CHAPTER 6

CHEMICAL EQUILIBRIUM

6.1 Dynamic Equilibrium

6.2 Equilibrium Constants
6.3 Le Chatelier’s
Principle
1
CHAPTER 6
CHEMICAL EQUILIBRIUM

6.1 Dynamic Equilibrium

2
 Learning Outcomes

At the end of the lesson, students should be able to:

a) Explain the following terms :

i. a reversible reaction
ii. dynamic equilibrium
iii. law of mass action
b) State the characteristics of a system in equilibrium
c) Interpret the curve of concentration reactants and
products against time for a reversible reaction
3
 Dynamic Equilibrium
REVERSIBLE REACTION
• Most chemical reactions proceed to completion.
• The reaction continues until one of the reactants is
completely used up and the reaction stops.
• Reaction takes place in one direction.

A + B  C + D

uv
Example : CH4 + Cl2  CH3Cl + HCl

4
 Dynamic Equilibrium
REVERSIBLE REACTION
- However many other reaction do not proceed to
completion.
- Not all reactants are changed to product because the
product can dissociate to form the reactants again.
- Reaction takes place in both directions.

A B
reactant product

5
 Dynamic Equilibrium

A B
reactant product

• The reaction proceeding from left to right is called

the forward reaction.
• The reaction proceeding from right to left is called
the reverse reaction.
• Chemical reactions which take place in both forward
and reverse directions are called reversible reaction.
= indicates reversible reaction

Example : H2(g) + I2(g) 2HI (g) 6

 Dynamic Equilibrium

H2(g) + I2(g) 2HI (g)

• In a reversible reaction, initially the reaction proceeds

toward the formation of products (HI).
• As soon as some product molecules formed, the
reverse process begins to take place.
• Reactant molecules, H2 and I2 are formed from
dissociation of the product molecules.

7
 Dynamic Equilibrium
Consider the following reversible reaction:

A B

The concentration-time graph for reaction between A

and B :
From the graph :
• [A] decrease with time
• [B] increase with time
• After time, t1, [A] and [B]
remains constant.

8
 Dynamic Equilibrium
Consider the following reversible reaction:

A B

The concentration-time graph for reaction between A

and B :
Take note that :
• As reaction proceeds, the
rate of forward reaction
decreases, the rate of
reverse reaction increases.
• When the rate of forward
and reverse reaction
becomes equal,[A] and
[B] remain constant. 9
 Dynamic Equilibrium
Consider the following reversible reaction:

A B

The concentration-time graph for reaction between A

and B :
• At this point, the system is
said to be in chemical
equilibrium.
• After t1, the reaction
continues indefinitely
even after equilibrium
has been attained.
• This equilibrium is
dynamic equilibrium
 Dynamic Equilibrium

EQUILIBRIUM
A state in which there are no observable changes as time
goes by.

Two types of equilibrium :

physical equilibrium
chemical equilibrium

11
 Dynamic Equilibrium

EQUILIBRIUM
Physical Equilibrium

Involves Physical change

H2O (l) H2O (g)

Number of H2O
Number of H2O
molecules leaving = molecules returning
to liquid phase
12
 Dynamic Equilibrium

EQUILIBRIUM
Chemical Equilibrium
Most chemical reactions are reversible.
Consider : N2O4(g) 2NO2(g)
colorless brown
When we introduce some N2O4(l) into a sealed flask
kept at 100oC, a change occurs immediately.
The liquid vaporizes (bp = 21oC) and the gas begins to
turn pale brown.
The color slowly darkens, but after awhile,
no further color change can be seen : [ratefwd = raterev]
A B C D

At equilibrium,
N2O4 molecules decompose
as fast as
NO2 molecules combine

A : Start N2O4(g) 2NO2(g)

B : Mixture becomes pale brown
 N2O4 decompose to reddish brown NO2
C : Mixture reaches final color
 reaction reaches equilibrium
D : Concentrations (and color) remain constant 14
 Dynamic Equilibrium

DYNAMIC EQUILIBRIUM
- In a reversible reaction, both forward and reverse
reaction continue indefinitely even though equilibrium
has been established.
- Therefore, chemical equilibrium is a dynamic process.
- Reactant and product concentrations stop changing
because the forward and reverse rates have become
equal.

ratefwd = raterev
15
 Dynamic Equilibrium

DYNAMIC EQUILIBRIUM
Remember that …
For the reaction : N2O4(g) 2NO2(g)
At equilibrium,

Rate of forward reaction Rate of reverse reaction

N2O4(g)  2NO2(g) = 2NO2(g)  N2O4(g)

[N2O4(g)] and [NO2(g)] remain constant, but ….

[N2O4(g)] ≠ [NO2(g)] 16
 Dynamic Equilibrium

CHARACTERISTICS OF A SYSTEM IN EQUILIBRIUM

Note : Equilibrium can only occur in a closed system !

i. Concentration of the reactants and products are

constant over time.

ii. Forward reaction rate = reverse reaction rate

iii. The reaction quotient (Q ) = The equilibrium

constant (K )
Q=K
(Will be discussed further in 6.2) 17
 Dynamic Equilibrium
N2O4(g) 2NO2(g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4
Even though equilibrium is reached in all cases, the
equilibrium concentrations of NO2 and N2O4 are …
not the same ! 18
 Dynamic Equilibrium

N2O4(g) 2NO2(g)

The NO2-N2O4 system at 25°C

Constant !

