1

The transformation of raw materials into products

of greater value by means of chemical reaction is a
major industry, and a vast array of commercial
products is obtained by chemical synthesis.
Sulfuric acid, ammonia, ethylene, propylene,
phosphoric acid, chlorine, nitric acid, urea,
benzene, methanol, ethanol, and ethylene glycol
fibers, paints, detergents, plastics, rubber, paper,
fertilizers, insecticides, etc.
2
Clearly, the chemical engineer must be familiar
with chemical-reactor design and operation.
3
Both the rate and the equilibrium conversion of a
chemical reaction depend on the temperature,
pressure, and composition of reactants.
Consider the oxidation of SO
2
to SO
3
.

2 SO
2
(g) + O
2
(g) 2 SO
3
(g)

The rate of reaction increases as temperature
increases.
The equilibrium conversion to SO
3
falls as temperature
rises, decreasing from about 90% at 520C to 50% at
about 680C.
V
2
O
5
300C

4
The equilibrium conversions represent maximum
possible conversions regardless of catalyst or reaction
rate.
The evident conclusion is that both equilibrium and
rate must be considered in the exploitation of chemical
reactions for commercial purposes.
Although reaction rates are not susceptible to
thermodynamic treatment, equilibrium conversions
are.
Therefore, the purpose of this chapter is to determine
the effect of temperature, pressure, and initial
composition on the equilibrium conversions of
chemical reactions.
5
Many industrial reactions are not carried to
equilibrium; reactor design is then based
primarily on reaction rate.
However, the choice of operating conditions
may still be influenced by equilibrium
considerations.
Moreover, the equilibrium conversion of a
reaction provides a goal by which to measure
improvements in a process.
6
Similarly, it may determine whether or not an
experimental investigation of a new process is
worthwhile.
For example, if thermodynamic analysis indicates
that a yield of only 20% is possible at equilibrium
and if a 50% yield is necessary for the process to be
economically attractive, there is no purpose to an
experimental study.
On the other hand, if the equilibrium yield is 80%,
an experimental program to determine the reaction
rate for various conditions of operation (catalyst,
temperature, pressure, etc.) may be warranted.
7
8
Reaksi secara umum:
. . . A A . . . A A
4 4 3 3 2 2 1 1
+ v + v + v + v
i
v adalah koefisien stoikiometri reaksi
Konvensi tanda untuk v
i
:
Positif (+) untuk produk
Negatif () untuk reaktan
CONTOH:
CH
4
+ H
2
O CO + 3 H
2

3 1 1 1
2 2 4
H CO O H CH
= v = v = v = v
(1)
9
Perubahan mol spesies yang ada dalam reaksi berbanding
lurus dengan bilangan stoikiometrinya.
Jika 3 mol CH
4
berkurang karena bereaksi, maka H
2
O juga
berkurang 3 mol, sementara itu 3 mol CO dan 9 mol H
2

terbentuk.
. dst
dn dn dn dn
1
1
3
3
1
1
2
2
v
=
v v
=
v
c
v
= =
v
=
v
=
v
=
v
d
dn dn dn dn dn
i
i
4
4
3
3
2
2
1
1

c v = d dn
i i
( i = 1, 2, 3, ..., N)
Koordinat reaksi
(2)
(3)
10
CH
4
+ H
2
O CO + 3 H
2

(1) (2)

(3)

(4)
3
1
3 dn
1
1
=

=
v
3
1
3 dn
2
2
=

=
v
3
1
3 dn
3
3
=
+
+
=
v
3
3
9 dn
4
4
=
+
+
=
v
CH
4
H
2
O

H
2
CO

11
(4)
Pers. (2) dan (3) menyatakan perubahan c akibat
perubahan jumlah mol spesies yang bereaksi.
Definisi dari c dilengkapi dengan pernyataan c = 0 untuk
kondisi awal sistem, sebelum reaksi.
Jadi integrasi pers. (3) dari kondisi awal sebelum reaksi
dengan c = 0 dan n
i
= n
i0
ke kondisi setelah reaksi:
}
c v =
}
c
0
i
n
n
i
d dn
i
0
i
c v + =
i i i
0
n n
( i = 1, 2, 3, ..., N)
12
c v =
i i i
0
n n
Penjumlahan untuk semua spesies:

