addition of inert decreases equilibrium conversion.
Effect of excess reactants: Presence of excess reactants increases equilibrium
conversion of the limiting reactant
Presence of products in feed: decreases the equilibrium conversion of reactants.
Eg. CH
3
COOH + C
2
H
5
OH CH
3
COOC
2
H
5
+ H
2
O
If water is added by 1.0 mole to the feed, equilibrium conversion of CH
3
COOH
reduces from 30% to 15%
HCN is produced by the reaction N
2
(g)+ C
2
H
2
(g) 2HCN (g). The reactants are
taken in stoichiometric ratio at 1.0 atmosphere and 300
0
C. At this temperature G
0
= -
30100 k J / k mol. Calculate equilibrium composition of product stream and
maximum conversion of C
2
H
2
n=2 (1+1) = 0
0 3
30100
we have ln or lnK = or K = 1.8029x10
8.314(573)
G RT K

A =
Component
Moles
in feed
Moles
reacted
Moles
present
Mole
fraction
N
2
1 X 1 X (1 X) / 2
C
2
H
2
1 X 1 X (1 X) / 2
HCN -- 2X 2X
(2X) / X =
X
2 2 2
0
2 2
3
1 1
Assume 1 and 1
1.8029(10) , X = 0.0207
1 1
2 2
Equilibrium Composition:
n n
y
HCN
y
N C H
K K K K P K K P P
y X
K K Solving for X
X X y y

A A

= = = = =
= = = =
| |
| |
\ .\ .
2
2 2
1 1 0.0207
N 100 100 48.965%
2 2
1 1 0.0207
100 100 48.965%
2 2
( )100 2.007%
X
X
C H
HCN X
Equilibrium Conversi
| |
= = =
| |
\ . \ .
| |
= = =
| |
\ . \ .
= =
2 2
2 2
2 2
2 2
max for reversible reaction
of 0.0207
Max. Conversion of 100 100 100 2.07%
of in feed 1 1
on of C H
Equilibriumconversion is imum
Moles C H reacted X
C H
Moles C H
= = = =
Workout the problem, when the pressure is changed to 203 bar. Fugacity co efficients
of N
2,,
C
2
H
2
and HCN are 1.1, 0.928, and 0.54 Assume K

= 1
c c
0 C C
a b a
A B A
2 2
-3
y
= (1) 203 where a,b, and c are stoichiometric co efficients
y
0.54 X
and K is known already = 1.8029x10 = .(1)
(1.1)(0928) 1-X 1-X
2 2
solving
n
y
b
B
K K K K P
y

A
| |
=
| |
| |
\ . \ .
1
(
| |
]
| |
\ . \ .
2 2
2 2
2 2
X = 0.0382
then equilibrium Composion of C H is ( Max reversible reaction)
moles C H 0.0382
= x 100 = 3.82%
moles of C H in feed 1
reacted
Calculate the K at 673K & 1.0 bar for N
2
(g) + 3 H
2
(g) 2NH
3
(g).
Assume heat of reaction remains constant. Take standard heat of formation and
standard free energy of formation of NH
3
at 298 K to be - 46110 J / mol and 16450 J
/ mol respectively.
0
298 0
298 298
0
298
0
298 1
2( 16450) 32900 J
ln
2 (-46110) = -92 220 J
ln
G
G RT K
H
G RT K
A = =

A =
`
A =

)
A =
1
1
0
2
1 2 1
2
- 32900 = - 8.314 (298) ln K
K 564861.1
K 1 1
have ln
K
K 92220 1 1
ln
584861.1 8.314 673 298
H
we
R T T
=
| A
=
|
\ .
|
=
|
\ .
4
2
K 5.75 10 X

