= 0
i i
A v
Extent of reaction, c
dn
1
/v
1
= dn
2
/v
2
= dn
3
/v
3
= = dn
i
/v
i
= dc
c = (n
i
n
i0
)/v
i
Conversion, X
X = (n
i0
n
i
)/n
i0
=  (v
i/
n
io
)
c
Examples:
2HI
2 2
+ I H r
f
=
k
f
C
H
2
C
I
2
r
b
=
k
b
C
HI
2
and
Forward reaction is 1st order in C
H
2
and C
I
2
( 2nd order overall)
Reverse reaction is 2nd order in C
HI
Stoichiometric Equation
This describes the overall reaction but the reaction order cannot
be deduced from it.
Compare the above reaction with the analogous nonelementary
reaction between H
2
and Br
2 .
2HBr
2 2
+ Br H
2
2
2
2
2 1
1
Br HBr
Br H
f
C C k
C C k
r
+
=
k
1
k
2
Chemical Reaction Equilibrium
Kinetics vs. Themodynamics
Chemical Reaction Equilibria
Equilibrium state for given T and P
Criteria :
(AG)
T,P
= (oG/oc)
T, P
=
= 0
i i
v
(AG) : Gibbs free energy change,
i
: the chemical potential
0 ) ln ( ) (
,
= + = A
i
i
o
i i P T
a RT G v G
 RT ln K
a
= AG
o
a a
a a
a b
B A
a d
D
a c
C
RT G
/
/ /
ln
0
= A
Consider the general reversible reaction:
D cC d bB aA + +
At equilibrium r
A
=0
Therefore:
Therefore:
b
B
a
A
d
D
c
C
C
bB
fA
C C
C C
K
k
k
= =
Thermodynamic equilibrium relationship
b
B
a
A fA fA
C C k r =
d
D
c
C bA bA
C C k r =
0 = + =
bA fA A
r r r
r
fA
= r
bA
d
D
c
C bA
b
B
a
A fA
C C k C C k =
Thermodynamic equilibrium constant
(


.

\

A
=
T T R
H
T K T K
RX
C C
1 1
exp ) ( ) (
1
1
(


.

\

A
=
T T R
H
T K T K
RX
C C
1 1
exp ) ( ) (
1
1
K
C
T
K
C
T
Endothermic
Exothermic
All reactions are reversible in principle.
The extent of reversibility depends on AG, the Gibbs
Free Energy change.
p
RTInK G = A
Where K
p
is the equilibrium constant in
terms of partial pressures.
Chemical equilibrium
If K
p
is large, reaction is essentially irreversible, which
means that the equilibrium position lies very far to the
product side.
Equilibrium Constants
P a
K K K
=
a
i
= f
i
/ f
i,o
=
i
P
i
C C
C C
a b
B A
a d
D
a c
C
C
K
/
/ /
=
C C
C C
a b
B A
a d
D
a c
C
C
K
/
/ /
=
P a
K K K
=
o
) (RT K K
C P
=
Impact of T, P, Inert changes
Total pressure change
Pi=yi P
K
P
=K
y
P
o
d ln K/dT = AH
o
(T) /RT
2
Temperature change
dT C H T H
o
p o
o
}
A + A = A ) (
plot log K vs 1/T , slope = (AH
o
/R), (see Fig EC1.1)
Exo. Reaction (AH
o
negative), K decreases with increasing T
Endo. Reaction (AH
o
positive), K increases with increasing T
K
a
=K
f/P
[P/n
A
+ n
B
+n
C
+n
D
+ n
I
]
c+dab
) (
d
D
c
C
b
B
a
A
n n
n n
Inert change
Impact of T, P, Inert changes
Calculation Procedure
Determine (AG
o
) or (AH
o
).
a A + b B c C + d D maka:
AX
o
= c. AX
o
f,C
+ d. AX
o
f,D
a. AX
o
f,A
b. AX
o
f,B
, X : G, H
Calculate K
P
at T
with AH
o
(T) = AH
o
(25
o
C) +}AC
p
dT
2
) ( ln
RT
T H
dT
K d
o
P
A
=
{ } ) ( ) ( ln T G T K RT
o
A =
Calculation Procedure
Combine equilibrium composition and Equilibrium
constant
b
B
a
A
d
D
c
C
a a
a a
K
.
.
=
i i
a K H =
Express in Extent of reaction, composition or conversion
0 = E
i i
A v c


.

\

=
=
oi
i
oi
i oi
i
n
v
n
n n
X
Solve analytically/graph or numerically
Example 36 The reversible gasphase decomposition of nitrogen
tetroxide, N
2
O
4
, to nitrogen dioxide, NO
2
, is to be carried out at
constant temperature. The feed consists of pure N
2
O
4
at 340 K and
202.6 kPa (2 atm). The concentration equilibrium constant, K
c
, at 340
K is 0.1 mol/dm
3.
B A 2
concentration equilibrium constant:
at
equilibrium !!
(a) Calculate the equilibrium conversion of N
2
O
4
in a constant
volume batch reactor.
at
equilibrium !!
(b) Calculate the equilibrium conversion of N
2
O
4
in a flow
reactor.
at
equilibrium !!
for batch system
for flow system
(c) Assuming the reaction is elementary, express the rate of
reaction solely as a function of conversion for a flow system
and for a batch system.
Elementary reaction:
B A 2
(d) Determine the CSTR volume necessary to achieve 80% of
the equilibrium conversion.
CSTR design equation
HW2
Scott Fogler
P311A
P315B
P316B