v c +

=
i
i
i
i
i
i
0
n n n
cv + =
0
n n

=
i
i
n n
=
i
i 0
0
n n

v = v
i
i
Dengan:
Jadi fraksi mol y
i
dari satu spesies jika dihubungkan
dengan c:
vc +
c v +
= =
0
i i
i
i
n
n
n
n
y
0
(5)
13
CONTOH
Untuk sistem dengan reaksi:
CH
4
+ H
2
O CO + 3 H
2
Mula-mula ada 2 mol CH
4
, 1 mol H
2
O, 1 mol CO, dan 4 mol
H
2
. Tentukan pernyataan untuk y
i
sebagai fungsi c.
PENYELESAIAN
2 1 1 1 3
i
i
= + =

v = v
8 4 1 1 2 n n
i
i 0
0
= + + + =

=
14
vc +
c v +
= =
0
i i
i
i
n
n
n
n
y
0
c +
c
=
2 8
2
y
4
CH
c +
c
=
2 8
1
y
O H
2
c +
c +
=
2 8
1
y
CO
c +
c +
=
2 8
3 4
y
2
H
15
CONTOH
Sebuah tangki berisi hanya n
0
uap air. Jika dekomposisi
terjadi menurut reaksi
H
2
O H
2
+ O
2
Tentukan pernyataan yang menghubungkan jumlah mol
dan fraksi mol tiap spesies dengan koordinat reaksi.
PENYELESAIAN
5 , 0 1 5 , 0 1
i
i
= + =

v = v
Jumlah mol masing-masing spesies:
c v + =
i i i
0
n n
16
c =
0 O H
n n
2
c =
2
H
n
c = 5 , 0 n
2
O
c + = 5 , 0 n n
0
c +
c
=
5 , 0 n
n
y
0
0
O H
2
c +
c
=
5 , 0 n
y
0
H
2
c +
c
=
5 , 0 n
5 , 0
y
0
O
2
c v + =
i i i
0
n n
17
Jika ada dua atau lebih reaksi independen yang
berlangsung bersamaan, maka digunakan subskrip j
sebagai indeks untuk reaksi.
c
j
: koordinat untuk reaksi j.
v
i,j
: bilangan stoikiometri untuk spesies i dalam
reaksi j
Karena jumlah mol satu spesies n
i
dapat berubah karena
beberapa reaksi, maka persamaan umum yang analog
dengan persamaan (3) adalah:

c v =
j
j j , i i
d dn
( i = 1, 2, 3, ..., N)
c v = d dn
i i
18
Integrasi dari n
i
= n
i0
dan c
j
= 0:

c v + =
j
j j , i i i
0
n n
( i = 1, 2, 3, ..., N) (6)
Jika semua spesies dijumlahkan:

c
|
.
|

\
|

v + =

c v +

=
j
j
i
j , i 0
i j
j j , i
i
i
i
i
n n n n
0
Definisi dari bilangan stoikiometri total v ( E
i
v
i
):

v v
i
j , i j

c v +
j
j j 0
n n

c v +

c v +
= =
j
j j
j
j j , i i
i
i
n
n
n
n
y
0
( i = 1, 2, 3, ..., N) (7)
19
20

c v + =
j
j j , 1 1 1
0
n n

c v + =
j
j j , 2 2 2
0
n n

(+)
+
|
.
|

\
|

c v + +
|
.
|

\
|

c v + = + + =
j
j j , 2 2
j
j j , 1 1 2 1
0 0
n n n n n

c v +

|
.
|

\
|

c v + =

=
i j
j j , i
i
i
i j
j j , i i
i
i
0 0
n n n n
CONTOH
Untuk sistem dengan reaksi:
CH
4
+ H
2
O CO + 3 H
2
(1)

CH
4
+ 2H
2
O CO
2
+ 4 H
2
(2)

Mula-mula ada 2 mol CH
4
dan 3 mol H
2
O, tentukan
pernyataan untuk y
i
sebagai fungsi c
1
dan c
2
.
21
PENYELESAIAN
Tabel bilangan stoikiometri:
CH
4
H
2
O CO CO
2
H
2
v
j

1 1 1 1 0 3 2
2 1 2 0 1 4 2
i
j

c v + =
j
j j , i i i
0
n n
2 1
j
j j , 1 1 1 CH
2 n n n
0 4
c c =

c v + = =
2 1
j
j j , 2 2 2 O H
2 3 n n n
0 2
c c =

c v + = =
22
CH
4
+ H
2
O CO + 3 H
2
(1)

CH
4
+ 2H
2
O CO
2
+ 4 H
2
(2)

