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Equilibria
Equilibria
9
EQUILIBRIA
NEB Syllabus:
Introduction
Equilibrium involving in physical change
Chemical equilibrium
Reversible and irreversible reactions
Dynamic nature of chemical equilibrium and its characteristics
Law of mass action
Equilibrium constant ( KC) and its characteristics
Homogeneous and heterogeneous equilibrium
Relation between KP and KC (Derivation )
Le-chatelier’s principle and its application
Introduction:
In a chemical reaction, chemical equilibrium is the state in which both reactants and products are present in constant
concentrations which have no further tendency to change with time, so that there is no observable change in the
properties of the system.
Forward reaction:
The reaction having the direction from reactants to products side is called forward reaction.
Backward reaction:
The reaction having the direction from products to reactants side is called backward reaction.
Reversible reaction:
The chemical reaction in which the reactants react to form products while the products also recombine to form the
reactants is called reversible reaction. Reversible reaction is denoted by double headed arrow (⇌ ) which is placed
between the reactants and products.
For examples,
3H2 + N2 ⇌ 2NH3 H2 + I2 ⇌ 2HI
2SO2 + O2 ⇌ 2SO3 N2O4 ⇌ 2NO2
Irreversible reaction:
The chemical reaction in which the reactants react to form products but products do not react to form reactants is called
irreversible reaction. Irreversible reaction is denoted by single headed arrow ( ) which is placed between reactants
and products.
For examples,
2KClO3 2KCl + 3O2 2Mg + O2 2MgO
Zn + H2SO4 ZnSO4 + H2 NaCl + AgNO3 AgCl + NaNO3
Forward reaction
Rate of reaction
Dynamic equilibrium
Backward reaction
Time
Fig: Reversible reaction and state of equilibrium
Heterogeneous equilibrium:
When the participating chemical species of a chemical equilibrium exists in different phases ( states ), then such type of
equilibrium is called heterogeneous equilibrium.
Example:
CaCO3(s) ⇌ CaO(s) + CO2(g)
No of moles
Active mass or Molar concentration =
Volume of solution in liter
Similarly,
Rate of backward reaction α [C]c [D]d
Rf α [C]c [D]d
Rf = Kb [C]c [D]d ………………….. (ii)
Where Kb is the rate constant for the backward reaction and [C] and [D] are active mass or molar concentrations of
products C and D respectively.
[C]c [D]d
KC =
[A]a [B]b
Where, KC is equilibrium constant and is the ratio of rate constant for forward reaction to rate constant of backward
reaction.
The equilibrium constant is defined as the ratio of product of the active masses of the products to products of active
masses of reactants when each concentration term is raised to a power equal to the stoichiometric coefficient of the
substance in the balanced chemical equation.
n
P = CRT Where, C = , Molar concentration or active mass
V
i. e. PA = CA RT = [A] RT
PA α [A]
[C]c [D]d
KP = × (RT)(c+d)−(a+b)
[A]a [B]b
KP = KC (RT)Δn
Where, Δn = (c + d) – (a + b)
= difference between total numbers of moles of the products and the total number of moles of reactants
When Δn = 0 , KP = KC
Effect of concentration:
According to the Le-Chatelier’s principle, On increasing concentration, the equilibrium shifts to the direction where the
increased concentration is consumed. In this reaction, an increase in concentration of reactants ( H 2 and N2 ) the
equilibrium shift in the forward direction. And vice versa.
Effect of pressure:
According to the Le-Chatelier’s principle, On increasing pressure, the equilibrium shifts to the direction where volume
or number of mole is decreased. In this reaction, 4 moles of reactants ( 3 moles of hydrogen and 1 mole of nitrogen )
combine to give 2 moles of products ( 2 moles of ammonia ). The number of moles are decreases from reactant to
product side, so increase in pressure the equilibrium shifts to the forward direction.
Effect of Temperature:
According to Le-Chatelier’s principle, On increasing temperature, the equilibrium shifts to the direction where heat is
absorbed. The above reaction is exothermic in forward direction and endothermic in backward direction. On increasing
the temperature, the equilibrium shifts to the backward side and vice versa.
Question: Define equilibrium constant. Write the expression of equilibrium constant ( KC ) for the following reaction:
CaCO3(s) ⇌ CaO(s) + CO2(g)
Ans: For a reversible reaction, the ratio of product of the active masses of the products to the product of the active
masses of the reactants when each concentration term is raised to the power equal to the corresponding stoichiometric
coefficient in the balanced chemical equation is called equilibrium constant.
The equilibrium constant (KC) for the above reaction can be expressed as,
[CaO(s)][CO2 (g)]
KC =
[CaCO3 (s)]
Since, CaO(s) and CaCO3(s) are solids, therefore their active mass taken as unity i.e. 1
1 × [CO2 (g)]
KC =
1
KC = [CO2(g)]
Ans:
(i) For the reaction, PCl5(g) ⇌ PCl3 (g) + Cl2(g)
Δn = No of moles of products – no of moles of reactants
Δn = 2-1 = 1
Then, KP = KC (RT)1
KP = KC RT
Question: How do increase in temperature and pressure affect the equilibrium of the following reaction?
2SO2(g) + O2(g) ⇌ 2SO3(g) + heat
Ans:
Effect of increase in temperature:
Since the reaction is exothermic in forward direction, According to Le-Chatelier’s principle increase in temperature
shifts the equilibrium in backward direction.
Effect of increase in pressure:
In above reaction no of moles of species decreases in product side, According to Le-Chatelier’s principle increase in
pressure shifts the equilibrium in forward direction.
Question: What happens when pressure is increased in the following equilibrium reactions?
(i) N2O4(g) ⇌ 2NO2(g)
(ii) H2 (g) + I2 (g) ⇌ 2HI (g)
Ans: (i) The given reaction is N2O4(g) ⇌ 2NO2(g)
No of moles of species increases in forward direction, According to Le-Chatelier’s principle increase in pressure shifts
the equilibrium in backward direction.
(ii) The given reaction is H2 (g) + I2 (g) ⇌ 2HI (g)
No of moles of species are equal in both side, According to Le-Chatelier’s principle increase in pressure does not shifts
the equilibrium in any direction.