1

Chapter 16: Principles of Reactivity: Chemical Equilibria

2
I. Equilibrium
e.g., H
2
O + CO
2
H
2
CO
3

conc.
time
[H
2
O]
[CO
2
]
[H
2
CO
3
]
Dynamic equilibrium

Rate
forward
= Rate
reverse

3
I. Equilibrium
General: A B
c
o
n
c
.

time
[A]
[B]
c
o
n
c
.

time
[A]
[B]
Equilibrium lies on side of product.
Rate
forward
= Rate
reverse

k
f
[A] = k
r
[B]
1
] A [
] B [
r
f
> =
k
k
k
f
> k
r

Equilibrium lies on side of reactant.
Rate
forward
= Rate
reverse

k
f
[A] = k
r
[B]
1
] A [
] B [
r
f
< =
k
k
k
f
< k
r

4
I. Equilibrium
A. Equilibrium expressions
For the reaction, aA + bB cC + dD
concentration
equilibrium constant
(at a given temperature)
At equilibrium: Rate
forward
= Rate
reverse


k
f
[A]
a
[B]
b
= k
r
[C]
c
[D]
d

b a
d c
c
r
f
[B] [A]
[D] [C]
= = K
k
k
equilibirum expression
5
I. Equilibrium
A. Equilibrium expressions
Also, for the reaction, aA + bB cC + dD
b
B
a
A
d
D
c
C
p
p p
p p
K =
pressure
e.g., 2N
2
O
5
(g)

What are K
c
and K
p
?
4 NO
2
(g) + O
2
(g)
6
I. Equilibrium
A. Equilibrium expressions
Heterogeneous equilibria:

1. insoluble solids are not included in K
c
or K
p

2
3
2 3 '
c
] NH )][ ( AgCl [
] Cl ][ ) Ag(NH [
s
K
+
=
constant
Ag(NH
3
)
2
+
(aq) + Cl

(aq) e.g., AgCl(s) + 2NH

3
(aq)
2
3
2 3
c
'
c
] NH [
] Cl ][ ) Ag(NH [
)] ( AgCl [
+
= = K s K
7
I. Equilibrium
A. Equilibrium expressions
Heterogeneous equilibria:

2. solids, liquids are not included in K
p

3 2
4 2
SO O H
SO H
'
p
p p
p
K =
H
2
SO
4
(l) e.g., H
2
O(g) + SO
3
(g)
3 2 4 2
SO O H
p
SO H
'
p
1
p p
K
p
K
= =
constant (p
vap
at T)
8
I. Equilibrium
A. Equilibrium expressions
e.g., Write the equilibrium expression for each of the following reactions.
Cu(OH)
2
(s) Cu
2+
(aq) + 2 OH

(aq) (K
c
)
Ni(s) + 2Ag
+
(aq) Ni
2+
(aq) + 2 Ag(s) (K
c
)
2 NH
3
(g) + CO
2
(g) + H
2
O(g) (NH
4
)
2
CO
3
(s) (K
p
)
9
10
11
12
I. Equilibrium
B. Manipulating equilibrium expressions
1. reversing the equation
H
2
+ Cl
2
2HCl K
c
=
[HCl]
2

[H
2
][Cl
2
]
2HCl H
2
+ Cl
2
K
c
=
[H
2
][Cl
2
]
[HCl]
2
K
c
=
1
K
c

When reversing a chemical equation, take the inverse
of the equilibrium constant.
13
I. Equilibrium
B. Manipulating equilibrium expressions
2. multiplying equations by some factor
2H
2
+ 2Cl
2
4HCl K
c
=
[HCl]
4

[H
2
]
2
[Cl
2
]
2

When multiplying a chemical equation by some factor,
raise the equilibrium constant to that power.
K
c
= (K
c
)
2

H
2
+ Cl
2
HCl K
c
=
[HCl]
[H
2
]

[Cl
2
]

K
c
= (K
c
)

