In this article we shall study the application of Le-Chatelier’s principle in Haber’s process, contact proces, etc.

Statement of Le-Chatelier’s Principle:

This principle is given by, a French chemist Le-Chatelier in 1888. It states that “If an external stress is applied to a reacting system at equilibrium, the system will adjust itself in such a way that the effect of the stress is nullified”.

Application of Le-Chatelier’s Principle to Haber’s process (Synthesis of Ammonia):

Ammonia is manufactured by using Haber’s process. In this reaction Nitrogen and Hydrogen in ratio 1:3 by volume are made to react at 773 K and 200 atm. Pressure.

The chemical reaction is

N_2(g)  +   3H_2(g)   ⇌   2 NH_3(g)  + 96.3 kJ

1 Vol         3 Vol              2 Vol

4 Vol                2 Vol

From this reaction it is clear that, the reaction is exothermic and accompanied by the decrease in volume.

Effect of Concentration:

By the law of mass action; the increase in concentration of one of the reactant will shift equilibrium towards right.  And here increase in concentration of hydrogen (as more moles of it are used) in preference to Nitrogen has more effect.

Effect of Pressure:

Above reaction indicate that formation of ammonia takes place with decrease in volume.  Hence increase in pressure will favour forward reaction. Optimum pressure for maximum yield of ammonia is about 200 atm.

Effect of Temperature:

The reaction is exothermic, so lowering the temperature will favour forward reaction. But decrease in temperature results in the decrease in the rate of reaction. Hence temperature of 773K is maintained and iron is used as catalyst.

Application of Le-Chatelier’s Principle to Contact process (Synthesis of Sulphur Trioxide):

H₂SO₄ is manufactured by contact process. In this reaction SO₂ is oxidized to SO₃. Sulphur trioxide is further used for manufacturing of sulphuric acid.

2SO_2(g) + O_2(g)   ⇌   2 SO_3(g) +  189 kJ

2 Vol           1 Vol          2 Vol

From this reaction it is clear that, the reaction is exothermic and accompanied by the decrease in volume.

Effect of Concentration:

By the law of mass action; increase in concentration of one of the reactant will shift equilibrium towards right.  And here increase in concentration of sulphur dioxide in preference to oxygen has more effect.

Effect of Pressure:

Above reaction indicate that formation of sulphur trioxide takes place with decrease in volume.  Hence increase in pressure will favour forward reaction. Optimum pressure for maximum yield of sulphur trioxide is about 1.5 atm to 1.7 atm

Effect of Temperature:

The reaction is exothermic, so lowering the temperature will favour forward reaction. But decrease in temperature results in the decrease in the rate of reaction. Hence temperature of 723 K is maintained and vanadium pentoxide is used as catalyst.

Application of Le-Chatelier’s Principle to  Manufacture of Ozone:

Ozone is manufactured by passing silent electric discharge through pure oxygen.

3O_2(g)   ⇌  2 O_3(g) –  288.56 kJ

3 Vol               2 Vol

From this reaction it is clear that, the reaction is endothermic and accompanied by the decrease in volume.

Effect of Concentration:

By the law of mass action; increase in concentration of one of the reactant will shift equilibrium towards right.  And here increase in concentration of oxygen increases the rate of forward reaction.

Effect of Pressure:

Above reaction indicate that formation of ozone takes place with decrease in volume.  Hence increase in pressure will favour forward reaction.

Effect of Temperature:

The reaction is endothermic, so increasing the temperature will favour forward reaction. Due to increase in temperature heat will be absorbed by the reaction.

Application of Le-Chatelier’s Principle to  Manufacture of Nitric oxide:

The reaction is

N_2(g) +  O_2(g)   ⇌  2 NO_(g) –  181 kJ

1Vol  + 1 Vol        →       2 Vol

From this reaction it is clear that, the reaction is endothermic and accompanied by no change in volume.

Effect of Concentration:

By the law of mass action; increase in concentration of one of the reactant will shift equilibrium towards right.  And here increase in concentration of nitrogen or oxygen increases the rate of forward reaction.

Effect of Pressure:

Above reaction indicate that formation of nitric oxide takes place with no change in volume.  Hence pressure has no effect on the equilibrium.

Effect of Temperature:

The reaction is endothermic, so increasing the temperature will favour forward reaction. Due to increase in temperature heat will be absorbed by the reaction.

Application of Le-Chatelier’s Principle to Manufacture of Nitrogen dioxide:

The reaction is

2NO_(g) +  O_2(g)   ⇌  2 NO_2(g) +  116.4 kJ

2Vol  + 1 Vol        →       2 Vol

From this reaction it is clear that, the reaction is exothermic and accompanied by decrease in volume.

Effect of Concentration:

By the law of mass action; increase in concentration of one of the reactant will shift equilibrium towards right.  And here increase in concentration of nitrogen or oxygen increases the rate of forward reaction. Due to use of more number of moles, the increase in concentration of nitrogen oxide has a prominent effect.

