LEARNING OUTCOMES

• Describe equilibrium in chemical process

• Predict the reaction conditions based on le

Chatelier’s principle

• Apply equilibrium constant to solve

problems

2
 CHEMICAL REACTION

Irreversible Reaction Reversible Reaction

• reaction proceeds in • reaction proceeds in
only single direction both directions

• a complete reaction • not a complete reaction,

but equilibrium reaction
Ex: Combustion
3H2 + N2 2NH3
CH4 + 2O2 CO2 H2O
+ hydrogen nitrogen Ammonia
methane oxygen
Ex: Haber process 4
 Closed System Open System
Chemistry for the IB Diploma 2nd Edition, Hodder Education.

• No CO2 escapes • CaCO3 is continually

decomposing as the
CO2 is lost.
• _____________ is • Reaction goes to
achieved. ______________.
4
 CHARACTERISTICS OF DYNAMIC
EQUILIBRIUM

1. It is an ______________ process.

2. The forward and reverse reactions occur at

the _________________.

3. The concentrations of reactants and

products remain _________ at equilibrium.

4. It requires a ___________ system.

5
 [REACTANTS] AND [PRODUCTS]
REMAIN CONSTANT AT EQUILIBRIUM

Hydrogen iodide

6
 RATE OF FORWARD REACTION
EQUAL TO THE RATE OF REVERSE
REACTION AT EQUILIBRIUM

7
 FACTORS AFFECTING EQUILIBRIUM

Concentration Pressure
(mol dm-3) Temperature (atm)
(°C)

8
LE CHATELIER’S PRINCIPLE

When a system in equilibrium is

disturbed, the equilibrium composition
changes (shifts to the left or right) as
to minimize the disturbance
(concentration, temperature,
or pressure).

French chemist: Henri Le Chatelier

(1850 – 1936)
9
 COUNTERACT → OPPOSE !
Make it hotter –> equilibrium moves to cool it
Make it cooler –> equilibrium moves to heat it
Raise the pressure –> equilibrium moves to lower it
Lower the pressure –> equilibrium moves to raise it

Chemistry for the IB Diploma 2nd Edition, Hodder Education.

10
 CHANGES IN CONCENTRATION
Fe3+ + SCN- [Fe(SCN)]2+
iron(III) thiocyanate blood red colour
thiocyanatoiron(III)
disturbance

• If excess SCN- is added to the system, the equilibrium will

shift to the right to produce more [Fe(SCN)]2+.

Effect: Solution becomes redder
• If SCN- is removed from the system, the [Fe(SCN)]2+ will
convert to SCN- & Fe3+ & equilibrium will shift to the left.
Effect: Solution becomes pale red
11
PRODUCTION OF NH3: N2(g) + 3H2(g) ⇌ 2NH3(g)
What would be the effect on the equilibrium of
increasing the concentration of the N2 gas in the
reaction mixture?

Chemistry for the IB Diploma 2nd Edition, Hodder

Education.
An eq. is established After the eq. has been disturbed,
between N2, H2 and NH3 a new eq. position is established
12
containing more NH3
EXERCISE 1

CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O

Explain what happens to the position of

equilibrium when:

I. more CH3COOC2H5 is added.

II. some C2H5OH is removed.

13
EXERCISE 2

Ce4+ + Fe2+ ⇌ Ce3+ + Fe3+

Explain what happens to the position of

equilibrium when:

I. the concentration of Fe2+ ions is increased.

II. water is added to the equilibrium mixture.

14
 CHANGES IN TEMPERATURE

∆H = -94.9 kJ mol-1

2SO2 + O2 2SO3

disturbance

• When temperature , shift to left (absorb

heat), produce more SO2 & O2

• When temperature , shift to right (release

heat), produce more SO3
15
 The effects of temperature changes on chemical equilibrium

16
Chemistry for the IB Diploma 2nd Edition, Hodder Education.
EXERCISE 3
ΔHr = +41.2 kJ mol-1

H2(g) + CO2(g) ⇌ H2O(g) + CO(g)

Predict the effect of increasing the temperature

on the reaction above.

