UNIT

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

1 | Page © Jay Prakash Paudel / Department of Chemistry ||

Physical Equilibrium:
Some physical processes also are reversible processes.

(A) Liquid-vapor equilibrium:

Let’s consider water is taken in closed vessel undergoing evaporation into vapor and condensation into liquid at constant
temperature.
H2O (l) ⇌ H2O (g)
When the rate of evaporation of water becomes equal to the rate of condensation, the system is said to be in equilibrium.
The equilibrium existing between the liquid and vapor phases is termed as liquid-vapor equilibrium.

(B) Solid - liquid equilibrium:

Let’s consider ice at 0oC and one atmospheric pressure in an insulated vessel.
H2O (s) ⇌ H2O (l)
When the rate of melting of ice becomes equal to the rate of freezing, equilibrium is reached. The equilibrium existing
between the solid and liquid phases at freezing or melting point is termed as solid – liquid equilibrium.

(C) Solid - solution equilibrium:

Let’s consider sugar is dissolved in water to make saturated solution.
Sugar (solid) ⇌ Sugar (solution )
When the rate of dissolution becomes equal to rate of precipitation, equilibrium is reached. Where the concentration of
the solution remains constant. The equilibrium existing between solid and solution is termed as solid – solution
equilibrium.

Concept of chemical equilibrium:

In a reversible reaction, the rate of forward reaction is being gradually decreased due to the decreased concentration of
reactants with time. Initially the concentration of product is zero and the forward reaction proceeds, concentration of
products is increased. These products react to give back the reactants. When concentration of products goes on increasing
the rate of backward reaction goes on increasing. During this process, a state will come when the rate of forward reaction
is equals to rate of backward reaction which is called equilibrium. Thus the chemical equilibrium is defined as the state
of reversible reaction at which the rate of forward reaction becomes equal to rate of backward reaction.
At equilibrium state, concentration of reactants and products do not change with time and reaction seems to be stopped
but actually that is not so. The cause behind this is due to the equal rate of forward and backward reaction. Due to this
chemical equilibrium is dynamic in nature rather than static.

Forward reaction
Rate of reaction

Dynamic equilibrium

Backward reaction

Time
Fig: Reversible reaction and state of equilibrium

2 | Page © Jay Prakash Paudel / Department of Chemistry ||

Homogeneous and Heterogeneous equilibrium:
Homogeneous equilibrium:
When all reactants and products of a chemical equilibrium are present in the same phases (states), then such type of
equilibrium is called homogeneous equilibrium.
Examples:
N2 (g) + O2 (g) ⇌ 2NO(g)
H2(g) + Cl2(g) ⇌ 2HCl(g)

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)

Characteristics of chemical equilibrium:

1. Chemical equilibrium is dynamic in nature. At equilibrium, the rate of forward reaction is rate of back ward
reaction.
2. Concentration of each of reactants and products remains constant at equilibrium condition.
3. The equilibrium condition can be attained from either direction.
4. A catalyst helps to attain equilibrium fast but it has no effect on the state of equilibrium.

Law of mass action:

Rate of chemical reaction is affected by concentration of reacting species. This facts was studied by two Norwegian
chemists C.M. Guldberg and P. Waage in 1867 and gave a quantitative relationship between rate of reaction and
concentration of reacting species, which is known as law of mass action.
It states that, “ the rate at which the substance reacts is directly proportional to its molar concentration (active mass)
and the rate of chemical reaction is directly proportional to the products of molar concentrations (active masses) of
reacting species where each concentration terms raised to the powers equal to stoichiometric coefficients present in
the balanced chemical equation.”
The term molar concentration or active mass of a substance is the number of moles of the substance dissolved in per
liter of its solution. It is represented by enclosing the symbols or formulae of the substance in square brackets.

No of moles
Active mass or Molar concentration =
Volume of solution in liter

For example Active mass of A is represented as [A] or CA.

Let us consider a general reversible reaction,

aA + bB ⇌ cC + dD
Where, a, b, c and d are stoichiometric coefficient of chemical species A, B, C and D, respectively.

According to law of mass action,

Rate of forward reaction α [A]a [B]b
Rf α [A]a [B]b
Rf = Kf [A]a [B]b ………………… (i)
Where Kf is the rate constant for the forward reaction and [A] and [B] are active mass or molar concentrations of
reactants A and B respectively.

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.

3 | Page © Jay Prakash Paudel / Department of Chemistry ||

At equilibrium,
Rate of forward reaction = Rate of backward reaction
Kf [A]a [B]b = Kb [C]c [D]d
Kf [C]c [D]d
=
Kb [A]a [B]b

[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.