Effect of Pressure:

Above reaction indicate that formation of nitrogen dioxide takes place with decrease in volume.  Hence increase in pressure favour forward reaction.

Effect of Temperature:

The reaction is exothermic, so decreasing the temperature will favour forward reaction. Due to the decrease in temperature heat will be removed from the reaction.

Application of Le-Chatelier’s Principle to Dissociation of Phosphorous Pentachloride:

The reaction is

PCL_5(g)   ⇌  PCl_3(g)  +  Cl_2(g)    –  62.8kJ

1Vol  → 1 Vol      +    1 Vol

From this reaction it is clear that, the reaction is endothermic and accompanied by increase in volume.

Effect of Concentration:

By the law of mass action; increase in concentration of one of the reactant will shift equilibrium towards right.  And here increase in concentration of phosphorous pentachloride increases the rate of forward reaction.

Effect of Pressure:

Above reaction indicate that formation of nitrogen dioxide takes place with increase in volume.  Hence decrease in pressure favour forward reaction.

Effect of temperature:

The reaction is endothermic, so increasing the temperature will favour forward reaction. Due to the increase in temperature heat will be absorbed by the reaction.

Applications of Le-Chatelier’s Principle to Physical Equilibria:

Melting of Ice:

The reaction is

_Ice(s)   ⇌  Water_(l)     –  6.01 kJ

more vol  → less vol

From this reaction, it is clear that the reaction is endothermic and accompanied by decrease in volume.

Effect of Pressure:

Above reaction indicate that formation of liquid water takes place with decrease in volume.  Hence increase in pressure favour forward reaction.

Effect of Temperature:

The reaction is endothermic, so increasing the temperature will favour forward reaction. Due to the increase in temperature heat will be absorbed by the reaction.

Boiling of Water:

The reaction is

_Water(l)   ⇌  Water vapours_(g)     –  40.84 kJ

less vol  → more vol

From this reaction, it is clear that the reaction is endothermic and accompanied by increase in volume.

Effect of Pressure:

Above reaction indicate that formation of liquid water takes place with increase in volume.  Hence increase in pressure favour forward reaction. (Principle of pressure cooker).

Effect of Temperature:

The reaction is endothermic, so increasing the temperature will favour forward reaction. Due to the increase in temperature heat will be absorbed by the reaction.

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In this article, we shall study Le-Chatelier’s principle with examples.

Statement:

This principle is given by, a French chemist Le-Chatelier in 1888. It states that “If an external stress is applied to a reacting system at equilibrium, the system will adjust itself in such a way that the effect of the stress is nullified”.

Explanation:

Let us consider a general reversible reaction.

A  +  B  ⇌   C + D

The equilibrium constant for the reaction is given by

If the concentration of any one reactant say A is increased then by Le-Chatelier’s Principle the forward reaction should be favoured so that the increase in the concentration of A is nullified. It can be explained as follows. As the concentration of reactant, A increases the denominator of mass equation increases. To keep the value of the equilibrium constant the same the value of K_c constant the numerator should increase. This is possible only if the concentration of C and D is increased. It is possible if more and more C and D are formed thus the reaction proceeds in the forward direction. i.e. forward reaction is favoured.

If the concentration of any one product, say C is increased then by Le-Chatelier’s Principle the backward reaction should be favoured so that the increase in the concentration of C is nullified. It can be explained as follows. As the concentration of product C increases the numerator of mass equation increases. To keep the value of K_c, the denominator should increase. This is possible only if the concentration of A and B is increased. It is possible if more and more A and B are formed thus the reaction proceeds in the backward direction. i.e. backward reaction is favoured.

Effect of the Change of Concentration on the chemical Equilibrium:

According to Le-Chatelier’s principle, when the concentration of one of the substance in a system in equilibrium is increased, then the equilibrium will shift so as to use up the substance added.

Explanation Using Le-Chatelier’s Principle:

Let us consider a general reversible reaction.

A  +  B   ⇌   C + D

The equilibrium constant for the reaction is given by

If the concentration of any one reactant say A is increased then by Le-Chatelier’s Principle the forward reaction should be favoured so that the increase in the concentration of A is nullified. It can be explained as follows. As the concentration of reactant, A increases the denominator of mass equation increases. To keep the value of the equilibrium constant the same the value of K_c constant the numerator should increase. This is possible only if the concentration of C and D is increased. It is possible if more and more C and D are formed thus the reaction proceeds in the forward direction. i.e. forward reaction is favoured.

If the concentration of any one product say C is increased then by Le-Chatelier’s Principle the backward reaction should be favoured so that the increase in the concentration of C is nullified. It can be explained as follows. As the concentration of product C increases the numerator of mass equation increases. To keep the value of K_c, the denominator should increase. This is possible only if the concentration of A and B is increased. It is possible if more and more A and B are formed thus the reaction proceeds in the backward direction. i.e. backward reaction is favoured.

