CHEMICAL

EQUILIBRIUM
 Chemical Equilibrium
• In a chemical reaction, chemical equilibrium is the
state in which both reactants and products are present in
concentrations which have no further tendency to
change with time. The chemical equilibrium is
achieved when the rate of forward reaction is same as
the reverse reaction.
• A chemical reaction is in equilibrium when the
concentrations of reactants and products are constant.
Another way of defining equilibrium is to say that a
system is in equilibrium when the forward and reverse
reactions occur at equal rates.
The entire process can be graphically represented by this diagram.
 Types of Chemical Equilibria

• Homogeneous equilibria

• Heterogeneous equilibria
 Homogeneous Equilibria

• The equilibrium reactions in which all

the reactants and the products are in
the same phase are known as homogeneous
equilibrium reactions. These are divided into
two categories:
– The number of product molecules is equal to the
number of reactant molecules. For example:
• N (g) + O (g) ⇌ 2NO (g)
2 2

• H (g) I ⇌ 2HI (g)

2 2
 – The number of product molecules is not equal to
the number of reactant molecules.
• COCl (g) ⇌ CO (g) + Cl (g)
2 2

• 2SO (g) + O (g) ⇌ 2SO (g)

2 2 3

• In gaseous phase,
• In solution phase, the equilibrium
constant for the homogeneous
reaction in gaseous systems:
• Ideal gas equation is given by, pV = nRT
If concentration C is in mol L−1 or mol
dm−3 and p is in bar, then we can
write p = c RTOr, p = [gas] RT .
• (i)Where R = 0.0831 bar L mol−1 K−1For a
general reaction,
• In the above equation,
– Δn = (number of moles of gaseous products)−
(number of moles of gaseous reactants) in the
balanced chemical equation
– While calculating K , pressure should be expressed
p

in bar.
– 1 bar = 10 Pa = 10 Nm
5 5 −2
 Heterogeneous Equilibria
• The equilibrium reactions in which the
reactants and the products are present in
different phases are known as Heterogeneous
equilibrium reactions. For Example:
• The dissociation of solid calcium carbonate to
give solid calcium oxide and gaseous carbon
dioxide:
 – Here as CaO and CaCO are pure solids, [CaO] and
3

[CaCO ] are constants.

3

So,
• The concentrations of pure solids & pure
liquids assumed to be constant and these do
not appear in equilibrium concentration
expression. By convention [solid] = 1 and
[liquid] = 1
 Factors Affecting Chemical
Equilibrium
• Concentration Change
Concentration stress of an added reactant/
product is relieved by the net reaction in the
direction that consumes the added substance.
Concentration stress of a removed
reactant/product is relieved by the net reaction
in the direction that replenishes the removed
substance.
 Pressure Change
• In case of solids and liquids, the effect of
pressure change is neglected (because the
volume of solid or liquid is independent of
pressure).If the pressure is increased, then the
equilibrium shifts in the direction in which the
number of moles of gas or pressure
decreases
 Change in Temperature
• Change in the equilibrium constant with
temperature depends upon the sign of ΔH for
the reaction. For exothermic reaction
(negative ΔH), the equilibrium constant
decreases (Backward Shift) with the increase
in temperature. For endothermic reaction
(positive ΔH), the equilibrium constant
increases (Forward Shift) with the increase in
temperature.