14
I. Equilibrium
B. Manipulating equilibrium expressions
3. adding equations
SO
2
+ NO
2
NO + SO
3

SO
3
+ H
2
O H
2
SO
4

SO
2
+ NO
2
+ H
2
O NO + H
2
SO
4

K
c1
=
[NO][SO
3
]
[SO
2
][NO
2
]
K
c2
=
[H
2
SO
4
]
[SO
3
][H
2
O]
K
c3
=
[NO][H
2
SO
4
]
[SO
2
][NO
2
][H
2
O]
K
c3
= K
c1
K
c2
=


[NO][SO
3
]
[SO
2
][NO
2
]
[H
2
SO
4
]
[SO
3
][H
2
O]
=
[NO][H
2
SO
4
]
[SO
2
][NO
2
][H
2
O]
When adding equations, multiply the equilibrium constants.
15
I. Equilibrium
B. Manipulating equilibrium expressions
e.g., Given that for the reaction, N
2
(g) + 3H
2
(g) 2NH
3
(g), K
c
= 3.5 x 10
8
,
what is K
c
for the reaction NH
3
(g) 1/2 N
2
(g) + 3/2 H
2
(g)?
e.g., Given the following:
H
2
O(g) + CO(g) H
2
(g) + CO
2
(g) K
p
= 1.6
FeO(s) + CO(g) Fe(s) + CO
2
(g) K
p
= 0.67
What is K
p
for the reaction Fe(s) + H
2
O(g) FeO(s) + H
2
(g)
16
I. Equilibrium
C. Magnitude of K
2SO
2
+ O
2
2SO
3
K = 3 x 10
24

Equilibrium lies very far to the right; reaction goes to completion.
2HF H
2
+ F
2
K = 1 x 10
13

Equilibirum lies very far to the left; reaction doesnt go.
H
2
O + H
2
C=O
H C
OH
OH
H
K ~ 1
Equilibrium mixture of reactant and product.
17
I. Equilibrium
D. The reaction quotient, Q
For aA + bB cC + dD
b a
d c
c
[B] [A]
[D] [C]
= Q
not necessarily at equilibirum
If Q > K, reaction shifts left to achieve equilibrium

If Q < K, reaction shifts right to achieve equilibrium

If Q = K, reaction is at equilibrium
18
I. Equilibrium
D. The reaction quotient, Q
e.g., N
2
+ O
2
2NO K
c
= 4.0 x 10
4
at 2000 K
If [N
2
] = 0.50 M, [O
2
] = 0.25 M, and [NO] = 4.2 x 10
3
M,

Is the system at equilibrium? Which way will it shift?
19
20
21
II. Applications of Equilibrium Constants
A. Calculating equilibrium constants
e.g., 2SO
2
+ O
2
2SO
3

1.00 mol of SO
2
and 1.00 mol of O
2
were placed in a 1.00-L flask at 1000C.
When equilibrium was attained, it was found that the concentration of SO
3

was 0.925 M. What is K
c
?
1.00 1.00 0 M
-0.925 -0.925/2 +0.925 M
0.075 0.537 0.925 M
[SO
2
] [O
2
] [SO
3
]
[ ]
i

A[ ]
[ ]
eq

K
c
= = = 2.8 x 10
2

[SO
3
]
2

[SO
2
]
2
[O
2
]
(0.925)
2

(0.075)
2
(0.537)
22
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
1. SO
2
+ NO
2


0.50 mol of SO
2
and 0.50 mol of NO
2
are placed in a 10.0-L flask and
allowed to come to equilibrium. What are the equilibirum concentrations
of all species?
NO + SO
3
K
c
= 85.0
0.050 0.050 0 0
-x -x +x +x
0.050-x 0.050-x x x
[SO
2
] [NO
2
] [NO] [SO
3
]
[ ]
i

A[ ]
[ ]
eq

K
c
=
x = 0.045 M
[NO][SO
3
]
[SO
2
][NO
2
]
85.0 =
x
2

(0.050 - x)
2

\ both sides 9.22 =
x
0.050 - x
[SO
2
]
eq
= [NO
2
]
eq
= 0.005 M
[NO]
eq
= [SO
3
]
eq
= 0.045 M
23
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
2. SO
2
+ NO
2


