Chapter 16: Principles of Reactivity: Chemical Equilibria

I. Equilibrium
e.g., H2O + CO2

H2CO3
Dynamic equilibrium
Rateforward = Ratereverse
[H2O]

conc.
[CO2]
[H2CO3]
time
2

I. Equilibrium
General: A

conc.

[B]

[A]

Equilibrium lies on side of product.

Rateforward = Ratereverse
kf[A] = kr[B]

kf [B]

1
k r [ A]

kf > kr

time

conc.

[A]

[B]
time

Equilibrium lies on side of reactant.

Rateforward = Ratereverse
kf[A] = kr[B]

kf [B]

1
k r [ A]

kf < kr
3

I. Equilibrium
A. Equilibrium expressions
For the reaction, aA + bB
At equilibrium:

cC + dD

Rateforward = Ratereverse
kf[A]a[B]b = kr[C]c[D]d

kf
[C] c [D]d
Kc
kr
[A]a [B] b

equilibirum expression

concentration
equilibrium constant
(at a given temperature)

I. Equilibrium
A. Equilibrium expressions
Also, for the reaction, aA + bB

cC + dD

pCc pDd
Kp a b
pA pB
pressure

e.g., 2N2O5(g)

4 NO2(g) + O2(g)

What are Kc and Kp?

I. Equilibrium
A. Equilibrium expressions
Heterogeneous equilibria:

1. insoluble solids are not included in Kc or Kp

e.g., AgCl(s) + 2NH3(aq)

K c'

Ag(NH3)2+(aq) + Cl(aq)

[Ag(NH 3 ) 2 ][Cl ]

[AgCl ( s )][ NH 3 ]2
constant

K c' [AgCl ( s )]

[Ag(NH 3 ) 2 ][Cl ]
Kc
[ NH 3 ]2

I. Equilibrium
A. Equilibrium expressions
Heterogeneous equilibria:

2. solids, liquids are not included in Kp

e.g., H2O(g) + SO3(g)

K p'

pH 2SO 4
pH 2O pSO 3

K p'
pH 2SO 4

H2SO4(l)
constant (pvap at T)

1
Kp
pH 2O pSO 3

I. Equilibrium
A. Equilibrium expressions
e.g., Write the equilibrium expression for each of the following reactions.
Cu(OH)2(s)

Ni(s) + 2Ag+(aq)

Cu2+(aq) + 2 OH(aq)

Ni2+(aq) + 2 Ag(s)

2 NH3(g) + CO2(g) + H2O(g)

(Kc)

(Kc)

(NH4)2CO3(s)

(Kp)

10

11

I. Equilibrium
B. Manipulating equilibrium expressions
1. reversing the equation
H2 + Cl2
2HCl

2HCl

H2 + Cl2
Kc =

[HCl]2
Kc =
[H2][Cl2]
Kc =

[H2][Cl2]
[HCl]2

1
Kc

When reversing a chemical equation, take the inverse

of the equilibrium constant.

12

I. Equilibrium
B. Manipulating equilibrium expressions
2. multiplying equations by some factor
2H2 + 2Cl2

4HCl

[HCl]4
Kc =
[H2]2[Cl2]2

Kc = (Kc)2

H2 + Cl2

HCl

Kc =

[HCl]
[H2][Cl2]

Kc = (Kc)
When multiplying a chemical equation by some factor,
raise the equilibrium constant to that power.
13

I. Equilibrium
B. Manipulating equilibrium expressions
3. adding equations
SO2 + NO2

NO + SO3

SO3 + H2O

H2SO4

SO2 + NO2 + H2O

Kc3 = Kc1 Kc2 =

NO + H2SO4

[NO][SO3]
Kc1 = [SO ][NO ]
2
2
[H2SO4]
Kc2 =
[SO3][H2O]

Kc3 =

[NO][H2SO4]
[SO2][NO2][H2O]

[NO][H2SO4]
[NO][SO3]
[H2SO4]
=

[SO2][NO2] [SO3][H2O] [SO2][NO2][H2O]

When adding equations, multiply the equilibrium constants.

14

I. Equilibrium
B. Manipulating equilibrium expressions
e.g., Given that for the reaction, N2(g) + 3H2(g)
2NH3(g), Kc = 3.5 x 108,
what is Kc for the reaction NH3(g)
1/2 N2(g) + 3/2 H2(g)?

e.g., Given the following:

H2O(g) + CO(g)
H2(g) + CO2(g) Kp = 1.6
FeO(s) + CO(g)
Fe(s) + CO2(g) Kp = 0.67
What is Kp for the reaction Fe(s) + H2O(g)
FeO(s) + H2(g)

15

I. Equilibrium
C. Magnitude of K
2SO2 + O2

2SO3

K = 3 x 1024

Equilibrium lies very far to the right; reaction goes to completion.

