(12)

K f f

i
0
i i
i
= [
v
The expression of K in terms of fugacity coefficient is:
The standard state for a gas is the ideal-gas state of the
pure gas at the standard-state pressure P
0
of 1 bar.
Since the fugacity of an ideal gas is equal to its pressure,
f
i
0
= P
0
for each species i .
Thus for gas-phase reactions , and Eq. (12)
becomes:
0
i
0
i i
P f

f f

=
K
P
f

i
0
i
i
= |
.
|

\
|
[
v
(26)
The equilibrium constant K is a function of temperature
only.
However, Eq. (26) relates K to fugacities of the reacting
species as they exist in the real equilibrium mixture.
These fugacities reflect the nonidealities of the equili-
brium mixture and are functions of temperature,
pressure, and composition.
This means that for a fixed temperature the
composition at equilibrium must change with pressure
in such a way that remains constant
i
0
i
i
P f

v
[
The fugacity is related to the fugacity coefficient by
Substitution of this equation into Eq. (26) provides an
equilibrium expression displaying the pressure and the
composition:
P y

i i i
| =
K
P
P

y
0
i i
i
i
v
v
|
.
|

\
|
= | [
Where v = E
i
v
i
and P
0
i s the standard-state pressure of 1
bar, expressed in the same units used for P.
(27)
If the assumption that the equilibrium mixture is an ideal
solution is justified, then each becomes |
i
, the fugacity
coefficient of pure species i at T and P.
In this case, Eq. (27) becomes:
i

|
( ) K
P
P
y
0
i i
i
i
v
v
|
.
|

\
|
= | [
(27)
For pressures sufficiently low or temperatures sufficiently
high, the equilibrium mixture behaves essentially as an
ideal gas. In this event, each |
i
= 1, and Eq. (27) reduces to:
( ) K
P
P
y
0
i
i
i
v
v
|
.
|

\
|
= [
(28)
Although Eq. (28) holds only for an ideal-gas reaction,
we can base some conclusions on it that are true in
general:
According to Eq. (20), the effect of temperature on
the equilibrium constant K is determined by the sign
of AH
0
:
o AH
0
> 0 (the reaction is endothermic) T>> K >>.
Eq. (28) shows that K >> at constant P >>
c >>
o AH
0
< 0 (the reaction is exothermic) T>> K <<.
Eq. (28) shows that K << at constant P <<
c
e
<<
( )
i
i
i
y
v
[
( )
i
i
i
y
v
[
If the total stoichiometric number v ( E
i
v
i
) is
negative, Eq. (28) shows that am increase in P at
constant T causes an increase in , implying a
shift of the reaction to the right.
If the total stoichiometric number v ( E
i
v
i
) is
positive, Eq. (28) shows that am increase in P at
constant T causes a decrease in , implying a
shift of the reaction to the left, and a decrease in c
e
.
( )
i
i
i
y
v
[
( )
i
i
i
y
v
[
For a reaction occurring in the liquid phase, we return to
(12)
K f f

i
0
i i
i
= [
v
For the usual standard state for liquids f
0
i
is the fugacity
of pure liquid i at the temperature of the system and at 1
bar.
The activity coefficient is related to fugacity according to:
i i i i
f x f

=
(29)
The fugacity ratio can now be expressed
|
.
|

\
|
=

=
0
i
i
i i
0
i
i i i
0
i
i
f
f
x
f
f x
f
f

(30)
(31)
Gibbs free energy for pure species i in its standard state at
the same temperature:
( )
0
i i
0
i
f ln RT T G + I =
(7)
Gibbs free energy for pure species i at P and the same
temperature:
( )
i i i
f ln RT T G + I = (7.a)
The difference between these two equations is:
0
i
i
0
i i
f
f
ln RT G G =
Fundamental equation for Gibbs energy:
dT S dP V dG
i i i
=
(32)
For a constant-temperature process:
dP V dG
i i
=
(32)
For a pure substance undergone a constant-temperature
process from P
0
to P, the Gibbs free energy change is:
}
=
}
P
P
i
G
G
0
i
0
i
dP V dG
(33)
(34)
( )
0
i
0
i i
P P V G G =
Combining eqs. (31) and (34) yields:
(35)
( )
RT
P P V
f
f
ln
0
i
0
i
i