17
EXERCISE 4

Ag2CO3(s) ⇌ Ag2O(s) + CO2(g)

In the reaction above, increasing the

temperature increases the amount of carbon
dioxide formed at constant pressure. Is this
reaction exothermic or endothermic? Explain
your answer.
18
 Force N
CHANGES IN PRESSURE ( , 2 )
Area m

Higher pressure Lower pressure

- More molecules in - Less molecules
specific area in specific area
- Smaller space
- Larger space

19
 CHANGES IN PRESSURE
• Pressure is affected by no. of gas molecules

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

3 molecules 2 molecules
disturbance

• When pressure , shift to right (favours fewer

number of gas molecules)
• When pressure , shift to left (favours more
number of gas molecules) 20
 DECOMPOSITION OF N2O4

Pressure increase Pressure decrease

Chemistry for the IB Diploma 2nd Edition, Hodder Education.

The effect of changing pressure on the gaseous

equilibrium involving nitrogen dioxide can be followed
by observing the changes in colour intensity. 21
EXERCISE 5

(a) Predict the effect of increasing the pressure

on the following reactions:
I. N2O4(g) ⇌ 2NO2(g)
II. CaCO3(s) ⇌ CaO(s) + CO2(g)

(b) Predict the effect of increasing the pressure

on the reaction: 2NO2(g) ⇌ 2NO(g) + O2(g)
22
EXERCISE 6
Look at each of the following equations and
decide whether an increase of pressure will
increase, decrease or have no effect on the
amounts of products.

(a) CO(g) + Cl2(g) ⇌ COCl2(g)

(b) 2H2S(g) ⇌ 2H2(g) + S2(g)

(c) C(graphite) + S2(g) ⇌ CS2 (g)

23
 CHANGES WITH CATALYSTS
Adding a catalyst
✓ does not change the equilibrium composition of
a reaction mixture
✓ does not shift the position of an equilibrium
system
✓ system will reach equilibrium sooner

uncatalysed catalysed 24
EQUILIBRIUM CONSTANT

equilibrium
expression

* Kc & Kp are affected by TEMPERATURE only!!

25
 [] indicates the
The ‘products’
concentrations
are on the top
in mol dm-3 at
of the
equilibrium
expression

K is the
symbol for the
equilibrium
constant
Exponents or
Subscript c ‘powers’ are the
indicates the coefficients
use of used in the
concentration equation for
values the reaction
26
EXERCISE 7

(a)Write the equilibrium-constant expression Kc

for catalytic methanation.
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

(b) Write the equilibrium-constant expression Kc

for the reverse reaction.
CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)
27
EQUILIBRIUM-CONSTANT EXPRESSIONS

Write the equilibrium-constant expression for

the following reaction and calculate the value of
Kc: H2 + I2 ⇌ 2HI
[H2] / mol dm-3 [I2] / mol dm-3 [HI] / mol dm-3

0.68 x 10-3 0.68 x 10-3 8.64 x 10-3

0.50 x 10-3 0.50 x 10-3 6.30 x 10-3
1.10 x 10-3 2.00 x 10-3 18.8 x 10-3
2.50 x 10-3 0.65 x 10-3 16.1 x 10-3
28
The equilibrium concentrations for the
reaction between carbon monoxide and
molecular chlorine to form COCl2(g) at 74°C
are [CO] = 0.012 M, [Cl2] = 0.054 M, and
[COCl2] = 0.14 M.
Calculate the equilibrium constant Kc.

CO(g) + Cl2(g) ⇌ COCl2(g)

29
The equilibrium constant Kp for the
reaction is 158 at 1000K. What is the
equilibrium pressure of O2 if the PNO =
2
0.400 atm and PNO = 0.270 atm?

2NO2(g) ⇌ 2NO(g) + O2(g)

30
Homogeneous equilibrium is an equilibrium that
involves reactants and products in a single phase.

Heterogenous equilibrium applies to reactions in

which reactants and products are in more than one
phase.
CaCO3 (s) ⇌ CaO(s) + CO2(g)

Kc = [CO2] Kp = PCO 2

The concentration of solids and pure liquids are

not included in the equilibrium expression.
31
EQUILIBRIUM-CONSTANT EXPRESSIONS

We can use the value of the equilibrium

constant in ____ ways:

1. We can qualitatively describe the content of

the reaction mixture by looking at the
magnitude ofKc.