=
Acetic acid is esterified in the liquid phase with ethanol at 373 K and 1.0 bar according
to
CH
3
COOH (L) + C
2
H
5
OH (L) CH
3
COOC
2
H
5
(L) + H
2
O (L)
The feed consists of 1.0 mol each of acetic acid & ethanol, estimate the mole fraction of
ethyl acetate in the reacting mixture at equilibrium. The standard heat of formation
and standard free energy of formation at 298 K are given below.
Assume that the heat of reaction is independent of T and liquid mixture behaves as
ideal solution.
G
0
298
= 318218 237130 + 389900 + 174780 = 9332 J
H
0
298
= 463250 285830 + 277690 + 484500 = 13110 J
We have, G
0
298
= RT ln K
9332 = 8.314 (298) ln K
1
or K
1
= 0.02313
and for K
2
at 373K we have
Component
Moles
in feed
Moles
reacted
Moles
present
Mole
fraction
CH
3
COOH 1 X 1 X (1 X) / 2
C
2
H
5
OH 1 X 1 X (1 X) / 2
CH
3
COOC
2
H
5
-- X X X / 2
H
2
O -- X X X / 2
2
2
2
0
2
2 2
3 2 5
x
2
0.067= solving, x = 0.252
(1 )
1
2
0.252
mole fraction of CH 0.126
2 2
y
x
K K P
x
x
x
COOC H
|
|
\ .
= =

|
|
\ .
= = =
CH
3
COOH
(L)
C
2
H
5
OH
(L)
CH
3
COOC
2
H
5
(L) H
2
O (L)
f
0
f
(J)
- 484500 - 277690 - 463250 - 285830
G
0
f
(J)
- 389900 -174780 - 318218 - 237130
1
2 1 2
2
2
1 1
ln
0.02313 12110 1 1
ln OR K 0.067
8.314 298 373
K H
K R T T
K
A
=
`
' )

= =
`
' )
The standard free energy change for the reaction C
4
H
8
(g) C
4
H
6
(g) + H
2
(g)
is given by G
T
0
=1.03665 X 10
5
20.9759T ln T 12.9372 T, where range of G
T
0
in J
/ mol and T in K
a) Over what range of T, is the reaction promising from thermodynamic view
point?
b) For a reaction of pure butene at 800K, calculate equilibrium conversion at 1.0
bar & 5.0 bar
c) Repeat part (b) for the feed with the 50 mol% butene and the rest inerts
a. For the reaction at G = 0, T 812.4 K, above this temperature G <
0, reaction is promising below 550 K, G > 0, reaction is unfavorable,
b. At 800K, G
0
= 1842.16 J / mol
G
0
= - RT ln K, or 1842.16 = - 8.314 ( 800 ) ln K or
K = 1.3191
K = k
y
P
n
= k
y
P
( 2- 1 )
= k
y
P
Therefore at 1.0 bar K = k
y
P 1.3191 = k
y
( 1 )
k
y
= 1.31910At 5 bar, 1.3191 = k
y
( 5 )
k
y
= 0.26382
Moles in
feed
Moles in product stream
y
i
C
4
H
8
1 1 - X
(1 X ) / (1 +
X)
C
4
H
6
X X / (1 + X)
H
2
X X / (1 + X)
1 + X
4 6
4
' '
2
C H H2
Y
' 2
C H8
2
y
2
x x
Y Y
x 1 x 1 x
k or 1.3191 = or x = 0.7541
1 x Y 1 x
1 x
Conversion of betene = 75.41%
x
At 5.0 bar, k = 0.26382 = , x = 0.4569, Conversion of b
1 x
| |
| |
+ +
\ .\ .
= =
|
|
+
\ .

etene = 45.69 %
C.
Moles in
feed
Moles in product stream
y
i
C
4
H
8
1 1 - X (1 X ) / (2 + X)
C
4
H
6
X X / (2 + X)
H
2
X X / (2 + X)
Inerts 1.0 1 1 / (2 + X)
2 + x
, )
, )
2
Y 2
2
Y 2
x 2 x
at 1.0 bar, k K 1.3191
1 x
2 x
x = 0.8194
K x 2 x
at 5.0 bar k 0.26382
5 1 x
2 x
x = 0.5501
+ |
= = ==
|

\ . +
+ |
= = =
|

\ . +