Chapter 6

Reaction Equilibrium
in Ideal Gas Mixtures
Physical Chemistry
Chapter 6
Chemical Potentials in
an Ideal Gas Mixture
Chemical Potential of a Pure Ideal Gas
VdP SdT dG + = (4.36)
dP
P
RT
dP V d
m
|
.
|

\
|
= =
isothermal, pure ideal gas
} }
=
2
1
1
2
1
P
P
dP
P
RT d
1
2
1 2
ln ) , ( ) , (
P
P
RT P T P T =
isothermal, pure ideal gas (6.1)
o
o
P
P
RT T ln ) ( + = pure ideal gas, P
o
1 bar (6.2)
dP V dT S d dG
m m m
+ = =
(4.86)*
i m
P T
G
n
G
,
,
i
i
=
|
|
.
|

\
|
c
c

one-phase pure
substance
Physical Chemistry
Chapter 6
Chemical Potentials
in an Ideal Gas Mixture
Fig. 6.1 T is fixed
P/P
o
-
o
0
1 2 3
RT
-RT
-2RT
m m m
TS H G = =
) (T f H
m
=
) (P f S
m
=
0 P as
For a pure ideal gas
Physical Chemistry
Chapter 6
Chemical Potentials
in an Ideal Gas Mixture
Fig. 6.2
) , ( ) , ( ) , , , , (
* *
2 1 i i i i i
P T P x T x x P T = =
An ideal gas mixture
Ideal gas
mixture at
T and P
P x P
i i

*
i
P
Pure gas
mixture at
and T
membrane
(1)
RT n PV
tot
=
(2) The mixture is separated by
thermally conducting rigid membrane
permeable to gas i only, and
P x P
i i

bar P
o
1
ideal gas mixture
(6.3)
Physical Chemistry
Chapter 6
Chemical Potentials
in an Ideal Gas Mixture
Fig. 6.2
) , ( ) , ( ) , , , , (
* *
2 1 i i i i i
P T P x T x x P T = =
Ideal gas
mixture at
T and P
P x P
i i

*
i
P
Pure gas
mixture at
and T
membrane
ideal gas mixture
(6.3)
o
i
o
i i
P
P
RT T ln ) ( + =
ideal gas mixture (6.4)*
bar P
o
1
The fundamental thermodynamic equation
No intermolecular interaction, no effect on
from other gases in the mixture.
i

Physical Chemistry
Chapter 6
Chemical Potentials
in an Ideal Gas Mixture
Fig. 6.1 (modified)
P
i
/P
o

i
-
i

o
0
1 2 3
RT
-RT
-2RT
) ( ) (
,
T G T
o
i m
o
i
=
) (T f
o
i
=
bar P
o
1
For an ideal gas mixture
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
For the ideal-gas reaction
dD cC bB aA + + (4.36)
the equilibrium condition

=
i
i i
0 v
D C B A
d c b a + = +
0 = +
B A D C
b a d c
o
i
o
i i
P
P
RT T ln ) ( + =
(6.4)*
0 ln ln
ln ln
=
+ + +
o
B
o
B
o
A
o
A
o
D
o
D
o
C
o
C
P
P
bRT b
P
P
aRT a
P
P
dRT d
P
P
cRT c


Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
(6.5)
) ln ln ln ln (
o
B
o
A
o
D
o
C
o
B
o
A
o
D
o
C
P
P
b
P
P
a
P
P
d
P
P
c RT
b a d c
+
= +
0 ln ln
ln ln
=
+ + +
o
B
o
B
o
A
o
A
o
D
o
D
o
C
o
C
P
P
bRT b
P
P
aRT a
P
P
dRT d
P
P
cRT c


o
B
o
A
o
D
o
C
i
i
o
i i
o
i T m i
o
T
b a d c T G G v v + = = A

) (
, ,
(
(

|
.
|

\
|

|
.
|

\
|

|
.
|

\
|
+
|
.
|

\
|
= A
b
o
B
a
o
A
d
o
D
c
o
C
o
P
P
P
P
P
P
P
P
RT G ln ln ln ln
Physical Chemistry
Chapter 6
the equilibrium condition
Ideal Gas Reaction Equilibrium
(6.6)
(6.7)
) ln ln ln (ln
b
o
B
a
o
A
d
o
D
c
o
C
o
P
P
P
P
P
P
P
P
RT G
|
.
|

