CHAPTER 14

CHEMICAL EQUILIBRIUM
‘Every system in chemical equilibrium, under the influence of a change of any one
of the factors of the equilibrium, undergoes a transformation … [that produces a
change]… in the opposite direction of the factor in question.’
- Henri Le Châtelier (1850-1936)
Overview and Learning Objectives
Chapter 13: Kinetics determine how fast a chemical reaction proceeds from
reactants to products

Chapter 14: Equilibrium determines the extent that reactants are transformed
to products based on the thermodynamics of the chemical system (Chapter 17)

Learning Objectives:
1. Describe and quantify how far a reaction proceeds based on
experimental data using the equilibrium constant
2. A reaction with a small equilibrium constant barely proceeds at all, while
one with a large equilibrium constant goes to near complete
consumption of the reactants
3. Use the equilibrium constant to predict and quantify the extent of a
reaction
2
Hemoglobin (Hb) and Equilibrium
• Iron centres in Hb proteins can
reversibly bind O2
• O2 can be released when red
blood cells visit body tissues
needing oxygen
• This reversibility of the Hb + O2
reaction is an equilibrium
process

𝐻𝑏 + 𝑂2 ⇋ 𝐻𝑏𝑂2
3
Concept: Dynamic Equilibrium
𝐻2 𝑔 + 𝐼2 𝑔 ⇋ 2 𝐻𝐼 (𝑔) A reversible reaction can proceed in
both directions.
Start (a):
Only H2(g)+I2(g), so reaction moves
forward, but slows down
During (b, c):
2 HI can begin reacting in reverse
direction
Eventually (d):
Forward and reverse rates are equal

4
Concept: Dynamic Equilibrium
𝐻2 𝑔 + 𝐼2 𝑔 ⇋ 2 𝐻𝐼 (𝑔)
Start (a):
Only H2(g) and I2(g), so reaction
moves forward, but slows down
as reactants consumed
During (b, c):
2 HI can begin reacting faster in
reverse direction
Eventually (d):
Forward and reverse rates are
equal and equilibrium is reached
5
Concept: Dynamic Equilibrium
Dynamic equilibrium for a chemical reaction is the
condition in which the rate of the forward reaction
equals the rate of the reverse reaction.
PH 2 PI 2
PHI
= = =0
t t t
Does this mean the
partial pressures or
concentrations are
equal at equilibrium?
(A)YES
(B)NO
6
Expressing the Equilibrium Constant

• Equilibrium concentrations
of reactants and products
are NOT necessarily equal
• Rate of forward and reverse
reactions IS equal
• Describe using the
equilibrium constant (K)

7
Expressing the Equilibrium Constant
The equilibrium constant (K):
1. Applies to a system at
equilibrium which is
chemically balanced
2. Is the ratio of products to
reactants
3. The concentration of
reactant or product is raised
to the equivalent power of its
stoichiometry (law of mass
action)
8
Expressing the Equilibrium Constant
𝑎𝐴 𝑎𝑞 + 𝑏𝐵 𝑎𝑞 ⇋ 𝑐𝐶 𝑎𝑞 + 𝑑𝐷 (𝑎𝑞) We can express K using
concentrations (KC) or
 C   D
c d
pressures (KP)
KC =
 A  B 
a b

𝑎𝐴 𝑔 + 𝑏𝐵 𝑔 ⇋ 𝑐𝐶 𝑔 + 𝑑𝐷 (𝑔)

( PC ) ( PD )
c d

KP =
( PA ) ( PB )
a b

9
Relating Equilibrium Constants KP and KC
 C   D
c d

KC = In the gas phase amounts are

 A  B 
a b
easily expressed in
concentration and pressure

How might we interconvert

between these systems?

( PC ) ( PD )
c d

KP =
( PA ) ( PB )
a b
10
Relating Equilibrium Constants KP and KC
 C   D
c d

KC = Recall: Ideal gas law.