The following graph shows the variation in concentration of the species on increasing the concentration of hydrogen in a reaction to produce ammonia from nitrogen and hydrogen.

Everyday Life Examples to Explain the Effect of the Change of Concentration on the Equilibrium:

Clothes dry quicker when there is a breeze.

Due to breeze or by shaking clothes in the air, the water vapours in the nearby air are removed or carried away. To establish the equilibrium the water from wet clothes starts evaporating. Thus they get dried fast.

On a humid day, we sweat more

Our body is losing water continuously by forming sweat. On a normal day, this sweat gets evaporated as soon as it is formed on the surface of the body. On a humid day the surrounding air contains a large amount of water vapours. Hence our body cannot lose water in the form of vapours. Thus the water remains on our body as sweat.

Transfer of oxygen by haemoglobin in the blood.

Haemoglobin is a protein present in red blood corpuscles which act as an oxygen carrier. The equilibrium is represented as

Hb_(s) +  O_2(g)  ⇌    HbO_2(s)

In lungs, there is an equilibrium of this reaction, when  HbO₂ (oxyhaemoglobin) reaches the site of tissues where the partial pressure is low. Now the equilibrium adjusts itself by shifting towards the right by releasing oxygen from oxyhaemoglobin. When the blood returns back to the lungs, where the partial pressure is higher, more oxyhaemoglobin is formed.

Removal of CO₂ from tissues

At the site of the tissues, the partial pressure of carbon dioxide is high. It dissolves into the blood and carried to lungs. In lungs partial pressure of carbon dioxide is low and it gets released from the blood.

Effect of the Pressure on the Chemical Equilibrium:

Change in pressure plays an important role in gaseous reactions.  The change of pressure has effect only on those equilibria which involves gaseous substances. There can be three types of gaseous reactions:

• Chemical reactions accompanied by an increase in volume
• Chemical reactions accompanied by a decrease in volume.
• Chemical reactions accompanied by no change in volume.

By Le-Chatelier’s principle, at a constant temperature, increase in pressure will favour a reaction which is accompanied by a decrease in volume and decrease in pressure will favour a reaction which is accompanied by the increase in volume.

Chemical reactions accompanied by an increase in volume:

Consider following reaction.

PCl_5(g)  ⇌ PCl_3(g)   +    Cl_2(g)

1 Vol             1 Vol           1 Vol

1 Vol             2 Vol

In this reaction, 1 volume of reactants gives 2 volumes of products.  Thus in this reaction volume is increased.

Chemical reactions involving gases and accompanied by an increase in volume are favoured by a reduction in pressure. Thus by decreasing the pressure at equilibrium, equilibrium is shifted towards the right.

Chemical reactions accompanied by a decrease in volume:

Consider following reaction.

N_2(g)  +   3H_2(g)   ⇌   2 NH_3(g)

1 Vol         3 Vol              2 Vol

4 Vol                2 Vol

In this reaction, 4 volumes of reactants give 2 volumes of products.  Thus in this reaction volume is decreased.

Chemical reactions involving gases and accompanied by a decrease in the volume are favoured by an increase in pressure. Thus by increasing the pressure at equilibrium, equilibrium is shifted towards the right.

Chemical reactions accompanied by no change in volume:

Consider following reaction.

H_2(g)    +   I_2(g) ⇌   2 HI_(g)

1 Vol          1 Vol          2 Vol

2 Vol              2 Vol

In this reaction, 2 volumes of reactants give 2 volumes of products.  Thus in this reaction volume is not changed.

Chemical reactions involving gases and accompanied by no change in volume are not affected by the change in pressure.

Effect of Temperature on the Chemical Equilibrium:

If the temperature of the exothermic chemical reaction is increased, then the concentration of products reduces and thus the equilibrium is shifted towards left.  Hence the reduction in temperature favours exothermic reaction at equilibrium. and increase in temperature favours endothermic reaction.

It is to be noted that in a reversible reaction if one reaction is exothermic then another reaction is endothermic. Thus the effect of change of temperature on the two reactions is different.

By Le-Chatelier’s principle. for an exothermic reaction at equilibrium lowering of temperature will favour the forward reaction And for an endothermic reaction, an increase in temperature will favour the forward reaction.

Effect of the Catalyst on the Chemical Equilibrium:

The catalyst is a substance which increases or decreases the rate of a reaction without taking part in the chemical reaction. In a reversible reaction at equilibrium, catalyst affects the rate of both forward reaction and backward reaction by the same extent.    Hence catalyst at equilibrium does not affect chemical equilibrium.

Effect of Inert Gas Addition:

If the volume is kept constant and an inert gas such as argon is added which does not take part in the reaction, the equilibrium remains undisturbed. It is due to the fact that the addition of an inert gas at constant volume does not change the partial pressure or the molar concentration of substances involved in the reaction. The change will take place if and only if the added gas is a reactant or product involved in the reaction.

Science > Chemistry > Chemical Equilibrium > Le-Chatelier’s Principle

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