=
( )
(

=
RT
P P V
exp x
f
f

0
i
i i
0
i
i
(36)
( )
(

=
RT
P P V
exp
f
f
0
i
0
i
i
or
Combining eqs. (31) and (35) yields:
( )
K
RT
P P V
exp x
0
i
i i
i
=
)
`

H
Combining eqs. (36) and (12) yields:
( )
( )
K
RT
P P V
exp x
u
i
0
i
i
i i
i
=
(

H H
v
v
( )
( )
u
i
RT
P P V
exp K x
0
i
i
i i
i
v
v
)
`

H = H
( )
( )
( )
(

= H
v
i
i i
0
i i
i
V
RT
P P
exp K x
i
(37)
For low and moderate pressure, the exponential term is
close to unity and may be omitted. Then,
( ) K x
i
i i
i
= H
v
(38)
and the only problem is determination of the activity
coefficients.
An equation such as the Wilson equation or the UNIFAC
method can in principle be applied, and the compositions
can be found from eq. (38) by a complex iterative
computer program.
However, the relative ease of experimental investigation
for liquid mixtures has worked against the application of
Eq. (38).
If the equilibrium mixture is an ideal solution, then
i
is
unity, and Eq. (38) becomes:
( ) K x
i
i
i
= H
v
(39)
This relation is known as THE LAW OF MASS ACTION.
Since liquids often form non-ideal solutions, Eq. (39) can
be expected in many instances to yield poor results.
Suppose a single reaction occurs in a homogeneous
system, and suppose the equilibrium constant is known.
In this event, the calculation of the phase composition
at equilibrium is straightforward if the phase is
assumed an ideal gas [Eq. (28)] or an ideal solution [Eq.
(27) or (39)].
When an assumption of ideality is not reasonable, the
problem is still tractable for gas-phase reactions
through application of an equation of state and solution
by computer.
For heterogeneous systems, where more than one
phase is present, the problem is more complicated and
requires the superposition of the criterion for phase
equilibrium developed in Sec. 11.6
Single-Phase Reactions
The water-gas shift reaction,
CO (g) + H
2
O (g) CO
2
(g) + H
2
(g)
Is carried out under the different set of conditions below.
Calculate the fraction of steam reacted in each case.
Assume the mixture behaves as an ideal gas.
The reactants consist of 1 mol of H
2
O vapor and 1 mol of
CO. The temperature is 1100 K and the pressure is 1 bar.
Example
Solution
CO

H
2
O CO
2
H
2

v 1 1 + 1 + 1
A 3,376 3,470 5,547 3,249
B 10
3
0,557

1,450

1,045 0,422

C 10
6
4,392

0 0 0

D 10
-5
0,031 0,121 1,157 0,083
AH
0
f,298
110.525 241.818 393.509 0
AG
0
f,298
137.169 228.572 394.359 0
950 , 1 A = A
3
10 540 , 0 B

= A
6
10 392 , 4 C

= A
5
10 164 , 1 D = A
1 0
298
mol J 166 . 41 H

= A
1 0
298
mol J 618 . 28 G

= A
( )( )
260 . 103
15 , 298 314 , 8
618 . 28
exp
RT
G
exp K
0
0
0
0
= = |
.
|

\
| A
=
20
(

|
.
|

\
|

A
=
T
T
1
RT
H
exp K
0
0
0
0
1
( )( )
6
10 527 , 5
1100
15 , 298
1
15 , 298 314 , 8
166 . 41
exp

=
(

|
.
|

\
|

=
6894 , 3
15 , 298
1100
T
T
0
= = = t
189 , 2 K
2
=
( )( )( ) 189 , 2 8354 , 3 10 527 , 5 261 . 103 K K K K
6
2 1 0
= = =