 A  B 
a b

How do we express gas

PV = nRT concentration (units: mol L-1)?
c d
 PC   PD 
   
KC = 
RT   RT  Stoichiometric difference is
a b
 PA   PB  the change in moles overall
   
 RT   RT 
between products and
reactants (Δn)
( PC ) ( PD )
c d

KP =
( PA ) ( PB )
a b ( c + d ) −( a +b )
 1 
KC = K P  
11  RT 
Relating Equilibrium Constants KP and KC
Stoichiometric difference is
( c + d ) −( a +b ) the change in moles overall
 1 
KC = K P   between products and
 RT  reactants (Δn)
n = nproducts − nreactants = (c + d ) − (a + b)
For what value of Δn are KP
and KC equivalent?
n
 1 
KC = K P  
 RT 
OR
K P = K C ( RT )
n

12
Example: Calculating KP and KC

13
Example: Calculating KP and KC Continued

14
Practice: Calculating KP and KC Continued

15
Thermodynamic Equilibrium Constant (K)
• In thermodynamics we Standard States
want to relate equilibrium
to reaction spontaneity Solutes (C°) Gases (P°)
• Requires a unitless
description of KC or KP
using activities
• Activity (a) is a measure
of deviation from the aX =
 X PX
aX = 
 P
standard state C
16
Examples: Expressing TEQ (K) as KC or KP
Write the thermodynamic equilibrium constant (TEQ, K)
for the following reaction:
𝐹𝑒 3+ 𝑎𝑞 + 𝑆𝐶𝑁 − 𝑎𝑞 ⇋ 𝐹𝑒 𝑆𝐶𝑁 2+
(𝑎𝑞)

17
Examples: Expressing TEQ (K) as KC or KP
Relate the thermodynamic equilibrium constant (TEQ, K)
to KC: 𝐹𝑒 3+ 𝑎𝑞 + 𝑆𝐶𝑁 − 𝑎𝑞 ⇋ 𝐹𝑒 𝑆𝐶𝑁 2+ (𝑎𝑞)

*Note: There is NO difference between these other than that K is

unitless and KC is not
18
Examples: Expressing TEQ (K) as KC or KP
Write the thermodynamic equilibrium constant (TEQ, K)
for the following reaction and relate it to KP:
2 𝑁2 𝑂5 𝑔 ⇋ 4 𝑁𝑂2 𝑔 + 𝑂2 (𝑔)

Again, there is NO difference between these other than that K is

unitless and KP is not
19
Heterogenous Equilibria: Solids & Liquids
Standard States
• Many reactions involve
pure solids or liquids as Solutes (C°) Gases (P°)
part of a balanced
equation aX =
 X PX
aX = 
 P
• What are the standard C
states that define the Pure Solids Pure Liquids
activity of solids and
liquids?

20
Practice: Heterogeneous Equilibria

21
Practice: Heterogeneous Equilibria

22
The Equilibrium Constant (K)
𝑎𝐴 𝑎𝑞 + 𝑏𝐵 𝑎𝑞 ⇋ 𝑐𝐶 𝑎𝑞 + 𝑑𝐷 (𝑎𝑞) • Considering activities is
𝑎𝐴 𝑔 + 𝑏𝐵 𝑔 ⇋ 𝑐𝐶 𝑔 + 𝑑𝐷 (𝑔) critical in systems with
high pressures or
( aC ) ( aD )
c d

K= concentrations
( a A ) ( aB )
a b

At high pressures and concentrations non-ideal behaviours arise from:

• Changing intermolecular forces
• Interdependence of molecules and/or ions in solution