19
 Dynamic Equilibrium
[NO2]2 [NO2]2
The ratio is a constant = 4.63 x 10-3
[N2O4] [N2O4]
= K
K is known as the equilibrium constant
The NO2-N2O4 system at 25°C
 Dynamic Equilibrium

LAW OF CHEMICAL EQUILIBRIUM

Also known as law of mass action.
States that …
For any equilibrium at a given temperature, the product
(multiplication) of the [product], each raised to a power
equal to its coefficient in the chemical equation, divided
by the product (multiplication) of the [reactants] each
raised to a power equal to its coefficient in the chemical
equation will be a constant.
For a particular system and temperature, the same
equilibrium state is attained regardless of how the
reaction is run. 21
 Dynamic Equilibrium

LAW OF CHEMICAL EQUILIBRIUM

Consider this general reaction equation:

aA + bB cC + dD

At equilibrium : [ C ]c [ D ]d
[ A ]a [ B ]b
= K
Where :
a, b, c, d - stoichiometric coefficients
K - equilibrium constant,
[] - concentration 22
 Dynamic Equilibrium

LAW OF CHEMICAL EQUILIBRIUM

Example 1 :

CH3COOC2H5(l) + H2O(l) CH3COOH(l) + C2H5OH(l)

At equilibrium :
[CH3COOH ]1 [C2H5OH ]1
K =
[CH3COOC2H5]1 [H2O]1
Where :
K - equilibrium constant,
[] - concentration 23
 Dynamic Equilibrium

LAW OF CHEMICAL EQUILIBRIUM

Example 2 :

2SO2 (g) + O2 (g) 2SO3 (g)

At equilibrium :
[SO3 ]2
K =
[SO2]2 [O2]1
Where :
K - equilibrium constant,
[] - concentration
24
CHAPTER 6
CHEMICAL EQUILIBRIUM

6.2 Equilibrium Constants

25
 Learning Outcomes

At the end of the lesson, students should be able to:

(a) Define homogeneous and heterogeneous

equilibria.
(b) write expressions for equilibrium constants in
terms of concentration, Kc and partial pressure, Kp
for homogeneous and heterogeneous systems.

26
 Equilibrium Constants
HOMOGENEOUS EQUILIBRIA
Chemical equilibrium in which all the reactants and the
products are in the same phase.

Writing the Kc and Kp Expressions

aA + bB cC + dD

[ C ]c [ D ]d
Kc = [ A ]a [ B ]b
27
 Equilibrium Constants
HOMOGENEOUS EQUILIBRIA
Chemical equilibrium in which all the reactants and the
products are in the same phase.

Writing the Kc and Kp Expressions

aA(g) + bB(g) cC(g) + dD(g)

(PC)c (PD)d
Kp = (PA)a (PB)b
28
 Equilibrium Constants
HETEROGENEOUS EQUILIBRIA
Chemical equilibria in which the reactants and products
are present in more than one phase.
Example :

liquid-gas Solid-gas
equilibrium equilibrium
29
 Equilibrium Constants
HETEROGENEOUS EQUILIBRIA
Chemical equilibria in which the reactants and products
are present in more than one phase.
Example :
CaCO3(s) CaO(s) + CO2(g)

[CaO][CO2] [CaCO3] = constant

KC =
[CaCO3] [CaO] = constant

KC = [CO2] KP = PCO2

Concentration of pure solid, pure liquid and solvent do

not appear in the expression of equilibrium constants.
30
 Equilibrium Constants
RELATING KP AND KC
Consider the general equation :
aA (g) + bB (g) cC (g) + dD (g)
[C]c [D]d PCc PDd
KC = KP =
[A]a [B]b PAa PBb

Assume gases behave ideally : PV = nRT

P = n RT
V Concentration !

PA = nA RT PB = nB RT PC = nC RT PD = nD RT
V V V V
= [A]RT = [B]RT = [C]RT = [D]RT
 Equilibrium Constants
RELATING KP AND KC
[C]c [D]d PCc PDd
KC = KP =
[A]a [B]b PAa PBb

PA = [A]RT PB = [B]RT PC = [C]RT PD = [D]RT

Substitute PA, PB, PC, and PD into KP

PCc PDd ([C]RT)c x ([D]RTd)
KP = =
PAa PBb ([A]RT)a x ([B]RTb)
[C]c [D]d
= x (RT)(c + d)–(a + b)
[A]a [B]b
= KC(RT)Δn Δn = (c + d) – (a + b)
 Equilibrium Constants
RELATING KP AND KC
KP = KC(RT)Δn

Δn = (
total mole of
gaseous products -) ( total mole of
gaseous reactants )
R = 0.0821 L atm mol-1 K-1

If Δn = 0 , KP = KC (RT)0 therefore, KP = KC
Example :
H2(g) + Br2(g) 2HBr(g)
Δn = 2 – (1 + 1) = 0
33
therefore, KP = KC