Equilibrium system

 A reaction is said to be in equilibrium when the rate of the

forward reaction is equal to that of the backward reaction.
 For example: evaporation and condensation of water in a
closed system.

evaporation
WATER (liquid) STEAM
condensation

evaporation = condensation

equilibrium
 Equilibrium equation format

 A chemical equation:
forward reaction

Reactants products

backward reaction reveribility sign

 Conditions for equilibrium
The conditions for equilibrium are;
1. The reaction must occur in a closed system.
2. The reaction must be a reversible reaction
e.g.

A + B C + D
reactants products

CaCO3(s) CaO(s) + CO2(g)

reactant products
 Equilibrium constant (k)
According to the law of mass action which
states that at constant temperature, the rate
of a reaction is proportional to the active
masses of each of the reactants.
r
mA + nB product

When m moles of A reacts with n moles of B,

therefore the rate of the reaction r is
proportional to the concentrations A and B
Mathematically:
∗
• Rate (r) α 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝐴 𝑚 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝐵 𝑛
i.e. r α 𝐴 𝑚 . 𝐵 𝑛
• Therefore: r = 𝑘 𝐴 𝑚 . 𝐵 𝑛
Where K is a constant.
Now for a reversible reaction at equilibrium;

r1
mA + nB pC + qD
r2

reactants products
 Therefore: r1 = 𝑘1 𝐴 𝑚 . 𝐵 𝑛
 And r2= 𝑘2 𝐶 𝑝 . 𝐷 𝑞
 recall that in an equilibrium reaction, the rate of
the forward reaction is equal to that of the
backward reaction (r1 = r2).
 If r1 = r2
 Therefore 𝑘1 𝐴 𝑚 . 𝐵 𝑛 = 𝑘2 𝐶 𝑝 . 𝐷 𝑞
𝑘1 𝐶 𝑝. 𝐷 𝑞
 Hence: =
𝑘2 𝐴 𝑚. 𝐵 𝑛
𝑘1
 And if K =
𝑘2
𝐶 𝑝. 𝐷 𝑞
 hence: equilibrium constant K =
𝐴 𝑚. 𝐵 𝑛
Generally the equilibrium constant of a reaction
is given as;
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑐𝑜𝑛𝑐.𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
K= 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
𝑐𝑜𝑛𝑐.𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
 Example 1
Show the equilibrium constant for the
following equation;
2SO2 + O2 2SO3
Solution
[𝑝𝑟𝑜𝑑𝑢𝑐𝑡]
recall K =
[𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡]

𝑆𝑂3 2
Therefore: K =
𝑆𝑂2 2 . [𝑂2]
 Exercise 1

 consider the equation for the equilibrium

reaction; N2(g) + 3H2(g) 2NH3(g) ∆H = -92kjmol-1
the equilibrium constant for the reaction
can be expressed as;
2[𝑁𝐻3] 𝑁𝐻3 2
(a) k= 𝑏 𝑘=
3 𝐻2 [𝑁2] 𝑁2 𝐻2 3

3 𝐻2 [𝑁2] 𝑁2 𝐻2 3
(c) 𝑘 = (𝑑) 𝑘 =
2[𝑁𝐻3] 𝑁𝐻3 2
 Le chatelier’s principle
 Le chatelier principle states that if an external
constraint such as a change in temperature, pressure
or concentration is imposed on a chemical system in
equilibrium, the equilibrium will shift so as to annul
or neutralize the constraint.
Describing le chatelier’s principle
 Effect of a change in temperature to an equilibrium
system

If the reaction is endothermic, i.e. change in

enthalpy (∆H) is positive, therefore an
increase in temperature will favour the
forward reaction and vice versa.

If the reaction is exothermic, i.e ∆H is

negative, therefore an increase in temperature
will only favour the backward reaction and
vice versa.
 Consider the illustrations
1. An endothermic reaction:
k-value is greater
high temperation

N2(g) + O2(g) 2NO(g) +90.4kj/mol

endothermic
low temperature
k-value is less
2. An exothermic reaction:

k-value is less
high temperation

SO2(g) + O2(g) 2SO3(g) - 395.7kj/mol

exothermic
low temperature
k-value is greater
 Consider the following reaction equation
1. N2(g) + O2(g) 2NO(g) ∆H = +90.4 kj/mol
endothermic
 Increasing the temperature will favour the forward
reaction (i.e. the formation of nitrogen monoxide [NO]
will be favoured).

• Since the product is favoured, the equilibrium constant

(K) will be having a greater value.

 lowering the temperature will favour the backward

reaction (i.e. formation of the reactants N2 and O2).

• Hence the K – value will be lower since the forward

reaction is not favoured.
2. 2SO2 + O2 2SO3 ∆H = -395.7kj/mol
exothermic
 An increase in the temperature will favour the
backward reaction (i.e. the formation of SO2 and
O 2)

• Hence the K – value will be less since forward

reaction was not favoured.

 A decrease in the temperature will favour the

forward reaction (i.e. the formation of SO3).

