Atkins Physical Chemistry

Eighth Edition
Chapter 7 Lecture 2
Chemical Equilibrium
Copyright 2006 by Peter Atkins and Julio de Paula


Peter Atkins Julio de Paula
How equilibria respond to pressure
K ln RT G
o
r
=
Defined at a single standard pressure, 1 bar

Therefore K is independent of pressure:

However, equilibrium composition is
NOT necessarily pressure-independent!
e.g., 3 H
2
(g) + N
2
(g) 2 NH
3
(g)

Recall two ways to pressurize a gas:
0
P
K
T
= |
.
|

\
|
c
c
Fig 4.11
Two methods of
applying pressure
to a condensed phase
Fig 7.6 Compression of a reaction at equilibrium
Consider: A 2B
A
B
A
2
B
P
P
K =
Le Chateliers principle:
If an external stress is applied to
a system at equilibrium, the
system will adjust itself in order
to minimize the stress
A 2B and K remains constant
as system is compressed,
Fig 7.7 Pressure dependence of degree of dissociation
Consider: A 2B
Pure A
Pure B
values of K
Example:
3 N
2
(g) + H
2
(g) 2 HN
3
(g)
Predict the effect on K of a ten-fold increase in pressure





so to preserve the initial value of K,

LeChaletiers principle says that K must increase by 100-fold
( )
( ) ( )
01 . 0
atm 10 atm 10
atm 10
P P
P
K
3
2
H
3
N
2
HN
2 2
3
= = =
How equilibria respond to temperature
System will shift in endothermic direction as T

System will shift in exothermic direction as T

Summary:

Exothermic reactions: Increased T favors reactants

Endothermic reactions: Increased T favors products

From Le Chateliers principle for a system at equilibrium:
How equilibria respond to temperature
The vant Hoff equation:
2
o
r
RT
H
dT
K ln d A
=
2
o
r
P
T
H
dT
G/T) ( d A
= |
.
|

\
| A
The Gibbs-Helmholtz equation (3.53):
K ln RT G
o
r
=
Since Eqn 7.17 is:
K ln R
T
G
o
r
=
R
H
d(1/T)
K ln d
o
r
A
=
2
T
1
dT
(1/T) d
=
Fig 7.8 Effect of temperature on a chemical equilibrium A B
in terms of the Boltzmann distribution
Endothermic
Exothermic
B increases at
expense of A
A increases at
expense of B
Fig 7.9 Plot of

ln K versus 1/T
Ag
2
CO
3
(s) Ag
2
O (s) + CO
2
(g)
R
H
d(1/T)
K ln d
o
r
A
=
Variation of K with temperature for:
How equilibria respond to temperature
The value of K at different temperatures
To find K
2
at T
2
, given K
1
at T
1
, integrate:
R
H
d(1/T)
K ln d
o
r
A
= ) T / 1 ( d
R
H
K ln d
o
r
A
=
} }
A
=
2
1
o
r
2
1
) T / 1 ( d
R
H
K ln d
Assuming H
r
o
is T-independent
|
|
.
|

\
|

=
1 2
o
r
1 2
T
1
T
1
R
H
K ln K ln