In this course: We will NOT consider equilibrium systems that depart from the
assumption of ideal conditions.
23
The Equilibrium Constant (K)
Therefore:
𝑎𝐴 𝑎𝑞 + 𝑏𝐵 𝑎𝑞 ⇋ 𝑐𝐶 𝑎𝑞 + 𝑑𝐷 (𝑎𝑞)
• Kc can be calculated so long as
𝑎𝐴 𝑔 + 𝑏𝐵 𝑔 ⇋ 𝑐𝐶 𝑔 + 𝑑𝐷 (𝑔) we have information to get
concentrations in mol L-1
( C) ( D)
AND
c d
a a
K= • KP where we have pressures in
( a A ) ( aB )
a b
bar

*Note: We will then be able to use thermodynamic

equilibrium constant values from the appendices to solve
equilibrium problems involving concentrations or
24 pressures in these same units
What does the Equilibrium Constant (K) mean?
1. When K is large it indicates:
• K>1
• Numerator > Denominator
• Amount of products
favoured over reactants
• ‘reaction lies to the right’

H 2( g ) + Br2( g ) ⇌ 2 HBr( g )
K = 1.9 10 (at 25 °C)
19

25
What does the Equilibrium Constant (K) mean?
2. When K is small it
indicates:
• K<1
• Numerator < Denominator
• Amount of reactants
favoured over products
• ‘reaction lies to the left’

N 2( g ) + O2( g ) ⇌ 2 NO( g )
−31
K = 4.110 (at 25 °C)
26
What does the Equilibrium Constant (K) mean?

Summary:
1. K < 1
• Reverse reaction is favoured
• Forward reaction does not proceed far
2. K ≈ 1
• Neither direction is favoured
• Forward reaction proceeds about halfway to
completion
3. K > 1
• Forward reaction is favoured
• Reaction proceeds nearly to completion

27
What does the Equilibrium Constant (K) mean?

An equilibrium constant (K) of 10 applies to

the reaction:
A( g ) ⇌ B( g )
Initially, the reaction mixture contains 11 mol of A and 0
mol of B in a fixed 1 L volume. When equilibrium is
reached, which statement is true?

(A) The reaction mixture will contain 10 mol A and 1 mol B

(B) The reaction mixture will contain 1 mol A and 10 mol B
(C) The reaction mixture will contain equal amounts of A
and B

28
Equilibrium Constant and Chemical Equations

1. Reversing an equation?
Invert the equilibrium constant

A + 2 B ⇌ 3C 3C ⇌ A + 2B
 C  A B 
3 2

K forward = K reverse =
Reverse

 A B  C 
2 3

K reverse =
29
Equilibrium Constant and Chemical Equations

2. Multiplying an equation by a factor (n)?

Raise the equilibrium constant to the same factor

A + 2 B ⇌ 3C nA + 2nB ⇌ 3nC
 C  C
3 3n
xn
K = K =
 A B   A  B 
2 n 2n

K = '
=K n
30
Equilibrium Constant and Chemical Equations
3. Adding equations into an overall reaction?
Overall equilibrium constant is the product of the
individual contributing reaction equilibrium constants
A ⇌ 2B
+ 2 B ⇌ 3C

 C
3

K overall = = = K1 K 2
 A
31
Practice

32
Calculating K from Measurements
Can easily obtain K from systems where ALL
concentrations or partial pressures are measured AT
equilibrium
H 2( g ) + I 2( g ) ⇌ 2 HI ( g )
If PH2 = 0.098 bar, PI2 = 0.098 bar and PHI = 0.804 bar at equilibrium, calculate
the equilibrium constant (K).