21
0 1 1 1 1
i
i
= + =

v = v
Since the reaction mixture is an ideal gas:
( ) K y
i
i
i
= H
v
189 , 2 K
y y
y y
O H CO
H CO
2
2 2
= =
e i i i
0
n n c v + =
v c + =
e 0
n n
The number of each species at equilibrium is:
While total number of all species at equilibrium is:
e CO
1 n c =
e O H
1 n
2
c =
e CO
2
n c =
e H
2
n c =
2 n=
2
1
y
e
CO
c
=
2
1
y
e
O H
2
c
=
2
y
e
CO
2
c
=
2
y
e
H
2
c
=
189 , 2 K
y y
y y
O H CO
H CO
2
2 2
= =
( )
189 , 2
1
2
2
=
c
c
( ) ( )
2 2 2
2 1 189 , 2 1 189 , 2 c + c = c = c
0 189 , 2 378 , 4 189 , 1
2
= + c c
5436 , 0
e
= c
Therefore the fraction of the steam that reacts is 0.5
Estimate the maximum conversion of ethylene to ethanol
by vapor-phase hydration at 523.15 K and 1.5 bars for an
initial steam-to-ethylene ratio of 5.
Example
Solution
Reaction:
C
2
H
4
(g) + H
2
O (g) C
2
H
5
OH (g)
C
2
H
4
H
2
O C
2
H
5
OH
v 1 1 + 1
A 1,424 3,470 3,518
B 14,394 10
-3
1,450 10
-3
20,001 10
-3
C 4,392 10
-6
0 6,002 10
-6
D 0 0,121 10
5
0
AH
0
f,298
52.510 241.818 235.100
AG
0
f,298
68.460 228.572 168.490
376 , 1 A = A
3
10 157 , 4 B

= A
6
10 610 , 1 C

= A
5
10 121 , 0 D = A
1 0
298
mol J 792 . 45 H

= A
1 0
298
mol J 378 . 8 G

= A
( )( )
366 , 29
15 , 298 314 , 8
378 . 8
exp
RT
G
exp K
0
0
0
0
= = |
.
|

\
| A
=
27
(

|
.
|

\
|

A
=
T
T
1
RT
H
exp K
0
0
0
0
1
( )( )
4
10 5 , 3
15 , 523
15 , 298
1
15 , 298 314 , 8
792 . 45
exp

=
(

|
.
|

\
|

=
7547 , 1
15 , 298
15 , 523
T
T
0
= = = t
9778 , 0 K
2
=
( )( )( )
3 4
2 1 0
10 05 . 10 9778 , 0 10 5 , 3 366 , 29 K K K K

= = =
1 1 1 1
i
i
= =

v = v
( ) K
P
P
y
0
i
i
i
|
.
|

\
|
= [
v
K
P
P
y y
y
0
O H H C
OH H C
2 4 2
5 2
|
.
|

\
|
=
( ) K
P
P
y
0
i
i
i
v
v
|
.
|

\
|
= [
For hign temperature and sufficiently low pressure:
e i i i
0
n n c v + =
e e 0
6 n n c = v c + =
The number of each species at equilibrium is:
While total number of all species at equilibrium is:
e H C
5 n
4 2
c =
e O H
1 n
2
c =
e OH H C
5 2
n c =
e
e
H C
6
5
y
4 2
c
c
=
e
e
O H
6
1
y
2
c
c
=
e
e
OH H C
6
y
5 2
c
c
=
K
P
P
y y
y
0
O H H C
OH H C
2 4 2
5 2
|
.
|

\
|
=
( )
( )( )
( ) ( )
3 3
e e
e e
10 07 . 15 10 05 . 10 5 . 1
1 5
6

= =
c c
c c
( ) ( )( )
e e
3
e e
1 5 10 07 . 15 6 c c = c c

0 0754 . 0 09045 . 6 01507 . 1
e
2
e
= + c c
0135 . 0
e
= c
The gas-phase oxidation of SO
2
to SO
3
is carried out at a
pressure of 1 bar with 20% excess air in an adiabatic
reactor. Assuming that the reactants enter at 298.15 K and
that equilibrium is attained at the exit, determine the
composition and temperature of the product stream from
the reactor.
Example
Solution
Reaction:
SO
2
(g) + O
2
(g) SO
3
(g)
Basis: 1 mole of SO
2
entering the reactor:
moles of O
2
entering = (0.5) (1.2) = 0.6
moles of N
2
entering = (0.6) (79/21) = 2.257

