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Equilibria (Equilibrium)
Course Content:

 Introduction, reversible and irreversible process, equilibrium involving in

physical change.
 Homogeneous and heterogeneous equilibrium.
 Chemical equilibrium, dynamic nature of chemical equilibrium and its
characteristics.
 Law of mass action, equilibrium constant and its characteristics.
 Relation between Kp and Kc.
 Le-Chatelier’s principle and its application.

Introduction

In a reversible process conversion of reactant into product as well as product into reactant
take place at the same time. In such process there is existence of equilibrium state.
Equilibrium is a state in a reversible process at which measurable properties of a system
do not change with time. When equilibrium is involved in physical change then it is called
physical equilibrium. When equilibrium is involved in chemical change then it is called
chemical equilibrium.

Reversible and Irreversible Reactions

The chemical reactions in which reactants react to give products and these products react to
give back the original reactants are called reversible reactions. In such reactions forward
and backward reactions occur simultaneously. These reactions do not proceed to
completion. Some examples of reversible reactions are:

N2 (g) + 3H2 (g) 2NH3 (g)

H2 (g) + I2 (g) 2HI (g)

CaCO3 (s) CaO (s) + CO2 (g)

The chemical reactions in which the products formed as a result of forward reaction do not
react under any given set of conditions to give back the original reactants are called
irreversible reactions. Such reactions proceed to only one direction. This type of reaction
proceeds to almost completion. Some examples of irreversible reactions are:

NaOH + HCl NaCl + H2O

AgNO3 (aq) + NaCl (aq) AgCl (s) + NaNO3 (aq)

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Physical Equilibrium

1. Solid-liquid equilibrium
The equilibrium exists between solid and liquid at its melting point is called solid-
liquid equilibrium. When ice and water is kept at 0oC and 1 atm pressure then the
amount of both remains constant for long time and it is said to be in equilibrium.
Ice Water
2. Solid-vapour equilibrium
When the rate of conversion of solid into vapour and rate of condensation of vapour
back to solid are equal then the system is said to be in solid-vapour equilibrium.
I2 (s) I2 (g)
3. Liquid-vapour equilibrium
When the rate of conversion of liquid into vapour and rate of condensation of
vapour back to liquid are equal then the system is said to be in liquid-vapour
equilibrium.
Water (l) Water (g)

Concept of Chemical Equilibrium

Chemical equilibrium is defined as a state of reversible reaction when the two opposing
reactions occur at same rate and concentrations of reactants and products do not change
with time.

In a reversible reaction, the reaction proceeds toward the formation of products during
initial stage. As soon as some products are formed, the reverse process begins to take place
and reactants are produced back from the products. When forward and backward reactions
take place with equal speed then the system is said to be in chemical equilibrium.
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Chemical equilibrium is dynamic in nature rather than static. Even at equilibrium state
reaction is not stopped.

Characteristics of Chemical Equilibrium

1. Chemical equilibrium is dynamic in nature. At equilibrium, rate of forward

reaction is equal to the rate of backward reaction.
2. When chemical equilibrium is attained then the concentration of reactants and
products remains constant.
3. Chemical equilibrium cannot be attained in open vessel as gaseous reactants and
products may escape.
4. A catalyst does not change the position of equilibrium but it helps to attain
equilibrium fast. It is because the catalyst changes the rate of forward and
backward reaction to the same extent.
5. Chemical equilibrium can be initiated from either side of reaction.
6. A chemical equilibrium is characterized by a constant called equilibrium constant
‘K’.

Homogeneous and Heterogeneous Equilibrium

On the basis of phases (i.e. states) of chemical species present as reactants and products in
a chemical reaction the equilibrium is classified into two types.

(a) Homogeneous equilibrium: When all reactants and products of a chemical

equilibrium are present in same phase then equilibrium is called homogeneous.
Examples:
N2 (g) + 3H2 (g) 2NH3 (g)
PCl5(g) PCl3(g) + Cl2(g)
(b) Heterogeneous equilibrium: When reactants and products of a chemical equilibrium
are present in different phase then equilibrium is called heterogeneous equilibrium.
Examples:
CaCO3(s) CaO(s) + CO2(g)
NH4HS(s) NH3(g) + H2S(g)

1. Write the differences between reversible and irreversible reactions.

2. Justify that equilibrium state is dynamic rather than static.
3. Define physical equilibrium and chemical equilibrium with suitable example.
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Law of Mass Action

The effect of concentration on the rate of reaction was studied by two Norwegian chemists
Guldberg and Waage in 1867 and gave the result in the form of law called Law of mass
action.

The law states that the rate at which chemical substance reacts is directly proportional to
its molar concentration (active mass) and the rate of a chemical reaction is directly
proportional to the product of molar concentration of reacting substances where each
concentration term raised to the power equal to stoichiometric coefficients present in the
balanced chemical equation.

Consider a reaction,

A Products

According to law of mass action, rate of reaction α [A]

Similarly for a reaction,

2A Products

Rate of reaction α [A]2

Similarly for a reaction,

A+B Products

Rate of reaction α [A][B]

For a general reaction,

aA + bB Products

Rate of reaction α [A]a [B]b

Where, [A] = molar concentration of A (active mass of A)

[B] = molar concentration of B (active mass of B)

Law of mass action and equilibrium constant

Let us consider a general reversible reaction,

aA + bB cC + dD

Here a, b, c and d are coefficients of chemical species A, B, C and D respectively.

Applying law of mass action,

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Rate of forward reaction (Rf) α [A]a[B]b

or, Rf = Kf[A]a[B]b . . . . . . . . . . . . . . (i)

Where, [A] and [B] are molar concentration (active mass) of A and B respectively.

Kf = rate constant (velocity constant) for forward raction.

Similarly, rate of backward reaction (Rb) α [C]c[D]d

or, Rb = Kb[C]c[D]d . . . . . . . . . . . . . . (ii)

Where, [C] and [D] are molar concentration (active mass) of C and D respectively.

Kb = rate constant (velocity constant) for backward raction.

At equilibrium state,

Rate of forward reaction(Rf) = Rate of backward reaction(Rb)

or, Kf[A]a[B]b = Kb[C]c[D]d [from eq.(i) and (ii)]

Kf [C]c [D]d
or, =
Kb [A]a [B]b

[C]c [D]d
or, Keq = . . . . . . . . . . . . . . (iii)
[A]a [B]b

Where, Keq = Constant called equilibrium constant which is ratio of velocity constant of
forward reaction to that of backward reaction.

When equilibrium constant is expressed in terms of concentration then Keq is represented as

Kc. So, equation (iii) can also be written as,

[C]c [D]d
Kc = . . . . . . . . . . . . . . (iv)
[A]a [B]b

Where, Kc = Equilibrium constant in terms of concentration of chemical species.

Equilibrium constant is defined as the ratio of product of molar concentration of products

to the product of molar concentration reactants where each concentration term raised to
the power equal to stoichiometric coefficients present in the balanced chemical equation.