2HF

H 2 + F2

K = 1 x 1013

Equilibirum lies very far to the left; reaction doesnt go.

OH

H2O + H2C=O

H C OH

K1

Equilibrium mixture of reactant and product.

16

I. Equilibrium
D. The reaction quotient, Q
For aA + bB

cC + dD

[C]c [D]d
Qc
[A]a [B]b

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

17

I. Equilibrium
D. The reaction quotient, Q
e.g., N2 + O2

2NO

Kc = 4.0 x 104 at 2000 K

If [N2] = 0.50 M, [O2] = 0.25 M, and [NO] = 4.2 x 103 M,

Is the system at equilibrium? Which way will it shift?

18

19

20

II. Applications of Equilibrium Constants

A. Calculating equilibrium constants
e.g., 2SO2 + O2
2SO3
1.00 mol of SO2 and 1.00 mol of O2 were placed in a 1.00-L flask at 1000C.
When equilibrium was attained, it was found that the concentration of SO3
was 0.925 M. What is Kc?

[ ]i
D[ ]
[ ]eq

[SO2]

[O2]

[SO3]

1.00
-0.925
0.075

1.00
-0.925/2
0.537

0M
+0.925 M
0.925 M

[SO3]2
(0.925)2
=
= 2.8 x 102
Kc =
2
2
[SO2] [O2]
(0.075) (0.537)
21

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
1. SO2 + NO2

NO + SO3

Kc = 85.0

0.50 mol of SO2 and 0.50 mol of NO2 are placed in a 10.0-L flask and
allowed to come to equilibrium. What are the equilibirum concentrations
of all species?

[ ]i
D[ ]
[ ]eq

[SO2]

[NO2]

[NO]

[SO3]

0.050
-x
0.050-x

0.050
-x
0.050-x

0
+x
x

0
+x
x

[NO][SO3]
Kc =
[SO2][NO2]
x2
85.0 =
(0.050 - x)2

x
0.050 - x
x = 0.045 M

both sides 9.22 =

[SO2]eq = [NO2]eq = 0.005 M

[NO]eq = [SO3]eq = 0.045 M

22

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
2. SO2 + NO2

NO + SO3

Kc = 85.0

Same as problem 1, but this time start with products: 0.050 M NO and
0.050 M SO3. What are the equilibirum concentrations of all species?
[SO2] [NO2] [NO]

[ ]i
D[ ]
[ ]eq

0
+x
x

0
+x
x

[NO][SO3]
Kc =
[SO2][NO2]
(0.050 - x)2
85.0 =
(x)2

[SO3]

0.050 0.050
-x
-x
0.050-x 0.050-x
0.050 - x
x
x = 0.005 M

both sides 9.22 =

[SO2]eq = [NO2]eq = 0.005 M

[NO]eq = [SO3]eq = 0.045 M

Same [ ]eqs
regardless of
where we start!

23

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
3. COCl2

Kc = 2.2 x 10-10

CO + Cl2

When 0.20 mol of COCl2 is placed in a 10.0-L flask, what are the
equilibirum concentrations of all species?

[ ]i
D[ ]

[COCl2]

[CO]

[Cl2]

0.020
-x

0
+x

0
+x

2.2 x

[CO][Cl2]
Kc =
[COCl2]
2.2 x 10-10 =

x2

(0.020 - x)

Solve quadratic?
Be my guest.

Rather, assume x << 0.020 M

{i.e., (0.020-x) 0.020}
10-10

x2
=
0.020

x = 2.1 x 10-6 M

(Assumption valid if x < 5% of [ ]i)

[CO]eq = [Cl2]eq = 2.1 x 10-6 M
[COCl2]eq = 0.020 M
24

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
Kc = 6.4 x 10-7 at 2000C

2CO + O2

4. 2CO2

Starting with 0.010 M CO2, what are the [ ]eqs of all species?

[ ]i
D[ ]

[CO2]

[CO]

[O2]

0.010
-2x

0
+2x

0
+x

[CO]2[O2]
Kc =
[CO2]2

Assume 2x << 0.010

3
4x
6.4 x 10-7 =
(0.010)2
x = 2.5 x 10-4 M

6.4 x

10-7

(2x)2(x)
=
(0.010 - 2x)2

(Assumption valid: 2x = 5% 0.010)

6.4 x

10-7

4x3
=
(0.010 - 2x)2

[CO2]eq = 0.010 M
[CO]eq = 5.0 x 10-4 M
[O2]eq = 2.5 x 10-4 M

Difficult to solve.

