Equilibria

Chemical equilibrium
25 nov
QUIZZ
Describe and explain what will happen when (a) sodium
chloride (b) silver nitrate is added separately to the system in
equilibrium at constant temperature.
[Cu(H2O)4]2+(aq) + 4Cl-(aq) [CuCl4]2-(aq) + 4H2O(l)
Blue Yellow
a) Add NaCl to the mixture
Describe and explain what will happen when (a) sodium chloride (b)
silver nitrate is added separately to the system in equilibrium at
constant temperature.
Blue Yellow
b) Add AgNO3 to the mixture
Blue Yellow
a) Add NaCl to the mixture
Observation: The mixture immediately turns from blue to
yellow
Explanation: Addition of NaCl increase the concentration of
Cl- ions.The equilibrium is disturbed. To offset this
disturbance, some [Cu(H2O)4]2+ reacts with the added Cl-
ions, and the equilibrium shifts from left to right.
Blue Yellow
b) Add AgNO3 to the mixture
Observation: Solution turns blue and a white precipitate is
formed.
Explanation: The added Ag+ reacts with Cl- to form insoluble
AgCl. The Cl- ions are removed from the equilibrium system.
So, the equilibrium shifts from right to left to form more Cl-
ions to replace the Cl- ions that have been removed. More
[Cu(H2O)4]2+ produced.
THE EFFECT OF TEMPERATURE ON
EQUILIBRIUM
EQUILIBRIUM
EQUILIBRIUM
EFFECT OF TEMPERATURE ON EQUILIBRIUM
1. According to Le Chatelier’s principle, when temperature increases,
the equilibrium will shift to the direction where heat is absorbed
(endothermic reaction) to reduce the increase in temperature.
a) Dissociation of dinitrogen tetraoxide:
N2O4(g) 2NO2(g) ΔH = + 58kJ
i. The forward reaction is an endothermic process.
ii. Increase in temperature will shift the equilibrium to the
right
iii. The forward reaction is favoured as it absorbed heat and
lowers the temperature of the system.
iv. As a result, the concentration of the NO2 inreases while the
concentration of N2O4 decreases. Hence Kc will increases
Kc = [NO2]2 will increase
[N2O4]
EFFECT OF TEMPERATURE ON EQUILIBRIUM
1. According to Le Chatelier’s principle, when temperature increases,
the equilibrium will shift to the direction where heat is absorbed
(endothermic reaction) to reduce the increase in temperature.
2. Synthesis of Ammonia:
N2(g) + 3H2(g) 2NH3(g) ΔH = -92kJ
i. The forward reaction is an exorthermic process.
ii. Increase in temperature will shift the equilibrium to the left
iii. The reverse reaction is favoured as it absorbed heat and
reduces the temperature of the system.
iv. The concentration of the N2 and H2 inreases while the
concentration of NH3 decreases. Hence Kc will decreases
Kc = [NH3]2 will decrease
[N2][H2]3
v. When the temperature is changed, the
concentrations change even though no chemical
substances have been added or removed and the
volume remains the same. Hence, there is a
change in the value of Kc.
a) Hydrolisis of Esters:
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O; ΔH =