\
|

|
.
|

\
|

|
.
|

\
|
+
|
.
|

\
|
= A
|
|
|
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
= A
b
o
B
a
o
A
d
o
D
c
o
C
o
P
P
P
P
P
P
P
P
RT G ln
b
o
B
a
o
A
d
o
D
c
o
C
o
P
P
P
P
P
P
P
P
P
K
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|

bar P
o
1
Physical Chemistry
Chapter 6
o
P
o
K RT G ln = A
Ideal Gas Reaction Equilibrium
o
P
o
K RT G ln = A
(6.7)
b
o
B
a
o
A
d
o
D
c
o
C
o
P
P
P
P
P
P
P
P
P
K
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|

bar P
o
1
0 ] ln [
,
=
|
|
.
|

\
|
+ =

o
eq i
o
i
i
i
i
i i
P
P
RT v v
0 ln ) (
,
=
|
|
.
|

\
|
+

i
o
eq i
o
i
i
i
P
P
RT T v
(6.8)

= + = +
i i
i i
i
i
i i
i i i
a c ca and b a b a ) (
Physical Chemistry
Chapter 6
0 =

i
i i
v
the equilibrium condition
Ideal Gas Reaction Equilibrium
(6.9)
) (
, ,
T G G
o
i
i
i
o
i T m
i
i
o
T
v v

= = A
(6.10)
[
= =
= = + + + =
n
i
i n n
n
i
i
a a a a a a a a
1
2 1 2 1
1
ln ) ln( ln ln ln ln
o
i T m
o
i
G T
, ,
) ( =

|
|
.
|

\
|
=
|
|
.
|

\
|
= A
i
o
eq i
o
eq i
i
i
o
T
i
P
P
RT
P
P
RT G
v
v
, ,
ln ln
Physical Chemistry
Chapter 6
[
=

n
i
n i
a a a a
1
2 1

(6.11)*
Ideal Gas Reaction Equilibrium
(6.12)
(
(

|
|
.
|

\
|
= A
[
=
i
n
i
o
eq i
o
T
P
P
RT G
v
1
,
ln
[
=

n
i
n i
a a a a
1
2 1

(6.11)*
i
i
o
eq i
o
P
P
P
K
v
[
|
|
.
|

\
|

,
o
P
o
T
K RT G ln = A
(6.13)*
(6.14)*
RT
G
o
P
o
e K
A

=
(6.15)
Physical Chemistry
Chapter 6
[
= =
=
n
i
i
n
i
i
a a
1 1
ln ln

|
|
.
|

\
|
= A
i
i
o
eq i
o
T
P
P
RT G
v
,
ln (6.10)
Ideal Gas Reaction Equilibrium
RT
G
o
P
o
e K
A

=
(6.15)
(6.9)
) (
, ,
T G G
o
i
i
i
o
i T m
i
i
o
T
v v

= = A
Since depends only on T, for a given ideal-gas
reaction is a function of T only.
o
T
G A
o
P
K
) ( ) ( T K K T G G
o
P
o
P
o o
= A = A
At a given temperature, is constant for a given reaction.
o
P
K
the standard equilibrium constant
the standard pressure equilibrium constant
o
P
K
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
( )
[

i
eq i P
i
P K
v
,
(6.19)
dD cC bB aA + +
Since is dimensionless, the standard equilibrium
constant is dimensionless.
o
i
P P
o
P
K
has dimensions of pressure raised to the change in mole
numbers for the reaction as written.
P
K
the equilibrium constant
the pressure equilibrium constant
P
K
i
i
o
eq i
o
P
P
P
K
v
[
|
|
.
|

