Chemical Equilibrium
1. Introduction
Chemical equilibrium refers to the state in which the rate of the forward reaction is equal to
the rate of the reverse reaction in a chemical system.
At equilibrium:
o The concentrations of reactants and products remain constant over time.
o There is no net change in the system, though the reactions continue to occur
dynamically.
Dynamic Nature of Equilibrium
Even at equilibrium, the reactions do not stop.
The rate of conversion of reactants to products (forward reaction) equals the rate of
conversion of products back to reactants (reverse reaction).
2. Types of Equilibrium
(i) Physical Equilibrium
Occurs in physical processes like phase changes or dissolution processes.
Example Processes:
o Solid-Liquid: When ice melts to water at 0°C, the rate of melting equals the rate of
freezing.
o Liquid-Gas: At equilibrium, the rate of evaporation equals the rate of condensation
in a closed container.
o Solid-Solution: Saturated solutions achieve equilibrium between dissolved solute
and undissolved solute.
(ii) Chemical Equilibrium
Occurs in chemical reactions where both the forward and reverse reactions occur.
Features:
o Requires a closed system.
o Concentrations of reactants and products remain constant but are not necessarily
equal.
3. Law of Mass Action
Proposed by Guldberg and Waage in 1864.
Statement: The rate of a chemical reaction is directly proportional to the product of the
active masses of the reactants, each raised to the power of their stoichiometric coefficients
in the balanced chemical equation.
Expression
For a general reaction:
The equilibrium constant Kc is expressed as:
Where:
[X] Molar concentration of species X.
a,b,c,d: Stoichiometric coefficients of reactants and products.
Significance of Kc
If Kc≫1: The reaction favors products, meaning equilibrium lies far to the right.
If Kc≪1: The reaction favors reactants, meaning equilibrium lies far to the left.
4. Factors Affecting Equilibrium
(i) Concentration Changes
Increasing the concentration of reactants shifts equilibrium toward products.
Increasing the concentration of products shifts equilibrium toward reactants.
(ii) Pressure Changes (Gaseous Systems)
Increasing pressure shifts equilibrium toward the side with fewer gas molecules.
Decreasing pressure shifts equilibrium toward the side with more gas molecules.
(iii) Temperature Changes
For exothermic reactions (ΔH<0):
o Increasing temperature shifts equilibrium toward reactants.
o Decreasing temperature shifts equilibrium toward products.
For endothermic reactions (ΔH>0):
o Increasing temperature shifts equilibrium toward products.
o Decreasing temperature shifts equilibrium toward reactants.
(iv) Addition of Inert Gas
At constant volume: No effect on equilibrium as partial pressures of reactants and products
remain unchanged.
At constant pressure: Total volume increases, reducing the partial pressures of gases and
shifting equilibrium depending on Δn (change in the number of moles of gas).
(v) Catalyst Addition
A catalyst speeds up the attainment of equilibrium by equally increasing the rates of
forward and reverse reactions.
It does not affect the equilibrium position or Kc.
5. Relation Between Kp and Kc
Kp: Equilibrium constant in terms of partial pressures.
Kc: Equilibrium constant in terms of molar concentrations.
For gaseous reactions:
Where:
R: Universal gas constant
T: Temperature in Kelvin
Δn: Change in the number of moles of gas (moles of products - moles of reactants).
6. Gibbs Free Energy and Equilibrium
Gibbs free energy change (ΔG) determines the spontaneity of a reaction.
At equilibrium: ΔG=0.
Relation between ΔG∘ (standard Gibbs energy) and K:
Where:
K: Equilibrium constant.
R: Universal gas constant.
T: Temperature in Kelvin.
Implications:
If K>1: ΔG∘<0, the reaction is spontaneous in the forward direction.
If K<1: ΔG∘>0, the reaction is non-spontaneous in the forward direction.
7. Ionic Equilibrium
Ionic equilibrium involves substances that dissolve or dissociate into ions in a solution.
Electrolytes: Substances that conduct electricity due to ion formation in solution.
o Strong Electrolytes: Completely dissociate (e.g., HCl, NaCl).
o Weak Electrolytes: Partially dissociate (e.g., CH3COOH, NH4OH).
Dissociation Constant for Weak Electrolytes
9. Points to Remember
At equilibrium, ΔG=0.
A larger Kc or Kp value indicates the reaction favors products.
Changes in external conditions shift equilibrium according to Le Chatelier’s principle.
Catalysts speed up the attainment of equilibrium but do not affect the equilibrium constant.
Kp and Kc are temperature-dependent but not affected by concentration, pressure, or
catalysts.