The amount of each species in the product stream is:
e i i i
0
n n c v + =
e SO
1 n
2
c =
e O
5 . 0 6 . 0 n
2
c =
e SO
3
n c =
257 . 2 n
3
N
=
e
5 . 0 857 . 3 n c =
Total amount of all species:
Mole fraction of each species:
e
e
SO
5 . 0 857 . 3
1
y
2
c
c
=
e
e
O
5 . 0 857 . 3
5 . 0 6 . 0
y
2
c
c
=
e
e
SO
5 . 0 857 . 3
y
3
c
c
=
e
N
5 . 0 857 . 3
257 . 2
y
2
c
=
Energy balance:
Reactant
T = 298.15 K
SO
2
= 1
O
2
= 0.6
N
2
= 2.257
Product
T = 298.15 K
SO
2
= 1 c
e

O
2
= 0.6 0.5 c
e

N
2
= 2.257
Reaction
c
e

Product
T
SO
2
= 1 c
e

O
2
= 0.6 0.5 c
e

N
2
= 2.257
0 H H H
0
P e
0
298
= A + c A = A

}
= A
i
T
T
P
i
0
P
0
i
dT
R
C
R n H
( )

}
+ + =

i
T
T
2
i i i i
0
dT T D T B A R n
}
(

|
.
|

\
|

+
|
.
|

\
|

+
|
.
|

\
|

= A

T
T
2
i
i i
i
i i
i
i i
0
P
0
dT T D n T B n A n R H
( ) ( )
(
(
(

|
.
|

\
|

|
.
|

\
|

|
.
|

\
|

+
|
.
|

\
|

=
0
i
i i
2
0
2
i
i i
0
i
i i
T
1
T
1
D n T T
2
B n
T T A n R
(a)
(b)
SO
2
O
2
SO
3

v 1 1 + 1
A 5.699 3.639 8.060
B 0.801 10
-3
0.506 10
-3
1.056 10
-3
C 0 0 0
D 1.015 10
5
0.227 10
5
2.028 10
5
AH
0
f,298
296 830 0 395 720
AG
0
f,298
300 194 0 371 060
278 . 1 A = A
3
10 251 , 0 B

= A
0 C = A
5
10 786 . 0 D = A
1 0
298
mol J 98890 H

= A
1 0
298
mol J 70866 G

= A
( )( )
12
0
0
0
0
10 6054 , 2
15 , 298 314 , 8
70866
exp
RT
G
exp K = = |
.
|

\
| A
=
38
(

|
.
|

\
|

A
=
T
T
1
RT
H
exp K
0
0
0
0
1
( )( )
(

|
.
|

\
|

=
T
15 , 298
1
15 , 298 314 , 8
98890
exp
( ) T f K
2
=
2 1 0
K K K K =
(

|
.
|

\
|
=
T
15 , 298
1 894 . 39 exp (c)
(d)
(e)
( )
5 . 0
e
e
e
e
05
O SO
SO
5 . 0 6 . 0
5 . 0 857 . 3
1 y y
y
K
2 2
3
|
.
|

\
|
c
c
c
c
= =
( ) K K
P
P
y
0
i
i
i
=
|
.
|

\
|
= [
v
v
For hign temperature and pressure of 1 bar:
(f)
Algorithm:
1. Assume a starting value of T
2. Evaluate K
1
[eq. (c)], K
2
[eq. (d)], and K [eq. (e)]
3. Solve for c
e
[eq. (f)]
4. Evaluate T [eq. (a)]
5. Find a new value of T as the arithmatic mean value
just calculated and the initial value; return to step
2.

The scheme converges on the value c
e
= 0.77 and T =
855.7 K
The composition of the product is:
( )( )
0662 . 0
472 . 3
23 . 0
77 . 0 5 . 0 857 . 3
77 . 0 1
5 . 0 857 . 3
1
y
e
e
SO
2
= =

=
c
c
=
( )( )
( )( )
0619 . 0
472 . 3
215 . 0
77 . 0 5 . 0 857 . 3
77 . 0 5 . 0 6 . 0
y
2
O
= =

=
2218 . 0
472 . 3
77 . 0
y
3
SO
= =
6501 . 0
472 . 3
257 . 2
y
2
N
= =