Same as problem 1, but this time start with products: 0.050 M NO and
0.050 M SO
3
. What are the equilibirum concentrations of all species?
NO + SO
3
K
c
= 85.0
0 0 0.050 0.050
+x +x -x -x
x x 0.050-x 0.050-x
[SO
2
] [NO
2
] [NO] [SO
3
]
[ ]
i

A[ ]
[ ]
eq

x = 0.005 M
K
c
=
[NO][SO
3
]
[SO
2
][NO
2
]
85.0 =
(0.050 - x)
2

(x)
2

\ both sides 9.22 =
0.050 - x
x
[SO
2
]
eq
= [NO
2
]
eq
= 0.005 M
[NO]
eq
= [SO
3
]
eq
= 0.045 M
Same [ ]
eq
s
regardless of
where we start!
24
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
3. COCl
2


When 0.20 mol of COCl
2
is placed in a 10.0-L flask, what are the
equilibirum concentrations of all species?
CO + Cl
2
K
c
= 2.2 x 10
-10

0.020 0 0
-x +x +x
[COCl
2
] [CO] [Cl
2
]
[ ]
i

A[ ]
K
c
=
[CO][Cl
2
]
[COCl
2
]
2.2 x 10
-10
=
x
2

(0.020 - x)
Solve quadratic?
Be my guest.
Rather, assume x << 0.020 M
{i.e., (0.020-x) ~ 0.020}
2.2 x 10
-10
=
x
2

0.020
x = 2.1 x 10
-6
M
(Assumption valid if x < 5% of [ ]
i
)
[CO]
eq
= [Cl
2
]
eq
= 2.1 x 10
-6
M
[COCl
2
]
eq
= 0.020 M
25
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
4. 2CO
2


Starting with 0.010 M CO
2
, what are the [ ]
eq
s of all species?
2CO + O
2
K
c
= 6.4 x 10
-7
at 2000C
0.010 0 0
-2x +2x +x
[CO
2
] [CO] [O
2
]
[ ]
i

A[ ]
K
c
=
[CO]
2
[O
2
]
[CO
2
]
2

6.4 x 10
-7
=
(2x)
2
(x)
(0.010 - 2x)
2

Assume 2x << 0.010
6.4 x 10
-7
=
4x
3

(0.010)
2

x = 2.5 x 10
-4
M
(Assumption valid: 2x = 5% 0.010)
[CO
2
]
eq
= 0.010 M
[CO]
eq
= 5.0 x 10
-4
M
[O
2
]
eq
= 2.5 x 10
-4
M
6.4 x 10
-7
=
4x
3

(0.010 - 2x)
2

Difficult to solve.
26
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
5. CO + H
2

0.15 0.20 M
H
2
CO K
c
= 4.6 x 10
9

0.15 0.20 0
-x -x +x
[CO] [H
2
] [H
2
CO]
[ ]
i

A[ ]
K
c
=
[H
2
CO]
[CO][H
2
]
4.6 x 10
9
=
x
(0.15-x)(0.20-x)
Cant assume x is small!
Cant solve quadratic!
Instead, carry reaction to completion,
then work back toward equilibrium:
27
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
5. (cont.) CO + H
2

0.15 0.20 M
H
2
CO K
c
= 4.6 x 10
9

0.15 0.20 0
0 0.05 0.15
+x +x -x
[CO] [H
2
] [H
2
CO]
[ ]
i

[ ]
f

A[ ]
4.6 x 10
9
=
0.15-x
(x)(0.05+x)
Assume x << 0.05 (or 0.15)
4.6 x 10
9
=
0.15
(x)(0.05)
x = 6.5 x 10
-10
M (assumption valid)
[CO] = 6.5 x 10
-10
M
[H
2
] = 0.05 M
[H
2
CO] = 0.15 M
General:
always work in the direction
of a small A[ ]
carry reaction to completion
toward the side on which the
equilibrium lies
28
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
6. 2SO
2
+ O
2