Pers. (7):
1
j
j j , 3 3 3 CO
0
n n n c =

c v + = =
2
j
j j , 4 4 4 CO
0 2
n n n c =

c v + = =
2 1
j
j j , 4 5 5 H
4 3 n n n
0 2
c + c =

c v + = =
2 1
j
j j 0
2 2 5 n n c + c + =

c v +

c v +

c v +
= =
j
j j
j
j j , i i
i
i
n
n
n
n
y
0
23
2 1
2 1
CH
CH
2 2 5
2
n
n
y
4
4
c + c +
c c
= =
2 1
2 1
O H
O H
2 2 5
2 3
n
n
y
2
2
c + c +
c c
= =
2 1
1 CO
CO
2 2 5 n
n
y
c + c +
c
= =
2 1
2
CO
CO
2 2 5 n
n
y
2
2
c + c +
c
= =
2 1
2 1
H
H
2 2 5
4 3
n
n
y
2
2
c + c +
c + c
= =
24
25
The total Gibbs energy of a closed system at constant T
and P must decrease during an irreversible process and
that the condition for equilibrium is reached when G
t

attains its minimum value.
At this equilibrium state,
( ) 0 dG
P , T
t
=
Thus if a mixture of chemical species is not in chemical
equilibrium, any reaction that occurs at constant T and P
must lead to a decrease in the total Gibbs energy of the
system.
The significance of this for a single chemical reaction is
seen in the following figure.
(1)
26
Figure 1. The total Gibbs energy in relation to the reaction coordinate
27
Since c is the single variable that characterizes the
progress of the reaction, and therefore the composition of
the system, the total Gibbs energy at constant T and P is
determined by c .
The arrows along the curve Figure 1 indicate the directions
of changes in (G )
T,P
that are possible on account of
reaction.
The reaction coordinate has its equilibrium value c, at the
minimum of the curve.
28
Figure 1 indicates the two distinctive features of the
equilibrium state for given temperature and pressure:
The total Gibbs energy G
t
is a minimum.
Its differential is zero.
Each of these may serve as a criterion of equilibrium.
Thus, we may write an expression for G
t
as a function of c
and seek the value of c which minimizes G
t
, or we may
differentiate the expression, equate it to zero, and solve
for c.
29
30
the fundamental property relation for single-phase
systems, provides an expression for the total differential
of the Gibbs energy:
( ) ( ) ( )

+ =
i
i i
dn dT nS dP nV nG d
If changes in the mole numbers n
i
occur as the result of a
single chemical reaction in a closed system, then by Eq. (2)
each dn
i
may be replaced by the product v
i
dc.
Equation (1) then becomes:
(2)
( ) ( ) ( )

c v + =
i
i i
d dT nS dP nV nG d
(3)
31
32
( ) ( ) ( )

c v + =
i
i i
d dT nS dP nV nG d
( )
( ) ( )

v +
c

c
=
c i
i i
d
dT
nS
d
dP
nV
d
nG d
P konstan dP = 0
T konstan dT = 0
( )

v =
c i
i i
d
nG d
(T dan P konstan)
( )

v =
(

c c
c
i
i i
P , T
nG
Since nG is a state function, the right side of this
equation is an exact differential expression; whence,
( ) ( )
P , T
t
P , T
i
i i
G nG
(

c c
c
=
(

c c
c
=

v
Thus the quantity E
i
v
i

i
represents, in general, the rate of
change of the total Gibbs energy of the system with the
reaction coordinate at constant T and P.
Figure 1 shows that this quantity is zero at the equilibrium
state.
A criterion of chemical-reaction equilibrium is therefore:
0
i
i i
=

v
(4)
(5)
33
Recall the definition of the fugacity of a species in solution
( )
i i i
f

ln RT T + I =
(6)
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)
The difference between these two equations is:
0
i
i
0
i i
f
f

ln RT G = (8)
34
35
0
i
i
0
i i
f
f

ln RT G =
0
i
i
0
i i
f
f

ln RT G + =
Combining Eq. (5) with Eq. (8) to eliminate
i
gives for
the equilibrium state of a chemical reaction:
0
f
f

