7.

Chemical Equilibrium
T =const, P =const:
dG
T,P
=

i
dn
i
0
equilibrium: G = min

i
dddn
i
=0
reaction

1
J
1
+
2
J
2
+

l
J
l
+
m
J
m
+

i
J
i
=0

i
positive for products

i
negative for reactants
extent of reaction
ddd
dddn
i

i
PChem I 7.1
independent of i due to mass balance
dG
T,P
=

i
dn
i
=

i
d
dG
T,P
=
_

i
_
d =
r
Gd
=
r
G =
_
G

_
T,P
equilibrium: dG
T,P
=0 =

i
d
dynamic equilibrium
each forward reaction step is exactly balanced by its
back reaction
equilibrium:
r
G =

i
=0

i
=

i
+RT lna
i

r
G =

i
_

i
+RT lna
i
_
=

i
+

i
RT lna
i
PChem I 7.2
=
r
G

+RT

i
ln
_
a

i
i
_

r
G =
r
G

+RT ln
_

i
a

i
i
_
reaction quotient Q

i
a

i
i

r
G =
r
G

+RT lnQ
equilibrium
r
G =0
equilibrium 0 =
r
G

+RT lnK

r
G

=RT lnK
K Q
eq
=

i
a

i
i ,eq
equilibrium constant

r
G =RT lnK +RT lnQ =RT ln
_
Q
K
_
if Q < K, then
r
G < 0: forward reaction dominates:
reactants products
if Q > K, then
r
G > 0: back reaction dominates:
products reactants
PChem I 7.3
[Figure: G vs ; Atkins 9th ed., Fig. 6.1]
activities
ideal gas a
i
=
P
i
P

real gas a
i
=
f
i
P

i
P
i
P

PChem I 7.4
pure solids and liquids (standard state: pure sub-
stance at 1bar): a
i
=1
justication (T =const):
RT lna
i
=
i
=
i

i
=
_
P
P

V
i
dP V
i
P 0
= lna
i
0 = a
i
1
compared to gases, G for liquids and solids is rather
insensitive to pressure changes, since V (s/l ) V (g)
[Figure: G vs P for gases, liquids, and solids; Atkins 9th ed., Fig. 3.21]
PChem I 7.5
as long as V
i
and P are not too large, a
i
(s/l ) 1
example: solid with molecular mass 200u and density
2.00g cm
3
, i.e., V
i
= 100cm
3
mol
1
, at T = 300K has
a
i
=1.08 1 at P =20bar
= in heterogeneous equilibria involving gases and
solids or liquids: a
i
(s/l ) =1
solutes:
a
i
=
i
c
i
c

c
i
c

, c

=1M
ideal gas reactions
K =

i
a

i
i
=

i
_
P
i
P

i
=K
P

r
G

=RT lnK
P
P
i
=x
i
P
K =K
P
=

i
_
x
i
P
P

i
=

i
x

i
i

i
_
P
P

i
PChem I 7.6
K =K
x
_
P
P

, =

i
c
i
=
n
i
V
=
P
i
RT
, P
i
=RTc
i
P
i
P

=
RTc
i
P

=
RTc
i
c

=
RTc

c
i
c

K =K
P
=

i
_
P
i
P

i
=

i
_
RTc

c
i
c

i
=

i
_
c
i
c

i
_
RTc

i
K =K
c

_
RTc

real gas reactions

K =

i
a

i
i
=

i
_
f
i
P

i
=

i
_

i
P
i
P

i
=

i
i

i
_
P
i
P

i
K =K

K
P
PChem I 7.7
K =

i
a

i
i
=exp
_

r
G

RT
_
equilibrium does not depend on a catalyst
equilibrium constant K does not depend on total
pressure
_
K
P
_
T
=0
however
equilibrium composition, {x
i
} or {c
i
}, generally de-
pends on P
K =K
x
_
P
P

=K
x
=K
_
P
P

or
K
x

1
P

PChem I 7.8
K
x
depends on P if =0
> 0: K
x
as P : increasing pressure favors re-
actants
< 0: K
x
as P : increasing pressure favors
products
illustration of
Le Chateliers principle: When a system at equilibri-
um is perturbed, it responds in a way that tends to
minimize the effect of the perturbation.
equilibrium constant K does depend on T
_
K
T
_
P
=
_

T
exp
_

r
G

RT
__
P
=exp
_

r
G

RT
_

1
R
_
d(
r
G

/T)
dT
dK
dT
=
K
R
d(
r
G

/T)
dT
1
K
dK
dT
=
1
R
d(
r
G

/T)
dT
dlnK
dT
=
1
R
d(
r
G

/T)
dT
PChem I 7.9
dlnK
dT
=
1
R
(
r
H

)
T
2
Gibbs-Helmholtz equation
dlnK
dT
=

r
H

RT
2
vant Hoff equation
another illustration of Le Chateliers principle

r
H

<0 (exothermic reaction under standard condi-

tions) = K as T : increasing temperature fa-
vors reactants

r
H

> 0 (endothermic reaction under standard con-

ditions) = K as T : increasing temperature fa-
vors products
integrate vant Hoff equation with the assumption
that
r
H

=const:
ln
_
K
2
K
1
_
=

r
H

R
_
1
T
2

1
T
1
_
PChem I 7.10
[Figure: lnK vs 1/T; Atkins 9th ed., Fig. 6.9]
PChem I 7.11