CHAPTER 14

CHEMICAL EQUILIBRIUM
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
Sections 14.1-14.3

3
Concept: Dynamic Equilibrium
A reversible reaction can proceed
H 2( g ) + I 2( g ) 2 HI ( g ) 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 faster in
reverse direction
Eventually (d):
Forward and reverse rates are
equal

4
Concept: Dynamic Equilibrium
H 2( g ) + I 2( g ) 2 HI ( g )
Start (a):
Only H2(g)+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
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

8
Expressing the Equilibrium Constant
aA( aq ) + bB( aq ) cC( aq ) + dD( aq ) The Law of Mass Action is the
relationship between a balanced
chemical equation and the
 C   D
c d

KC = expression of the equilibrium

 A  B 
a b
constant (K).

aA( g ) + bB( g ) cC( g ) + dD( g ) We can express K using

concentrations (KC) or pressures
(KP)
( PC ) ( PD )
c d

KP =
( PA ) ( PB )
a b

9
Relating Equilibrium Constants KP and KC
 C   D
c d
In the gas phase amounts are easily
KC =
 A  B  expressed in concentration and
a b
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
concentration (units: mol L-1)?
PV = nRT
c d
 PC   PD  Stoichiometric difference is the
   
KC = 
RT   RT  change in moles overall between
a b
 PA   PB  products and reactants (Δn)
   
 RT   RT 

( PC ) ( PD )
c d

KP =
( PA ) ( PB )
a b ( c + d ) −( a +b )
 1 
KC = K P  
 RT  11
Relating Equilibrium Constants KP and KC
Stoichiometric difference is the
change in moles overall between
( c + d ) −( a +b )
 1  products and reactants (Δn)
KC = K P  
 RT 

n = nproducts − nreactants = (c + d ) − (a + b) For what value of Δn are KP

and KC equivalent?
n (A) 4
 1 
KC = K P  
(B) 3
 RT  (C) 2
OR (D) 1
(E) 0
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 want to
relate equilibrium to reaction Standard States
spontaneity
Solutes (C°) Gases (P°)
• Requires a unitless
description of KC or KP using
activities
• Activity (a) is a measure of
deviation from the standard
state
aX =
 X PX
aX = 
 P
C
16
The rule for relating K to KC or KP

17
Heterogenous Equilibria: Solids & Liquids
Standard States
• Many reactions involve
pure solids or liquids as Solutes (C°) Gases (P°)
part of a balanced equation
• What are the standard aX =
 X PX
aX = 
states that define the  P
activity of solids and
C
liquids? Pure Solids Pure Liquids

18
Examples: Heterogenous Equilibria
Give the expression of the thermodynamic equilibrium constant (K)
and its relation to KP for the following reaction:

2CO( g ) CO2( g ) + C( s )
aCO2 ( g ) aC( s ) What is the value of K equivalent to?
K= (A) KP(P°)2

(a )
2
(B) KP(P°)-2
CO( g ) (C) KP(P°)
(D) KP(P°)-1
(E) KP
19
Examples: Heterogenous Equilibria
Give the expression of the thermodynamic equilibrium constant (K)
and its relation to KP for the following reaction:

2CO( g ) CO2( g ) + C( s )

aCO2 ( g ) aC( s )
K=
(a )
2
CO( g )

20
Examples: Acid-Base Equilibria
Give the expression of the thermodynamic equilibrium constant (K)
and its relation to KC for the following reaction:
+ −
NH 3( aq ) + H 2O( l ) NH 4 ( aq ) + OH ( aq )

21
Practice: Heterogeneous Equilibria

22
Practice: Heterogeneous Equilibria

23
Practice: Heterogeneous Equilibria

24
Sections 14.4-14.6

25
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

26
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)
27
What does the Equilibrium Constant (K) mean?
2. When K is small it
indicates:
• K<1 N 2( g ) + O2( g ) 2 NO( g )
• Numerator < Denominator −31
• Amount of reactants K = 4.110 (at 25 °C)
favoured over products
• ‘reaction lies to the left’ Why is this reaction unlikely
to proceed much?

Recall: K says NOTHING about how fast equilibrium is

reached, ONLY how far the reaction has gone when equilibrium
is reached.
28
What does the Equilibrium Constant (K) mean?
aA( g ) + bB( g ) cC( g ) + dD( g )
Summary:
1. K < 1 aA( aq ) + bB( aq ) cC( aq ) + dD( aq )
• 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

29
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

30
Equilibrium Constant and Chemical Equations

1. Reversing an equation?
Invert the equilibrium constant

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

K forward = K reverse =
Reverse

 A B  C 
2 3

K reverse =
31
Equilibrium Constant and Chemical Equations

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

Raise the equilibrium constant to the same factor

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

K =
'
=K n
32
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
+ 2B 3C

 C
3

K overall = = = K1 K 2
 A
33
Example

34
Practice

35
Practice

36
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).