25

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
H2CO
5. CO + H2
0.15 0.20 M

Kc = 4.6 x 109

[CO]

[H2]

[H2CO]

[ ]i
D[ ]

0.15
-x

0.20
-x

0
+x

Kc =

[H2CO]
[CO][H2]

4.6 x 109 =

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:
26

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
5. (cont.) CO + H2
0.15 0.20 M

[ ]i
[ ]f
D[ ]

H2CO

Kc = 4.6 x 109

[CO]

[H2]

[H2CO]

0.15
0
+x

0.20
0.05
+x

0
0.15
-x

4.6 x 109 =

0.15-x
(x)(0.05+x)

Assume x << 0.05 (or 0.15)

4.6 x

109

0.15
=
(x)(0.05)

x = 6.5 x 10-10 M (assumption valid)

[CO] = 6.5 x 10-10 M

[H2] = 0.05 M
[H2CO] = 0.15 M
General:
always work in the direction
of a small D[ ]
carry reaction to completion
toward the side on which the
equilibrium lies
27

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
Kp = 1.1 x 1012

2SO3
6. 2SO2 + O2
1.0 1.0 atm

Carry reaction to completion:

pi
pf
Dp

pSO2

pO2

pSO3

1.0
0
+2x

1.0
0.5
+x

0
1.0
-2x

pSO2 = 1.3 x 10-6 atm

pO2 = 0.5 atm
pSO3 = 1.0 atm

2
(1.0-2x)
1.1 x 1012 =
(2x)2(0.5+x)

Assume x << 0.5 (2x << 1.0)

1.1 x

1012

(1.0)2
1
=
=
(2x)2(0.5)
2x2

x = 6.7 x 10-7 atm (assumption valid)

28

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
e.g., For the decomposition of gaseous water at 500C,
2H2O(g)
2H2(g) + O2(g), Kc = 6.0 x 1028.
If 0.20 mol of H2O is placed in a 5.0-L container and allowed to come
to equilibrium at 500C, what will be the concentrations of all species?

29

II. Applications of Equilibrium Constants

B. Calculating equilibrium concentrations
e.g., For the reaction, CO(g) + Cl2(g)
COCl2(g), Kc = 4.6 x 109. If
0.15 mol of CO and 0.30 mol of Cl2 are placed in a 1.0-L flask and allowed
to react, what would be the concentration of each species at equilibrium?

30

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

31

III. Le Chteliers Principle

A. Change in quantity of reactant or product
A

B at equilibrium

increase [B]
K=

[B]
[A]

reaction shifts to left

A reaction will shift: away from a substance added,

toward a substance removed.
e.g., 3H2(g) + N2(g)

Kp

2
pNH
3

pH3 2 pN 2

2NH3(g)

Increase p H 2 : reaction shifts ______

Increase p NH3 : reaction shifts ______
Decrease p N 2 : reaction shifts ______
32

III. Le Chteliers Principle

A. Change in quantity of reactant or product
CH3

e.g., CH3

CH2

CH2

butane (B)

CH3

CH3

CH CH3

Kc = 2.5

isobutane (I)

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 [ ]eqs?
c. Is there be more or less butane after the reaction reaches equilibrium?

33

III. Le Chteliers Principle

B. Change in pressure or volume
A(g) + B(g)

C(g)

pC
Kp = p p
A B

Decrease V:
(increase PT)

reaction shifts to side with

fewer moles of gas

Increase V:
(decrease PT)

reaction shifts to side with

more moles of gas

e.g., 3H2(g) + N2(g)

2NH3(g)

Increase V: reaction shifts ________

Increase PT: reaction shifts ________

34

III. Le Chteliers Principle

C. Change in temperature
2NO2(g)

N2O4(g) + heat
product

DH = -57.2 kJ/mol

DH < 0: increasing T shifts equilibrium left (K gets smaller)

decreasing T shifts equilibrium right (K gets larger)
DH > 0: opposite effect
e.g., 2NOBr(g)

2NO(g) + Br2(g)

DH = +16.1 kJ/mol

Increase T: reaction shifts ________

Decrease T: reaction shifts ________

35

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., 2N2O(g) + O2(g)

4 NO (g)

DH = 199 kJ/mol

Will the amount of NO at equilibrium be greater, less, or the same if we:

add N2O?
__________
remove O2?

__________

add NO?

__________

increase V?

__________

raise T?

__________

add a catalyst? __________

36

III. Le Chteliers Principle

e.g., CaCO3(s)

CaO(s) + CO2(g)

DH = 278 kJ/mol

How will the amount of CO2 change if we:

add CaCO3(s)? __________
remove CO2(g)? __________
decrease V?

__________

decrease T?

__________

K p pCO 2

37