Equilibrium (Part I)

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EQUILIBRIUM (PART I)

Equilibrium represents a state in a process when the observable properties such as colour, temperature,
pressure, concentration etc do not show any change with time.

The word equilibrium means ‘balance’ which indicates that a chemical reaction represents a balance between
the reactants and products taking part in the reaction. The equilibrium state is also noticed in certain physical
processes such as the melting point of ice at 0℃, both ice and water are present at equilibrium.

Equilibrium

Physical Chemical

Physical Equilibrium

 Equilibrium involved in phase transformations


(i) Solid ⇌ Liquid equilibrium

eg. H2O(s) ⇌ H2O(l)

Rate of melting of ice = Rate of freezing of water at 273K and 1 atm pressure.

The above equilibrium state is represented by the relative amount of ice and water remains
constant over time.

(ii) Liquid ⇌ Gas equilibrium

eg. H2O(l) ⇌ H2O(g)

Rate of vapourisation of water = Rate of condensation of water vapour at a constant temperature


under atmospheric pressure.

 Vapour pressure is defined as the pressure exerted by the vapour on the surface of a liquid at a
particular temperature when the liquid is in equilibrium with its vapour.

 The vapour pressure increases with the rise of temperature.

 The temperature at which the vapour pressure of a liquid becomes equal to that of the
atmospheric pressure is defined as the boiling point of the liquid.

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(iii) Solid ⇌ Gas equilibrium

eg. I2(solid) ⇌ I2(vapour)

The above equilibrium state is identified by a fixed intensity of purple colour of iodine vapour.

Rate of sublimation = Rate of desublimation at a constant temperature under atmospheric pressure.

 Equilibrium involved in dissolution of solids or gases in liquids

Solids in liquids:

In a saturated solution, a dynamic equilibrium exists between solute molecules in the solid-state
and in the solution at a given temperature. The increase in temperature increases the solubility of
the solution i.e. solubility depends on temperature.

Sugar (solution) ⇌ sugar (solid)

Rate of dissolution of sugar = Rate of crystallisation of sugar.

Gases in Liquids:
The relation between the quantity of gas dissolved in a solution and the pressure of the gas over the
solution can be given by Henry’s Law. This law states that the mass of a gas dissolved in the
given amount of solvent at any temperature is proportional to the pressure of the gas above the
solvent.

 The solubility of gases increases with an increase in pressure.

 We hear a hissing sound when we open a soda water bottle or a bottle containing aerated
drink as the dissolved CO2 gas escapes out.

 The solubility of gases increases with a decrease in temperature.

 We notice that the gas fizzing out from the cold drink at room temperature is more than the
drink that is refrigerated.
 Boiled water tastes flat due to the release of the dissolved gases from water at higher
temperature.

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Chemical Equilibrium

In a chemical reaction, chemical equilibrium is defined as the state at which there is no further change in
concentration/mass/no. of moles/volume of reactants and products takes place.

Characteristics of Equilibrium
 Achieved in a reversible process carried out in a closed system.
 Dynamic in nature.
 Observable properties of the system remain constant with time.
 The forward and the backward process take place at the same rate.
 Can be attained from either end of a reversible process.
 Magnitude of the properties of the system at equilibrium indicates the extent to which a process has taken
place before achieving equilibrium.

Graphical representation of the state of equilibrium

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Chemical Equilibrium

Homogeneous Heterogeneous

Homogeneous Equilibrium - In this type, the reactants and the products of chemical equilibrium are all in
the same phase.
 H2 (g) + I2 (g) ⇌ 2HI (g)

 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

Heterogeneous Equilibrium - In this type, the reactants and the products of chemical equilibrium are all in
different phases.
 CO2 (g) + C (s) ⇌ 2CO (g)

 CaCO3 (s) ⇌ CaO (s) + CO2 (g)

Law of chemical equilibrium

For a reaction in equilibrium, at a given temperature, the ratio of the product of the concentration of the
reaction products raised to the respective stoichiometric coefficients as per the balanced chemical equation to
that of the product of concentration of the reactants raised to the respective stoichiometric coefficients has a
constant value.