• Hence the K – value will be greater since the

forward reaction was favoured.
 Exercise 2
1. Consider the reaction represented by the equation

N2O4(g) 2NO2(g) ∆H = +xkjmol-1

what happens when the temperature is reduced

at equilibrium.
a. Concentration of N2O4(g) decreases.
b. Concentration of NO2(g) increases.
c. Pressure exerted by the gases increases.
d. Pressure exerted by the gases remains constant.
2. Consider the following reaction equation:
X(g) + Y2(g) XY2(g) ∆H = +220kjmol-1

If the temperature of the system is increased, the

a) backward reaction would be favoured.
b) Forward reaction would be favoured.
c) Reaction would stop.
d) React ion would be at equilibrium.
Effect of a change in pressure to an equilibrium system
 For a change in pressure to affect a chemical equilibrium;
1. One of the reactants or products in the reversible reaction
must be gaseous.
2. The total number of moles or volumes of the gaseous
molecules on the left side of the equation must be different
from the total number of moles or volumes of the gaseous
molecule on the right side of the equation. For example;
N2(g) + 3H2(g) 2NH3(g)

1 + 3 2

4 moles 2moles
or or
volumes volumes
 High pressure on a gaseous equilibrium system will
favour the side with less volume.

 Low pressure on a gaseous equilibrium system will

favour the side with greater volume.

high pressure

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

2 + 1 = 3 volumes 2 volumes

low pressure
 Consider the reaction equation
 N2(g) + 3H2(g) 2NH3(g)

1 + 3 2

4 moles 2moles
 high pressure on the above system will favour the
forward reaction which is the side with less amount
(i.e. the formation of ammonia NH3)

 Low pressure imposed on the system will favour the

backward reaction which is the side with greater
amount (i.e. the formation of N2 and H2)

• The equilibrium constant k will remain constant

because the high or low pressure imposed will be
counteracted by the favoured side.
 Exercise 3
 consider the following equilibrium reaction:
2AB2(g) + B2(g) 2AB3(g) ∆H = -X kjmol-1
the backward reaction will be favoured by;

a) a decrease in pressure.
b) an increase in pressure.
c) a decrease in temperature.
d) an introduction of a positive catalyst.
 Effect of concentration on a system in equilibrium

 when the reactants concentration is increased, the

equilibrium will shift to the right, thereby favouring the
forward reaction (i.e. products formation).

 When the products’ concentration is increased, the

equilibrium will shit to the left, thereby favouring the
backward reaction (i.e. reactants formation).

• The equilibrium constant (K) will remain unchanged as

the concentration according to le chatelier’s principle.
 Consider the following reaction

 thermal decomposition of calcium carbonate:

high concentration of the reactant

favours the foward reaction

CaCO3(s) CaO(s) + CO2(g)

high concentation of the products

favour the the backward reaction
 Exercise 4

 consider the following equilibrium system:

2SO2(g) + O2(g) 2SO3(g)
the addition of O2(g) to the system will
shift the equilibrium position to the;
a) right leading to the production of more
SO3(g)
b) Right leading to the production of more SO2(g)
c) left leading to the production of more SO2(g)
d) Left leading to the production of more O2(g)
 Effect of a catalyst
 A catalyst has no effect on the yield of reactants or
products in an equilibrium system, hence cannot be
use to increase products or reactants formation. A
catalyst can only affect the speed (rate) for each
reaction to reach equilibrium.

 A positive catalyst increases the rate of the forward

and backward reaction by lowering the activation
energy of the reaction.

 A negative catalyst slows down the rate of a

reaction, so that a longer time is needed to reach
equilibrium.
 Exercise 5

1. consider the reaction represented by the following

equation: N2(g) + 3H2(g) 2NH3(g) ∆H = -92kjmol-1
finely divided iron is used as catalyst in the
reaction in order to;

a) lower the value of ∆H

b) increase in the time for attainment of equilibrium
c) shorten the time for attainment of equilibrium
d) decrease the yield of ammonia
2. Which of the following factors will affect the rate of
formation of S(s) in the reaction represented by the
equation below?
S2O2-3(aq) + 2H+ (aq) → SO2(g) + H2O(l) + S(s)

a) Increase the temperature

b) Increase the pressure
c) Removal of water
d) Use of catalyst
 Random Exercises
1. Consider the equilibrium reaction represented by
the following equation;
∆H = -395.kjmol-1
which of the following statement about the
equilibrium is correct?

a) Addition of catalyst changes the equilibrium

b) Decrease in pressure increase the yield of SO3
c) Decrease the pressure increases the equilibrium
concentration of O2
d) Increase in the temperature favours the forward
reaction
2. Consider the following equilibrium reaction:
X(g) + Y2(g) XY2(g) ∆H = -52kjmol-1

i. State what happens to the yield of XY2 when

the temperature is increased.
ii. Explain the effect of decrease in pressure on
the equilibrium position
iii. State the effect of catalyst on the
(a) position of equilibrium
(b) activation class
 The end

thanks for being attentive.