33
Calculating K from Measurements
Recall: At a given temperature for any reaction, the equilibrium partial
pressures or concentrations depend on the INITIAL values of the system,
but K DOES NOT

34
Calculating K from Measurements
A( aq ) ⇌ 2 B( aq ) • For many reactions, the
If initially, initial reaction quantities
[A] = 1.00 mol L-1 and [B] = 0.00 mol L-1 and ONE equilibrium
And at equilibrium:
[A]eq = 0.75 mol L-1 quantity are all we need
• Can calculate other
We can deduce [B]eq and K by
stoichiometry equilibrium quantities
AND equilibrium
  A =
constant (K) via
stoichiometry
  B =
35
The I-C-E Table
A( aq ) ⇌ 2 B( aq ) • We can summarize these
We now have equilibrium findings in an I-C-E table
concentrations for all species Initial
and can calculate the equilibrium
Change
constant (K)
Equilibrium

36
The I-C-E Table
A( aq ) ⇌ 2 B( aq )
 B
2
We now have equilibrium
K= =
concentrations for all species
and can calculate the equilibrium  A
constant (K)

37
Practice: The I-C-E Table

38
Practice: The I-C-E Table

39
The Reaction Quotient (Q)
For reactions that contain a aA( g ) + bB( g ) ⇌ cC( g ) + dD( g )
mixture of reactants and aA( aq ) + bB( aq ) ⇌ cC( aq ) + dD( aq )
products that are NOT at
equilibrium the reaction
quotient predicts the
direction of change (if we
know K)

40
The Reaction Quotient (Q)
• The reaction quotient (Q) has aA( g ) + bB( g ) ⇌ cC( g ) + dD( g )
the same form as the
equilibrium constant via The aA( aq ) + bB( aq )
⇌ cC( aq ) + dD( aq )
Law of Mass Action, BUT
denotes that the system IS
NOT at equilibrium QP =
• Q can have many different
values because it depends
ONLY on the CURRENT state
of the unequilibrated chemical QC =
system

41
The Reaction Quotient (Q)
What is the magnitude of QC in a system with
ONLY reactants?
(A) ∞ aA( aq ) + bB( aq ) ⇌ cC( aq ) + dD( aq )
(B) 1
(C) 0

 C   D
c d

QC = =
 A  B 
a b

42
The Reaction Quotient (Q)
What is the magnitude of QC in a system with
ONLY products?
(A) ∞ aA( aq ) + bB( aq )
⇌ cC( aq ) + dD( aq )
(B) 1
(C) 0

 C   D
c d

QC = =
 A  B 
a b

43
The Reaction Quotient (Q)

 C   D
c d

QC =
• If chemical system units are
 A  B 
a b
in bar or mol L-1 we can also
arrive at a Thermodynamic
Reaction Quotient that is
( PC ) ( PD )
c d
unitless
• Relies on same assumptions QP =
( PA ) ( PB )
a b
of ideality as K

44
Why is Q useful?
• If we know K, then Q tells
us how the reaction
concentrations must
change in order to reach
equilibrium where:
Q=K

45
The Reaction Quotient (Q) - Summary
Q is a measure of the progress of a reaction towards
equilibrium
Q<K
• Reaction proceeds right
• Products need to be formed
Q>K
• Reaction proceeds left
• Reactants need to be formed
Q=K
• Equilibrium has been reached
46
Practice: Comparing Q and K

47
The Reaction Quotient (Q)
For the following reaction with K = 0.15:
N 2O4( g ) ⇌ 2 NO2( g )
If the mixture initially contains N2O4 and NO2 in
their standard states, which statement is true of
the reaction mixture before any reaction occurs?
(A) Q = K; the reaction is at equilibrium
(B) Q < K; the reaction proceeds right
(C) Q > K; the reaction proceeds left

48
Finding Equilibrium Concentrations
K and Initial Amounts
• Can be approached using A( aq ) ⇌ 2 B( aq )
the I-C-E table
• Where changes in the
amount are NOT measured,
we represent them with the
variable x and account for
stoichiometry
• Given: initial [A] = 1.0 M,
[B] = 0 M, K = 0.33