37
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

38
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: quantity are all we need
[A]eq = 0.75 mol L-1
• Can calculate other
We can deduce [B]eq and K by equilibrium quantities
stoichiometry AND equilibrium constant
  A = (K) via stoichiometry

  B =
39
The I-C-E Table
A( aq ) 2 B( aq ) • We can summarize these
If initially, findings in an I-C-E table
[A] = 1.00 mol L-1 and [B] = 0.00 mol L-1 Initial
And at equilibrium: Change
[A]eq = 0.75 mol L-1
Equilibrium
We can deduce [B]eq and K by
stoichiometry

  A = -0.25 mol L-1

  B = 0.50 mol L-1

40
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

41
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)

42
Example: The I-C-E Table

43
Practice: The I-C-E Table

44
Practice: The I-C-E Table

45
Example: The I-C-E Table

46
Practice: The I-C-E Table

47
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:
1. Predicts the direction of
change (if we know K)
2. Always approaches
equilibrium as the final
state

48
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 QC =
chemical system

49
The Reaction Quotient (Q)
What is the value 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

50
The Reaction Quotient (Q)
What is the value 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

51
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
unitless
( PC ) ( PD )
c d
• Relies on same assumptions
of ideality as K QP =
( PA ) ( PB )
a b

52
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

53
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

54
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
55
Example: Comparing Q and K

56
Practice: Comparing Q and K

57
The Reaction Quotient (Q)
For the following reaction with KP = 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

58
Sections 14.7-14.8

59
Finding Equilibrium Concentrations

Sometimes we want to calculate equilibrium

concentrations using an equilibrium constant (K)

Two types of problems:

1. Finding equilibrium amounts when we know K and
ALL BUT ONE of the amounts of reactants and
products
2. Finding equilibrium amounts when we know K and
initial amount(s)

60
Example: Finding Equilibrium Concentrations
14.7: K and ALL BUT ONE

61
Practice: Finding Equilibrium Concentrations
14.7: K and ALL BUT ONE

62
Finding Equilibrium Concentrations
K and Initial Amounts
• This is the more common A( aq ) 2 B( aq )
calculation for equilibrium
amounts
• Can be approached using the
I-C-E table
• Where changes in the amount
are NOT measured, we
represent them with the
variable x and account for If K = 0.33, we can solve for x
stoichiometry

63
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=
2a 64
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
65
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
66
Example: Finding Equilibrium Concentrations
14.8: K and Initial Amounts

67
Example: Finding Equilibrium Concentrations
14.8: K and Initial Amounts

68
Practice: Finding Equilibrium Concentrations
14.8: K and Initial Amounts

69
Practice: Finding Equilibrium Concentrations
14.8: K and Initial Amounts

70
Example: Finding Equilibrium Concentrations
14.9: K and Initial Amounts

71
Example: Finding Equilibrium Concentrations
14.9: K and Initial Amounts

72
Practice: Finding Equilibrium Concentrations
14.9: K and Initial Amounts

73
Practice: Finding Equilibrium Concentrations
14.9: K and Initial Amounts

74
Example: Finding Equilibrium Concentrations
• Same approach can be used
for either partial pressures
or concentrations

75
Example: Finding Equilibrium Concentrations
• Same approach can be used
for either partial pressures
or concentrations

76
Practice: Finding Equilibrium Concentrations

77
Approximations to Simplify Eq’m Problems
• Sometimes we can simplify the A( aq ) 2 B( aq )
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
equilibrium concentration that K= =
is essentially unchanged  A (1.0 − x )
78
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

79
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
• This approximation works
x = 0.0029 (1.0 − x ) 1.0 where the equilibrium
concentrations change very
little from their initial state
% ERROR due to a very small value of K

x 0.0029 Can you think of another

%error = 100% = 100% = 0.29%
 Aeq 1.0
scenario where we can
simplify?

*Note: This often will NOT work. Solving the

80
expanded formula will ALWAYS work.
Example: Finding Equilibrium Concentrations

81
Example: Finding Equilibrium Concentrations

When this method does NOT work, the

estimated value of x can be used to
iteratively approximate its true value
until within the 5 % error tolerance

82
Practice: Finding Equilibrium Concentrations

83
Example: Finding Equilibrium Concentrations

84
Example: Finding Equilibrium Concentrations

85
Practice: Finding Equilibrium Concentrations

86
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

87
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
88
Le Châtelier’s Principle: Reactant/Product
• For gas phase reactions, changes
in partial pressures of reactant or N 2O4( g ) 2 NO2( g )
product
• For solution phase reactions, Before addition:

changes in concentration of
reactant or product
After addition:

• What happens if we add NO2 to this

system at equilibrium?
• Minimize disturbance Reaction proceeds:

• Create reactant to re-establish K

• Can use the reaction quotient
(Q) to assess
89
Le Châtelier’s Principle: Reactant/Product
• What happens if we add NO2 to this
system at equilibrium?
• Minimize disturbance
N 2O4( g ) 2 NO2( g )
• Create reactant to re-establish K Before addition:
• Can use the reaction quotient
(Q) to assess
After addition:

Reaction proceeds:

90
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

91
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

What happens when we decrease the

partial pressure or concentration of a
reactant or product?
92
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

93
Example: Le Châtelier’s Principle

94
Practice: Le Châtelier’s Principle

95
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

So, if the volume decreases,

pressure increases and vice versa

According to Le Châtelier’s
Principle, equilibrium systems move
to minimize these changes. Recall: The ideal gas law

96
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?

97
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
98
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

increase the pressure?

99
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
100
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

101
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?
N 2( g ) + 3H 2( g ) 2 NH 3( g )
(A) Left
(B) Right
(C) Neither

102
Example: Le Châtelier’s Principle

103
Practice: Le Châtelier’s Principle

104
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.
105
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:

106
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:
107
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

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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

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Example: Le Châtelier’s Principle

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Practice: Le Châtelier’s Principle

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