\
|

,
(6.13)*
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
b a d f
o
o
b o
eq B
a o
eq A
d o
eq D
f o
eq F
b o
eq B
a o
eq A
d o
eq D
f o
eq F
o
P
P
RT c
c c c c
c c c c
P RT c P RT c
P RT c P RT c
K
+
|
|
.
|

\
|
=
=
) / ( ) / (
) / ( ) / (
) / ( ) / (
) / ( ) / (
, ,
, ,
, ,
, ,
(6.23)
dD fF bB aA + +
i
i
o
eq i
o
P
P
P
K
v
[
|
|
.
|

\
|

,
(6.13)*
the molar concentration
V
n
c
i
i
(6.21)*
ideal gas mixture RT c
V
RT n
P
i
i
i
= = (6.22)
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
b a d f
o
o
b o
eq B
a o
eq A
d o
eq D
f o
eq F
b o
eq B
a o
eq A
d o
eq D
f o
eq F
o
P
P
RT c
c c c c
c c c c
P RT c P RT c
P RT c P RT c
K
+
|
|
.
|

\
|
=
=
) / ( ) / (
) / ( ) / (
) / ( ) / (
) / ( ) / (
, ,
, ,
, ,
, ,
(6.23)
dD fF bB aA + +
An/mol
same dimension as P
o
3
/ 1 / 1 dm mol liter mol c
o
=
i
i
o
eq i
o
P
c
c
K
v
[
|
|
.
|

\
|

,
(6.24)
i
i
o
eq i
o
P
P
P
K
v
[
|
|
.
|

\
|

,
(6.13)*
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
i
i
o
eq i
o
P
c
c
K
v
[
|
|
.
|

\
|

,
(6.24)
i
i
o
eq i
o
P
P
P
K
v
[
|
|
.
|

\
|

,
(6.13)*
the standard equilibrium constant
the concentration equilibrium constant
o
c
K
the standard equilibrium constant
the standard pressure equilibrium constant
o
P
K
3
/ 1 / 1 dm mol liter mol c
o
=
bar P
o
1
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
b a d f
o
o
b o
eq B
a o
eq A
d o
eq D
f o
eq F
b o
eq B
a o
eq A
d o
eq D
f o
eq F
o
P
P
RT c
c c c c
c c c c
P RT c P RT c
P RT c P RT c
K
+
|
|
.
|

\
|
=
=
) / ( ) / (
) / ( ) / (
) / ( ) / (
) / ( ) / (
, ,
, ,
, ,
, ,
(6.23)
mol n
o
o
o
c
o
P
P
RTc
K K
/ A
|
|
.
|

\
|
=
(6.25)
( )
i
i
eq i x
x K
v
[

,
(6.26)
mol n
o
x
o
P
P
P
K K
/ A
|
.
|

\
|
=
(6.27)
Physical Chemistry
Chapter 6
vant Hoff Equation
RT
G
K
o
o
P
A
= ln
From (6.14)
dT
G d
RT RT
G
dT
K d
o o o
P
) ( 1 ln
2
A

A
= (6.31)
(6.9)
) (
, ,
T G G
o
i
i
i
o
i T m
i
i
o
T
v v

= = A
(6.32)

= = A
i
o
i m
i
i
o
i m i
o
dT
dG
G
dT
d
G
dT
d
,
,
) ( v v
o
i m
i
i
o
G G
,
= A v
( )
dT
G d
RT dT
T d
R
G
dT
K d
o o o
P
) ( 1 / 1 ln A

|
.
|

\
|
A
=
2
1 1
T T dT
d
=
|
.
|

\
|
Physical Chemistry
Chapter 6
vant Hoff Equation
dP V dT S dG
m m m
+ =
From
m
P
m
S
T
G
=
|
.
|

\
|
c
c
(6.31)
(6.33)
o
i m
o
i m
S
dT
dG
,
,
=
(6.34)
o
i
o
i m i
o
S S G
dT
d
A = = A
,
) ( v
(6.32)