49
Finding Equilibrium Concentrations
K and Initial Amounts  B ( 2x)
2 2

K= = = 0.33
A( aq ) ⇌ 2 B( aq )  A (1.0 − x )
Rearrange to quadratic form

If K = 0.33, we can solve

for x
−b  b − 4ac
2
x=
50 2a
Finding Equilibrium Concentrations
K and Initial Amounts If,
a = 4; b = 0.33, and c = -0.33
A( aq ) ⇌ 2 B( aq )
Then the solution to quadratic
for x is:
x = 0.25 or − 0.33
(A) (B)
Which of these two
−b  b − 4ac
2
solutions is valid?
x=
2a
51
Finding Equilibrium Concentrations
K and Initial Amounts If,
a = 4; b = 0.33, and c = -0.33
A( aq ) ⇌ 2 B( aq )
Then the solution to quadratic
for x is:
x = 0.25 or − 0.33
We can then find the values of [A]eq
and [B]eq:
−b  b − 4ac
2
x=
2a
52
Example: Finding Equilibrium Concentrations

53
Example: Finding Equilibrium Concentrations

54
Example: Finding Equilibrium Concentrations

55
Approximations to Simplify Eq’m Problems
• Sometimes we can simplify A( aq ) ⇌ 2 B( aq )
the solutions to finding
equilibrium concentrations
without adding significant
(> 5 %) error
• Requires careful inspection
of K and the starting
conditions Consider when: K = 3.3 x 10-5
• Large initial [reactant] and
 B ( 2x)
2 2
small K can result in an K= =
equilibrium concentration
that is essentially unchanged
 A (1.0 − x )
56
Approximations to Simplify Eq’m Problems
• Large initial [reactant] and small K can result in an equilibrium
concentration that is essentially unchanged

 B ( 2x)
2 2 Simplify
−5
K= = = 3.3  10 4 x 2 = 3.3 10−5
 A (1.0 − x )
Since K is very small 3.3 10−5
x= = 0.0029
4
(1.0 − x ) ≈ 1.0
57
Approximations to Simplify Eq’m Problems
• Large initial [reactant] and small K can result in an equilibrium
concentration that is essentially unchanged
• Less than 5 % error is
RESULT ASSUMPTION acceptable in answers
x = 0.0029 (1.0 − x ) ≈ 1.0 • This approximation works
where the equilibrium
concentrations change very
% ERROR little from their initial state
due to a very small value of K

58
Finding Equilibrium Concentrations
Consider the value of K and initial concentration
of A. For which set below will the ‘x is small’
approximation MOST likely be valid?

(A) K = 1.0 x 10-5; [A]=0.250 mol L-1

(B) K = 1.0 x 10-2; [A]=0.250 mol L-1
(C) K = 1.0 x 10-5; [A]=0.00250 mol L-1
(D) K = 1.0 x 10-2; [A]=0.00250 mol L-1

59
Example: Finding Equilibrium Concentrations

60
Example: Finding Equilibrium Concentrations

61
Le Châtelier’s Principle
What happens when we perturb a system at equilibrium?
Le Châtelier’s Principle:
When a chemical system at equilibrium is disturbed, the
system shifts in a direction that minimizes the disturbance.
Ways to disturb an equilibrated chemical system:
1. Change the amount of a reactant
2. Change the amount of a product
3. Change the reaction volume
4. Change the reaction pressure
5. Change the reaction temperature
62
Le Châtelier’s Principle: Reactant/Product
• For gas phase reactions, changes
in partial pressures of reactant or N 2O4( g ) ⇌ 2 NO2( g )
product
Before addition of NO2:
• For solution phase reactions,
changes in concentration of
reactant or product
After addition of NO2

• What happens if we add NO2 to this

system at equilibrium?
Reaction proceeds:

63
Le Châtelier’s Principle: Reactant/Product
• What happens if we add NO2 to this
system at equilibrium?
• Minimize disturbance
• Create reactant to
re-establish K
• Can use the reaction quotient
(Q) to assess

64
Le Châtelier’s Principle: Reactant/Product
When we add N2O4 to this
system at equilibrium N 2O4( g ) ⇌ 2 NO2( g )
which is true?
(A) Q < K
(B) The system forms more
products
(C) The reaction proceeds
right
(D) All of the above