ln RT G
i
0
i
i
0
i i
=

+ v
0 f f

ln RT G
i
0
i i
i
0
i i
i
=

v
v
RT
G
f f

ln
i
0
i i
0
i i
i
i

v
= [
v
(9)
(11)
(10)
36

v =

v
v
i
0
i i
i
0
i i i
i
0
i i i
i
f f

ln RT f f

ln RT f f

ln RT
(
(

+ |
.
|

\
|
+ |
.
|

\
|
+ |
.
|

\
|
=
v v v

3 2 1
0
3
3
0
2
2
0
1
1
f
f

ln
f
f

ln
f
f

ln RT
(
(

|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
=
v v v

3 2 1
0
3
3
0
2
2
0
1
1
f
f

f
f

f
f

ln RT
(
(

|
.
|

\
|
H =
v
i
0
i
i
i
f
f

ln RT
37
38
0
f
f

ln RT G
i
0
i
i
i
i
0
i i
=
(
(

|
.
|

\
|
H +

v
v
0 f f

ln RT G
i
0
i i
i
0
i i
i
=

v
v
RT
G
f
f

ln
i
0
i i
0
i
i
i
i

v
=
(
(

|
.
|

\
|
H
v

v =
(
(

|
.
|

\
|
H
v
i
0
i i
0
i
i
i
G
f
f

ln RT
i
39
RT
G
K ln f f

ln
i
0
i i
0
i i
i
i

v
= = [
v
RT
G
K ln
i
0
i i

v
=
|
|
.
|

\
|

v
=
RT
G
exp K
i
0
i i
In exponential form, this equation becomes
(12)
K f f

i
0
i i
i
= [
v
|
.
|

\
| A
=
RT
G
exp K
0
This equation defines K; it is given alternative expression by
RT
G
K ln
0
A
=
Also by definition
(13)
(14)

v = A
i
0
i i
0
G G
(15)
40
Since G
i
0
is a property of pure species i in its
standard state at fixed pressure, it depends only on
temperature.
By Eq. (15) it follows that AG
0
and hence K, are also
functions of temperature only.
In spite of its dependence on temperature, K is
called the equilibrium constant for the
reaction; E
i
v
i
G
i
0
, represented by AG
0
, is called
the standard Gibbs-energy change of reaction.
41
The fugacity ratios in Eq. (12) provide the connection
between the equilibrium state of interest and the
standard states of the individual species, for which data
are presumed available.
The standard states are arbitrary, but must always be at
the equilibrium temperature T.
The standard states selected need not be the same for
all species taking part in a reaction.
However, for a particular species the standard state
represented by G
i
0
must be the same state as for the
fugacity f
i
0
.
42
The function AG
0
= E
i
v
i
G
i
0
in Eq. (15) is the difference
between the Gibbs energies of the products and reactants
(weighted by their stoichiometric coefficients) when each is
in its standard state as a pure substance at the standard-
state pressure, but at the system temperature.
Thus the value of AG
0
is fixed for a given reaction once the
temperature is established, and is independent of the
equilibrium pressure and composition.
Other standard property changes of reaction are similarly
defined.
Thus, for the general property M:

A = A
0
i
0
M M
(16)
43
For example, the relation between the standard heat of
reaction and the standard Gibbs energy change of
reaction may be written for species i in its standard
state:
( )
dT
RT G d
RT H
0
i
2 0
i
=
Total derivatives are appropriate here because the
properties in the standard state are functions of
temperature only.
(17)
44
Multiplication of both sides of Eq. (17) by v
i
and
summation over all species gives:
dT
RT G d
RT H
i
0
i i
2
i
0
i i
|
.
|

\
|

v
=

v
(18)
( )
dT
RT G d
RT H
0
2 0
A
= A
(19)
Or:
45
46
Since the standard-state temperature is that of the
equilibrium mixture, the standard property changes of
reaction, such as AG
0
and AH
0
, vary with the equilibrium
temperature.
The dependence of AG
0
on T is given by Eq. (17), which
may be rewritten:
( )
2
0 0
RT
H
dT
RT G d A
=
A
In view of Eq. (14), this becomes
2
0
RT
H
dT
K ln d A
=
(20)
RT
G
K ln
0
A
=
(14)
47
48
dT
RT
H
K ln d
2
0
A
=
}
A
=
}
2
1
2
1
T
T
2
0
K ln
K ln
dT
RT
H
K ln d
Equation (20) gives the effect of temperature on the
equilibrium constant, and hence on the equilibrium
conversion.
If AH
0
< 0 (exothermic) K decreases as T increases
If AH
0
> 0 (endothermic) K increases with T
If AH
0
is assumed independent of T, integration of Eq.
(20) from a particular temperature T' to an arbitrary
temperature T leads to the simple result:
|
.
|