= = A
i
o
i m
i
i
o
i m i
o
dT
dG
G
dT
d
G
dT
d
,
,
) ( v v
Physical Chemistry
Chapter 6
vant Hoff Equation
2 2
ln
RT
S T G
RT
S
RT
G
dT
K d
o o o o o
P
A + A
=
A
+
A
=
o o o
S T H G A A = A
(6.36)*
2
ln
RT
H
dT
K d
o o
P
A
=
(6.34)
o
i
o
i m i
o
S S G
dT
d
A = = A
,
) ( v
(6.32)

= = A
i
o
i m
i
i
o
i m i
o
dT
dG
G
dT
d
G
dT
d
,
,
) ( v v
Physical Chemistry
Chapter 6
Gibbs-Helmholtz Equation
TS H G =
T
H
T
G
T
H G
T
G
P
=

=
|
.
|

\
|
c
c
T
G H
S

=
T
H
T
G
T
G
P
=
|
.
|

\
|
c
c
P
P
T
G
T
T
T
G
T
G
|
|
.
|

\
|
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
P
P
P
T T
G
T
G
T T
G
T
|
|
.
|

\
|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
|
|
.
|

\
|
|
.
|

\
|
c
c 1 1
)
`

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
|
.
|

\
|
|
.
|

\
|
c
c
T
G
T
G
T T
G
T
G
T T
G
T
P P
P
1 1
2
Physical Chemistry
Chapter 6
Gibbs-Helmholtz Equation
)
`

|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
|
|
.
|

\
|
|
.
|

\
|
c
c
T
G
T
G
T T
G
T
G
T T
G
T
P P
P
1 1
2
T
H
T
G
T
T
P
=
|
|
.
|

\
|
|
.
|

\
|
c
c
2
T
H
T
G
T
P
=
|
|
.
|

\
|
|
.
|

\
|
c
c
2
T
H
T
G
T
P
A
=
|
|
.
|

\
|
|
.
|

\
|
A
c
c
When it is applied to changes
Physical Chemistry
Chapter 6
Differentiation of lnK
P
o
with respect to temperature gives
vant Hoff Equation
RT
G
K
o
o
P
A
= ln
From (6.14)
(6.36)*
|
|
.
|

\
|
A
=
T
G
dT
d
R dT
K d
o o
P
1 ln
The differentials are complete because K and G depend only
on temperature, not on pressure. Using Gibbs-Helmholtz
equation
2
T
H
T
G
T
P
A
=
|
|
.
|

\
|
|
.
|

\
|
A
c
c
2
ln
RT
H
dT
K d
o o
P
A
=
Physical Chemistry
Chapter 6
vant Hoff Equation
} }
A
=
2
1
2
1
2
) (
ln
T
T
o
T
T
o
P
dT
RT
T H
K
(6.36)*
2
ln
RT
H
dT
K d
o o
P
A
=
dT
RT
H
K d
o
o
P
2
ln
A
=
}
A
=
2
1
2
1
2
) (
) (
) (
ln
T
T
o
o
P
o
P
dT
RT
T H
T K
T K
(6.37)
4 2
ET CT BT A H
o
T
+ + + = A
(6.38)
|
|
.
|

\
|

A
~
2 1 1
2
1 1
) (
) (
ln
T T R
H
T K
T K
o
o
P
o
P
(6.39)
|
|
.
|

\
|

A
~
2 1
1 2
1 1
) ( ln ) ( ln
T T R
H
T K T K
o
o
P
o
P
Physical Chemistry
Chapter 6
vant Hoff Equation
(6.36)*
2
ln
RT
H
dT
K d
o o
P
A
=
R
H
T
d
K d
o o
P
A
=
|
.
|

