Chemical Equilibrium
Equilibrium State
Under given set of conditions if a reversible process or chemical reaction is carried out in a
closed container, a constancy in some observable properties like colour intensity, pressure,
density, is observed. Such a state is referred to as an equilibrium state.
Equilibrium may be classified as follows.
Physical Equilibrium
Equilibrium set up in physical processes like evaporation of water, melting of solids,
dissolution of solutes, etc., is called physical equilibrium, e.g.,
At equilibrium,
Rate of melting of ice = Rate of freezing of water
Chemical Equilibrium
If a reversible reaction is carried out in a closed vessel, a stage is attained where the speed
of the forward reaction equals the speed of the backward reaction. It corresponds to
chemical equilibrium. At equilibrium,
Rate of forward reaction = Rate of backward reaction
Characteristics of Chemical Equilibrium
1. Equilibrium can be attained from either side.
2. Equilibrium is dynamic in nature, i.e., at equilibrium reaction does not stop.
3. At equilibrium, there is no change in the concentration of various species.
4. The equilibrium state remains unaffected by the presence of catalyst. Catalyst helps to
attain the equilibrium state rapidly.
6. The observable physical properties of the process become constant.
Law of Mass Action
The rate of a chemical reaction is directly proportional to the product of the active masses
of the reacting substances.
where, kf and kb are rate constants.
In heterogeneous equilibrium, the active mass of pure solids and liquids are taken as
At equilibrium, Rf = Rb
1
Rate of forward reaction = Rate of backward reaction
Kc is called the equilibrium constant.
Use of Partial Pressures Instead of Concentration
For gaseous reactions, partial pressures are conveniently used since at any fixed
temperature partial pressure is directly proportional to concentration. For a general gaseous
reaction,
Relation between Kc and Kc
where, Δng = moles of products – moles of reactants (gaseous only)
Relation between Kc and Kp for different types of reactions
(i) When Δng = 0, Kp = Kc
(ii) When Δng = +ve, Kp > Kc
(iii) When Δng = -ve, Kp < Kc
Units of Kp and Kc
(i) Unit of Kp = (atm)Δn
(ii) Unit of Kc = (mol L-1)Δn
Types of Equilibrium
Homogeneous Equilibrium
In homogeneous equilibrium, the reactants and products are present in the same phase or
2SO2(g) + O2(g) ⇔ 2SO3(g)
physical suite (gaseous or liquid).
Heterogeneous Equilibrium
In heterogeneous equilibrium the reactants and products are present in two or more
3Fe(s) + 4H2O(g) ⇔ Fe3O4(s) + 4H2(g)
physical states or phases.
Reaction Quotient
For any reversible reaction at any stage other than equilibrium, the ratio of the molar
concentrations of the products to that of the reactants. where each concentration term is
raised to the power equal to the stoichiometric coefficient to the substance concerned, is
called the reaction quotient, Qc.
aA + bB ⇔ cC + dD
For a general reaction
2
which is not at equilibrium,
Qc = [C]c + [D]d / [A]a [B]b
If
(i) Qc > Kc, the value of Qc will tend to decrease to reach the value of Kc (towards equilibrium)
and the reaction will proceed in the reverse direction.
(ii) Qc < Kc it will lend to increase and the reaction will proceed in the forward direction.
(ii) Qc = Kc, the reaction is at equilibrium.
Le – Chatelier’s Principle
If a system at equilibrium is subjected to a change in concentration, pressure or
temperature, the system adjusts itself to undo the effect of changes imposed on it.
Effect of Change of Concentration
If at equilibrium the concentration of one of the reactants is increased, the equilibrium will
shift in the forward direction and vice-versa.
Effect of Change in Pressure
N2 + O2 ⇔ 2NO.
No effect of pressure on equilibria having same moles of reactants and products. e.g.,
When there is change in the number of moles, the equilibrium will shift in the direction
having smaller number of moles when the pressure is increased and vice-versa, e.g.,
N2 + 3H2 ⇔ 2NH3 [High p. high yield of NH3]
Effect of Temperature
When process is exothermic, low temperature favours the forward reaction. When process
is endothermic, high temperature favours the formation of products.
Effect of Addition of Inert Gas
(i) Addition of inert gas at constant pressure at constant pressure. if an inert gas is added, it
will increase the volume of the system. Therefore, the equilibrium will shift in a direction in
which there is an increase in the number of moles of gases.
(ii) Addition of inert gas at constant volume If keeping volume of the system constant, an
inert gas is added, the relative molar concentration of the substance will not change. Hence.
the equilibrium position of the reaction remains unaffected.
Effect of Catalyst
The presence of catalyst does not change the position of equilibrium. It simply fastens the
attainment of equilibrium.