0 kJ
i. Change of temperature has no effect on this
equilibrium
ii. For the reaction which ΔH = 0, its equilibrium
constant is not affected by temperature.
EFFECT OF PRESSURE ON EQUILIBRIUM
Le Chatelier’s principle predicts that
1. According to Le Chatelier’s principle, when pressure increases, the
equilibrium will shift to the direction where the total number of
moles of gases is reduced to reduce the increase in pressure
2. Only equilibrium systems containing gaseous reactants and/or
products are affected by changes in pressure
Dissociation of dinitrogen tetraoxide:
N2O4(g) 2NO2(g)
i. An Increase in pressure will shift the equilibrium to the left
ii. The reverse reaction involves decrease in the number of moles of
gases.
iii. The number of moles of N2O4 formed increases while the number
of moles of NO2 is decreased.
iv. The equilibrium constant, Kc and Kp remain unchanged with the
change of pressure
Synthesis of Ammonia:
N2(g) + 3H2(g) 2NH3(g)
i. An Increase in pressure will shift the equilibrium to the right to
form more NH3
ii. This is because the forward reaction involves a decrease in
number of moles of gases.
iii. The equilibrium constant, Kc and Kp remain unchanged with
the change of pressure
3. Other reactions : H2(g) + I2(g) 2HI(g)
4. 3Fe(s) + 4H2O(g) Fe3O(s) + 4H2(g)
5. Changing the pressure will not affect equilibrium constant , Kc and
Kp of the above equilibrium system since the number of moles of
gaseous reactants is the same as the number of moles of gaseous
products.
EFFECT OF INERT GASES ON THE EQUILIBRIUM
1. At Constant Pressure
i. If an inert gas is added to the equilibrium mixture at
constant pressure(increase volume), the partial pressure of
each of the gas in the mixture decreases. So, the effect is as
though the gases in the system are subjected to a lower
pressure.
ii. Equilibrium will shift to the direction that increases the
number of moles of gas.
2. At Constant Volume
i. If the inert gas is added to the equilibrium mixture at
constant volume, total pressure of the system increases, but
the partial pressure of each gas in the mixture remains
unchanged.
ii. Hence, the addition of an inert gas will not affect the
equilibrium position.
APPLICATION OF LE CHATELIER’S PRINCIPLE IN
THE INDUSTRIAL PROCESSES
1. The Contact Process –
Manufacture of sulphuric acid
2SO2(g) + O2(g) 2SO3(g) ΔH = -197kJ mol-1
a) The forward reaction is exothermic and
accompanied by a decrease in the number of
moles of gas. According to Le Chatelier’s Principle,
a high yield of SO3 is obtained at low temperature
and high pressure.
1. The Contact Process –
Manufacture of sulphuric acid
2SO2(g) + O2(g) 2SO3(g) ΔH = -197kJ mol-1
b) However, the rate of reaction is very low at low
temperature. By taking into account the effect of
both kinetic and equilibria factors, the optimum
temperature and pressure used in industry is
450°C and 1 atm. About 98% of SO 2 is converted
into SO3. A catalyst vanadium(V)oxide, V2O5 is used
so that the reaction will reach equilibrium faster.
2. The Haber Process – manufacture of ammonia
N2(g) + 3H2(g) 2NH3(g) ΔH=-92kJ mol-1
a) The forward reaction is an exothermic reaction.

A low temperature favours the forward reaction
and gives a high yield of ammonia but the reaction
rate is low.
b) So the optimum temperature is 500°C

2. The Haber Process – manufacture of ammonia
N2(g) + 3H2(g) 2NH3(g) ΔH=-92kJ mol-1
c) The forward reaction involves a decrease in the

number of moles of gases. Therefore, a high
pressure will increase the yield of ammonia but
the higher the pressure, the higher the cost to
maintain the pressure. Thus, the pressure used in
industry is 250 atm.
d) In order to increase the rate of raection, iron is
used as a catalyst and a mixture of K2O and Al2O3.
2. The Oswalt Process – manufacture of nitric acid
a) The raw material used for making nitric acid are liquid
ammonia (produced by Haber Process) and air
b) The Oswald Process involves in three stages
Stage 1: Catalytic Oxidation of Ammonia
- the gaseous mixture of ammonia and air is passed through
platinum-rhodium catalyst at 850°C and pressure 4 – 10 atm
to produce nitrogen monoxide and steam.
850°C
4NH3(g) + 5O2 4NO(g) + 6H2O(g) ΔH = - 900kJ mol-1
Pt/Rh catalyst
850°C
4NH3(g) + 5O2 4NO(g) + 6H2O(g) ΔH = - 900kJ mol-1
Pt/Rh catalyst
ii. The forward reaction is highly exothermic and involves
an increase in the number of moles of gases.
According to Le Chatelier’s Principle, a high yield of
nitric oxide at equilibrium is obtained at low
temperature and low pressure. Platinum-rhodium is
used to speed up the reaction.
a) The raw material used for making nitric acid are
liquid ammonia (produced by Haber Process) and
air
b) The Oswald Process involves in three stages
Stage 2: Oxidation of NO to NO2
i. The nitrogen monoxide formed is cooled and
passed through the oxidation chamber where is
oxidised(by air) to form nitrogen dioxide
2NO(g) + O2 2NO2(g)
Stage 3: Disproportionation of NO2 in water.
i. The nitrogen dioxide formed is then mixed with
water to form 60% of nitric(V) acid
3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)
ii. The nitric acid can be concentrated up to 95-
98% by adding concentrated sulphuric acid.

Equilibria

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Chemical equilibrium

CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O; ΔH =

a) The forward reaction is an exothermic reaction.

b) So the optimum temperature is 500°C

c) The forward reaction involves a decrease in the

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