Equilibrium constant in terms of partial pressure:

Partial pressure of the gaseous substance is directly proportional to its molar concentration or active mass, which can be
shown as,
From ideal gas equation,
PV = nRT
n
P = RT
V

Where, P is partial pressure

V is volume in liter
n is number of moles
R is universal gas constant
T is absolute temperature

n
P = CRT Where, C = , Molar concentration or active mass
V
i. e. PA = CA RT = [A] RT
PA α [A]

Let us consider a general reversible reaction,

aA + bB ⇌ cC + dD

The equilibrium constant in terms of partial pressure is represented by KP.

[PC ]c [PD ]d
KP = [PA ]a [PB ]b
… … … … … … … … .. (ii)
Where, PA, PB, PC and PD are partial pressures of A, B, C and D respectively

Characteristics of equilibrium constant:

The characteristics of equilibrium constants are as follows:
1. Equilibrium constant is fixed for a particular reaction at a particular temperature.
2. It does not depend upon the concentration of reactants and products.
3. It is independent of the presence of catalyst.
4. It depends upon the temperature. For exothermic reaction, it is inversely proportional to the temperature and for
endothermic reaction, it is directly proportional to the temperature.

Significance of equilibrium constant:

If the value of equilibrium constant is high ( KC > 1) , it shows that higher the concentration of products than reactants
i.e. rate of forward reaction is higher than rate of backward reaction.
If the value of equilibrium constant is low ( KC < 1 ), it shows that higher the concentration of reactants than products
i.e. rate of backward reaction is higher than rate of forward reaction.

4 | Page © Jay Prakash Paudel / Department of Chemistry ||

Equilibrium expression of some reactions:
While writing equilibrium expressions certain conventions are used.
1. If solid is involved in the equilibrium, its concentration remains constant. Therefore by convention, the
concentration of active mass of all solids are taken as unity, i.e. [Solid] = 1
2. If pure liquid is in equilibrium with some gases, the concentration of pure liquid is taken as unity, i.e. [Pure
liquid] = 1

Relationship between KC and KP :

Let us consider a general reversible reaction,
aA + bB ⇌ cC + dD

Equilibrium constant in terms of concentration or active mass can be written as

[C]c [D]d
KC = … … … … … … … … (i)
[A]a [B]b
Where, [A], [B], [C] and [D] are active masses of A, B, C and D respectively
And ,
the equilibrium constant in terms of partial pressure can be written as,
[PC ]c [PD ]d
KP = … … … … … … … … .. (ii)
[PA ]a [PB ]b
Where, PA, PB, PC and PD are partial pressures of A, B, C and D respectively

From ideal gas equation,

PV = nRT
n
P = RT
V
n
P = CRT Where, C = , Molar concentration or active mass
V
i. e. PA = CA RT = [A] RT
Similarly, PB = [B] RT, PC = [C] RT and PD = [D] RT
Substituting these values in equation (ii),
[C]c (RT)𝑐 [D]d (RT)𝑑
KP =
[A]a (RT)𝑎 [B]b (RT)𝑏

[C]c [D]d (RT)c+d

KP =
[A]a [B]b (RT)a+b

[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

5 | Page © Jay Prakash Paudel / Department of Chemistry ||

Le - Chatelier’s Principle:
A French chemist Le-Chatelier, in 1884, studied the effect of concentration, pressure and temperature on the state of
equilibrium. Le-Chatelier principle states that, “If a system in equilibrium is subjected to change in concentration,
pressure or temperature then the equilibrium shifts in such a way so as to nullify the effect of the change.”
The important conclusions of the principle can be expressed as:

Effect of change in concentration:

On increasing concentration, the equilibrium shifts to the direction where the increased concentration is consumed

Effect of change in pressure:

On increasing pressure, the equilibrium shifts to the direction where volume or number of mole is decreased.

Effect of change in temperature:

On increasing temperature, the equilibrium shifts to the direction where heat is absorbed

Application of Le-Chateliers Principle:

Formation of ammonia from hydrogen and nitrogen:
3H2(g) + N2(g) ⇌ 2NH3(g) , ΔH = -92.5K J

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)]

6 | Page © Jay Prakash Paudel / Department of Chemistry ||

Question: Write down the relationship between KP and KC for the following reaction.
(i) PCl5(g) ⇌ PCl3 (g) + Cl2(g)
(ii) 3H2(g) + N2(g) ⇌ 2NH3(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

(ii) For the reaction, 3H2(g) + N2(g) ⇌ 2NH3(g)

Δn = No of moles of products – no of moles of reactants
Δn = 2- 4 = -2
Then, KP = KC (RT) -2
KP = KC (RT) -2

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.

7 | Page © Jay Prakash Paudel / Department of Chemistry ||