\
|

A
=
' T
1
T
1
R
H
' K
K
ln
0
(21)
49
50
However, if AH
0
is T dependent, as defined in Eq. (11) of
previous Chapter:
2
0
RT
H
dT
K ln d A
=
}
|
.
|

\
|
A + A = A
o
o
T
T
P
0
0
0
dT
R
C
R H H
dT dT
R
C
T
1
RT
H
K ln d
T
T
P
2
0
0
(

}
|
.
|

\
|
A +
A
=
o o
51
52
dT dT
R
C
T
1
RT
H
K ln d
T
T
P
2
0
0
(

}
|
.
|

\
|
A +
A
=
o o
}
(

}
|
.
|

\
|
A +
A
=
}
o o
T
T
T
T
P
2
0
K ln
K ln
0 0 0
dT dT
R
C
T
1
RT
H
K ln d
}
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
P
2
0
0
0 0
dT dT
R
C
T
1
RT
H
K ln K ln
}
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
P
2
0
0
0 0
dT dT
R
C
T
1
RT
H
K
K
ln
53
}
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
P
2
0
0
0 0
dT dT
R
C
T
1
RT
H
K
K
ln
)
`

}
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
P
2
0
0
0 0
dT dT
R
C
T
1
RT
H
exp
K
K
)
`

}
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
P
2
0
0
0 0
dT dT
R
C
T
1
RT
H
exp K K
54
)
`

}
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
P
2
0
0
0 0
dT dT
R
C
T
1
RT
H
exp K K
)
`

}
(

}
|
.
|

\
|
A
)
`

}
(

A
=
o o
T
T
T
T
P
T
T
2
0
0
0 0 0
dT dT
R
C
T
1
exp dT
RT
H
exp K K
K
1

K
2

)
`

} }
(

}
|
.
|

\
|
A +
A
=
o o
T
T
T
T
T
T
P
2
0
0
0 0 0
dT dT
R
C
T
1
dT
RT
H
exp K K
Integration from T
0
to T results in:
2 1 0
K K K K =
|
.
|

\
| A
=
0
0
0
0
RT
G
exp K
(

|
.
|

\
|
t

A
=
(

|
.
|

\
|

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

|
.
|

\
|
t
t
t A =
2
0 2
1
T B
2
1 1
ln A exp K
( ) ( ) ( )
)
`

t
t A
+
t
+ t t
A +
2
2
2
0
2
2
0
1
T
D
2
1 2 1
T C
6
1
(22)
(23)
(24)
(25)
55
EXAMPLE
Calculate the equilibrium constant for the vapor-phase
hydration of ethylene at 418.15 to 593.15K.
SOLUTION
Reaction:
C
2
H
4
(g) + H
2
O (g) C
2
H
5
OH (g)
56
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
4,450 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
57
376 , 1 470 , 3 424 , 1 518 , 3 A = = A
( )
3 3
10 157 , 4 10 450 , 1 394 , 14 001 , 20 B

= = A
( )
6 6
10 610 , 1 10 000 , 0 392 , 4 002 , 6 C

= + = A
( )
5 5
10 121 , 0 10 121 , 0 000 , 0 000 , 0 D = = A
( )
1 0
298
mol J 792 . 45 818 . 241 510 . 52 100 . 235 H

= = A
( )
1 0
298
mol J 378 . 8 572 . 228 490 . 68 490 . 168 G

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

\
| A
=
58
For T = 418.15K
(

|
.
|

\
|

A
=
T
T
1
RT
H
exp K
0
0
0
0
1
( )( )
3
10 985 , 4
15 , 418
15 , 298
1
15 , 298 314 , 8
792 . 45
exp

=
(

|
.
|

\
|

=
4025 , 1
15 , 298
15 , 418
T
T
0
= = = t
9860 , 0 K
2
=
( )( )( )
1 3
2 1 0
10 443 , 1 9860 , 0 10 985 , 4 366 , 29 K K K K

= = =
59
For T = 593.15K
(

|
.
|

\
|

A
=
T
T
1
RT
H
exp K
0
0
0
0
1
( )( )
4
10 023 , 1
15 , 593
15 , 298
1
15 , 298 314 , 8
792 . 45
exp

=
(

|
.
|

\
|

=
9894 , 1
15 , 298
15 , 593
T
T
0
= = = t
9794 , 0 K
2
=
( )( )( )
3 4
2 1 0
10 942 , 2 9794 , 0 10 023 , 1 366 , 29 K K K K

= = =
60