1.0 1.0 atm
2SO
3
K
p
= 1.1 x 10
12

1.0 1.0 0
0 0.5 1.0
+2x +x -2x
pSO
2
pO
2
pSO
3

p
i

p
f

Ap
1.1 x 10
12
=
(1.0-2x)
2

(2x)
2
(0.5+x)
Assume x << 0.5 (2x << 1.0)
x = 6.7 x 10
-7
atm (assumption valid)
pSO
2
= 1.3 x 10
-6
atm
pO
2
= 0.5 atm
pSO
3
= 1.0 atm
Carry reaction to completion:
1.1 x 10
12
=
(1.0)
2

(2x)
2
(0.5)
=
1
2x
2

29
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
e.g., For the decomposition of gaseous water at 500C,
2H
2
O(g) 2H
2
(g) + O
2
(g), K
c
= 6.0 x 10
28
.
If 0.20 mol of H
2
O is placed in a 5.0-L container and allowed to come
to equilibrium at 500C, what will be the concentrations of all species?
30
II. Applications of Equilibrium Constants
B. Calculating equilibrium concentrations
e.g., For the reaction, CO(g) + Cl
2
(g) COCl
2
(g), K
c
= 4.6 x 10
9
. If
0.15 mol of CO and 0.30 mol of Cl
2
are placed in a 1.0-L flask and allowed
to react, what would be the concentration of each species at equilibrium?
31
III. Le Chteliers Principle
Any change imposed on a system at equilibrium will cause the system
to shift in such a way to re-establish equilibrium.
Reactants Products
32
III. Le Chteliers Principle
A. Change in quantity of reactant or product
A B at equilibrium
K =
[B]
[A]
increase [B]
reaction shifts to left
A reaction will shift: away from a substance added,
toward a substance removed.
e.g., 3H
2
(g) + N
2
(g) 2NH
3
(g)
2 2
3
N
3
H
2
NH
p
p p
p
K =
Increase : reaction shifts ______
Increase : reaction shifts ______
Decrease : reaction shifts ______
2
H
p
3
NH
p
2
N
p
33
III. Le Chteliers Principle
A. Change in quantity of reactant or product
e.g., CH
3
CH
2
CH
2
CH
3
CH
3
CH CH
3
CH
3
butane (B) isobutane (I)
K
c
= 2.5
At equilibrium, [B] = 0.20 M and [I] = 0.50 M. If 0.10 mol of butane is added
and the system returns to equilibrium,
a. Which way will the reaction shift to re-establish equilibrium?
b. What will be the new [ ]
eq
s?
c. Is there be more or less butane after the reaction reaches equilibrium?
34
III. Le Chteliers Principle
B. Change in pressure or volume
A(g) + B(g) C(g) K
p
=
p
C

p
A
p
B

Decrease V: reaction shifts to side with
(increase P
T
) fewer moles of gas
e.g., 3H
2
(g) + N
2
(g) 2NH
3
(g)
Increase V: reaction shifts ________
Increase P
T
: reaction shifts ________
Increase V: reaction shifts to side with
(decrease P
T
) more moles of gas
35
III. Le Chteliers Principle
C. Change in temperature
2NO
2
(g) N
2
O
4
(g) AH = -57.2 kJ/mol + heat
product
AH < 0: increasing T shifts equilibrium left (K gets smaller)
decreasing T shifts equilibrium right (K gets larger)

AH > 0: opposite effect
e.g., 2NOBr(g) 2NO(g) + Br
2
(g) AH = +16.1 kJ/mol
Increase T: reaction shifts ________
Decrease T: reaction shifts ________
36
III. Le Chteliers Principle
D. Effect of catalysts
No effect on position of equilibrium
(neither a reactant nor a product of the reaction)
- increases rate at which equilibrium is established
e.g., 2N
2
O(g) + O
2
(g)

Will the amount of NO at equilibrium be greater, less, or the same if we:
add N
2
O? __________
remove O
2
? __________
add NO? __________
increase V? __________
raise T? __________
add a catalyst? __________
4 NO (g) AH = 199 kJ/mol
37
III. Le Chteliers Principle
e.g., CaCO
3
(s)

How will the amount of CO
2
change if we:
add CaCO
3
(s)? __________
remove CO
2
(g)? __________
decrease V? __________
decrease T? __________
CaO(s) + CO
2
(g) AH = 278 kJ/mol
2
CO p
p K =