\
|
1
ln
(6.40)
2
1 1
T T dT
d
=
|
.
|

\
|
dT
T T
d
2
1 1
=
|
.
|

\
|
The vant Hoff equation is an expression for the
slope of a graph of the equilibrium constant (specially,
lnK) plotted against the temperature. It may be expressed
in either of two ways:
Physical Chemistry
Chapter 6
Ideal Gas Reaction Equilibrium
) ( 2 ) ( 3 ) (
3 2 2
g NH g H g N +
The
equilibrium
extent of
reaction
the reaction quotient
3
2
2 2
3
H N
NH
P
P P
P
Q
(6.41)
P P
K Q < The reaction goes to right
P P
K Q = The reaction reaches equilibrium
P P
K Q > The reaction goes to left
0 >
eq

0 <
eq

0 =
eq

( )
[

i
eq i P
i
P K
v
,
(6.19) the equilibrium constant
The extent of
reaction
Physical Chemistry
Chapter 6
Simultaneous Equilibria
A system with several simultaneous reactions that have
species in common.
(6.47)
mol n mol n
mol n mol n mol n
CO H
CO O H CH
2 , 1
, 1 , 1 , 1
, 0 , 0
, 0 , 0 , 0
2
2 2 4
= =
= = =
2
3
1 ,
2 4
2
) (
|
|
.
|

\
|
=
tot
o
O H CH
H CO
o
P
n P
P
n n
n n
K
(6.48)
2 2 4
3H CO O H CH + +
2 2 2 4
4 2 H CO O H CH + +
2
2
4
2 ,
) (
) (
2 4
2 2
|
|
.
|

\
|
=
tot
o
O H CH
H CO
o
P
n P
P
n n
n n
K
Physical Chemistry
Chapter 6
Simultaneous Equilibria
At 600 K, CH
3
Cl(g) and H
2
O(g) react to form CH
3
OH, and
then form (CH
3
)
2
O with a simultaneous equilibrium shown:
(1)
, 6 . 10 , 00154 . 0
2 , 1 ,
= =
o
P
o
P
K K
Starting with equal amount of CH
3
Cl and H
2
O, find the
equilibrium amounts of all species.
) ( ) ( ) ( ) (
3 2 3
g HCl g OH CH g O H g Cl CH + +
) ( ) ( ) ( ) ( 2
2 2 3 3
g O H g O CH g OH CH +
(2)
Physical Chemistry
Chapter 6
Simultaneous Equilibria
Suppose that a system initially contains 1 mole of CH
3
Cl(g)
and H
2
O(g), x moles of HCl and y moles of (CH
3
)
2
O are
formed at equilibrium.
(1)
) ( ) ( ) ( ) (
3 2 3
g HCl g OH CH g O H g Cl CH + +
) ( ) ( ) ( ) ( 2
2 2 3 3
g O H g O CH g OH CH +
(2)
1-x 1-x+y x-2y x
x-2y y 1-x+y
6 . 10
) 2 (
) 1 (
00154 . 0
) 1 )( 1 (
) 2 (
2
2 ,
1 ,
=

+
=
=
+

=
y x
y x y
K
y x x
x y x
K
o
P
o
P
Physical Chemistry
Chapter 6
Simultaneous Equilibria
Suppose that a system initially contains 1 mole of CH
3
Cl(g)
and H
2
O(g), x moles of HCl and y moles of (CH
3
)
2
O are
formed at equilibrium.
6 . 10
) 2 (
) 1 (
00154 . 0
) 1 )( 1 (
) 2 (
2
2 ,
1 ,
=

+
=
=
+

=
y x
y x y
K
y x x
x y x
K
o
P
o
P
009 . 0
048 . 0
=
=
y
x
Physical Chemistry
Chapter 6
Simultaneous Equilibria
The equilibrium amounts of all species are
(1)
) ( ) ( ) ( ) (
3 2 3
g HCl g OH CH g O H g Cl CH + +
) ( ) ( ) ( ) ( 2
2 2 3 3
g O H g O CH g OH CH +
(2)
0.952 0.961 0.03 0.048
0.03 0.009 0.961
Physical Chemistry
Chapter 6