65
Le Châtelier’s Principle: Reactant/Product
SUMMARY
1. Increasing the amount of reactant (Q<K) causes a
shift to the right
2. Increasing the amount of product (Q>K) causes a
shift to the left
3. Decreasing the amount of reactant (Q>K) causes a
shift to the left
4. Decreasing the amount of product (Q<K) causes a
shift to the right

66
Example: Le Châtelier’s Principle

67
Le Châtelier’s Principle: Volume Change
• Volume changes affect gaseous
systems at equilibrium
• We are NOT adding any reactants
or products
• The SIZE of the reaction container
is the only change

According to Le Châtelier’s
Principle, equilibrium systems move
to minimize these changes.

68
Le Châtelier’s Principle: Volume Change
So, if the volume decreases, pressure
increases and vice versa

According to Le Châtelier’s Principle,

equilibrium systems move to minimize
these changes.

How does this system respond to

decrease the pressure?

• Equlibrium shifts in the direction of

fewer moles of gas
• Here, this means the reaction
shifts to the right
69
Le Châtelier’s Principle: Volume Change
So, here if the volume increases,
pressure decreases

According to Le Châtelier’s Principle,

equilibrium systems move to minimize
these changes.

How does this system respond to

decrease the pressure?

• Equlibrium shifts in the direction of

more moles of gas
• Here, this means the reaction
shifts to the left
70
Le Châtelier’s Principle: Volume Change
SUMMARY
1. Increasing the volume causes a shift in the
direction that has more moles of gas
2. Increasing the pressure causes a shift in the
direction that has fewer moles of gas
3. Decreasing the volume causes a shift in the
direction that has fewer moles of gas
4. Decreasing the pressure causes a shift in the
direction that has more moles of gas

71
Le Châtelier’s Principle: Pressure Change
When we add an inert
gas (e.g. He) to this
system at equilibrium
which direction does
the equilibrium shift?
Assume the volume of
N 2( g ) + 3H 2( g ) ⇌ 2 NH 3( g )
the system does NOT
change

(A) Left
(B) Right
(C) Neither
72
Practice: Le Châtelier’s Principle

73
Le Châtelier’s Principle: Temperature Change
In order to determine the direction of
change with temperature, we need to
know how heat participates in the
equilibrium
Heat released from a reaction called:

Heat absorbed by a reaction called:

According to Le Châtelier’s Principle,

equilibrium systems move to minimize
changes.
74
Le Châtelier’s Principle: Temperature Change
In order to determine the direction of
change with temperature, we need to
know how heat participates in the
equilibrium

According to Le Châtelier’s Principle,

equilibrium systems move to minimize
changes.

This reaction is:

75
Le Châtelier’s Principle: Temperature Change
In order to determine the direction of
change with temperature, we need to
know how heat participates in the
equilibrium

According to Le Châtelier’s
Principle, equilibrium systems move
to minimize changes.

If we add heat to this equilibrium it

will shift:

If we removed heat from this

equilibrium it will shift:
76
Le Châtelier’s Principle: Temperature Change
According to Le Châtelier’s
Principle, equilibrium systems move
to minimize changes.

Shifts in equilibrium due to a change

in temperature (T) also change the
value of equilibrium constant (K).

Exothermic reaction:
• Increase T, Shift Left, Decrease K

Endothermic reaction:
• Increase T, Shift Right, Increase K

77
Le Châtelier’s Principle: Temperature Change
SUMMARY
1. Increasing the temperature causes exothermic
reactions to shift left and decreases K
2. Increasing the temperature causes endothermic
reactions to shift right and increases K
3. Decreasing the temperature causes exothermic
reactions to to shift right and increases K
4. Decreasing the temperature causes endothermic
reactions to shift left and decreases K

78
Example: Le Châtelier’s Principle

79