2. We can determine the direction in which a

reaction will proceed by comparing Kc to the
value of the reaction quotient, Q, which has
the same expression as Kc but uses non-
equilibrium values. 32
 HOW FAR WILL A REACTION GO?

• When Kc is very large (>102), the equilibrium

mixture is mostly products.

• When Kc is very small (<10-2), the equilibrium

mixture is mostly reactants.

• When Kc approaches 1, the equilibrium mixture

contains appreciable amounts of both

reactants and products.
33
EXERCISE 8

Kc = 0.82 for a reaction. Describe the composition

of the equilibrium mixture.

34
 REACTION QUOTIENT, Q

The reaction quotient has the same form as the

equilibrium constant, but uses ______________
______________for its value.

➢When Kc > Q, the reaction proceeds to the right.

➢When Kc < Q, the reaction proceeds to the left.

➢When Kc = Q, the reaction is at equilibrium.

35
 Qc MUST MOVE TOWARDS Kc

Copyright © Cengage Learning. All rights reserved.

Here the Here the

numerator must denominator must
increase; more increase; more
products must be reactants must
produced. be produced. 36
A mixture of dinitrogen tetroxide (2 mol dm-3)
and nitrogen(IV) oxide (6 mol dm-3) is
contained in a sealed tube at 500 K, will the
reaction move the composition of the mixture
to the left or right?

N2O4(g) ⇌ 2NO2(g) Kc at 500 K = 41

37
 The decomposition of HI was studied by
injecting 2.50 mol of HI into a 10.32 L vessel at
25°C. What is [H2] at equilibrium for the
reaction 2HI(g) ⇌ H2(g) + I2(g); Kc = 1.26 x 10-3?

1. Calculate the molarity of the initial concentration

2. State the RICE

Reaction :
Initial conc. :
Chg in conc. :
Eq. conc. : 38
3. State the equilibrium expression

4. Calculate Kc

39
 And yes, it’s a quadratic equation. Doing a bit of
rearranging:
x2 −3
= 1.26 x10
[0.242 − 2 x]2
x 2 = 1.26x10 −3[0.242 − 2 x]2
= 1.26x10 −3[0.0586 − 0.968 x + 4 x 2 ]
= 7.38x10 −5 − 1.22x10 −3 x + 5.04x10 −3 x 2
0.995 x 2 + 1.22x10 −3 x − 7.38x10 −5 = 0
x = 0.00802 or –0.00925
− b  b − 4ac
2
Since we are using this to
x=
2a model a real, physical system,
we reject the negative root.
The [H2] at eq. is 0.00802 M. 40
At 12800C the equilibrium constant (Kc) for
the reaction is 1.1 x 10-3. If the initial
concentrations are [Br2] = 0.063 M and [Br] =
0.012 M, calculate the concentrations of
these species at equilibrium.

Br2(g) ⇌ 2Br(g)

41
A nitrogen-hydrogen mixture, initially in
the mole ratio of 1:3, reached equilibrium
with ammonia when 50% of the nitrogen
had reacted. The total final pressure was
10 atm.
N2(g) + 3H2(g) ⇌ 2NH3(g)

What was the partial pressure of ammonia

& Kp in the equilibrium mixture?

42
A flask is filled with 3.00 atm of dinitrogen
tetroxide gas and 2.00 atm of nitrogen
dioxide gas at 25°C and allowed to reach
equilibrium. It was found that the pressure
of the nitrogen dioxide decreased by 0.952
atm.

Estimate the value of Kp.

N2O4(g) ⇌ 2NO2(g)
43
 CHEMISTRY IN ACTION

Life at High Altitudes and Hemoglobin Production

Hb (aq) + O2 (aq) ⇌ HbO2 (aq)

[HbO2]
Kc =
[Hb][O2]

44