For a hypothetical reaction, aA + bB ⇌ cC + dD

[C]c × [D]d
Kc = ; Kc is called the equilibrium constant.
a b
[A] × [B]

Characteristics of Equilibrium Constant (K)

 Constant at a particular temperature.


 Determines the extent to which a reaction has proceeded before achieving the equilibrium.
[More is the value of K; more is the extent of forward process that has taken place before achieving
equilibrium].
 Equilibrium constant of the reverse reaction is inverse that of the equilibrium constant of a reaction.
 Its value is independent of the initial concentration of the reactants and that of the presence of the
catalyst.

Note: Presence of a catalyst changes the rate of the forward and the backward process of a reaction to the
same extent and hence the equilibrium point remains unaltered. However the equilibrium will be achieved
faster/slower in presence of a positive/negative catalyst.
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Types of Equilibrium Constant

Equilibrium constant Equilibrium constant Equilibrium constant


in terms of molar concentration in terms of partial pressure in terms of mole fraction
(Kc) (Kp) (Kx)

Equilibrium constant expression and unit for different reactions

While writing the expression for equilibrium constant, we consider the concentration of a pure solid and that

of a pure liquid as unity.

Examples:
a) For the reaction: CaCO3(s) ⇌ CaO(s) + CO2(g)

Kc = = [CO2(g)] (∵[CaO(s)] = [CaCO3(s)] = 1 molL-1).

Unit of Kc = molL-1

b) For the reaction: 2SO2(g) + O2(g) ⇌ 2SO3(g)

Kc =

Unit of Kc = (molL-1)-1 = mol-1L

Kp =

Unit of Kp = bar-1

Relation between Kc and Kp : Kp = Kc × (RT)n ; n represents change in no. of moles of gases in a


reaction.

Example of a reaction in which Kp = Kc


H2(g) + Cl2(g) diffused sunlight 2HCl(g) [n = 0]

Example of a reaction in which Kp > Kc


PCl5(g) ⇌ PCl3(g) + Cl2(g) [n > 0]

Example of a reaction in which Kp < Kc


N2(g) + 3H2(g) ⇌ 2NH3(g) [n < 0]

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Applications of Equilibrium Constants (K)

 To predict the extent of a reaction before reaching equilibrium.

 If K > 103; it is considered to be a large value and the reaction proceeds nearly to completion before
achieving the state of equilibrium.

 If K < 10-3; it is considered to be a small value and the reaction hardly proceeds in the forward
direction before achieving the state of equilibrium.

 If 10-3 < K < 103; it is an intermediate value and the extent of the forward reaction depends on the
value of K. Higher is the value of K, greater is the extent of the forward reaction.

 To predict the direction of a reaction at a particular time.

We determine the reaction quotient (Q) for this purpose.

 If Q = K; the reaction is at equilibrium and there is no net direction of the reaction.

 If Q < K; the reaction is not at equilibrium and it proceeds in the forward direction till reaching
equilibrium.

 If Q > K; the reaction is not at equilibrium and it proceeds in the backward direction till reaching
equilibrium.

 To calculate the equilibrium concentrations of the reactants and the products.

NCERT Exercises Q8

Reaction between nitrogen and oxygen takes place as follows:


2N2(g) + O2(g) ⇌ 2N2O(g)
If a mixture of 0.482 mol of N2 and 0.933 mol of O2 is placed in a reaction vessel of volume 10 L and
allowed to form N2O at a temperature for which Kc = 2.0 x 10-37, determine the composition of the
equilibrium mixture.

Solution: Let x moles of N2(g) take part in the reaction. According to the equation, x/2 moles of O2 (g)
will react to form x moles of N2O(g). The molar concentration per litre of different species before the
reaction and at the equilibrium point is:

The value of equilibrium constant (2.0 x 10-37) is extremely small. This means that only small amounts of
reactants have reacted. Therefore, ‘x’ is extremely small and can be omitted as far as the reactants are
concerned.
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Relationship between Equilibrium Constant K, Reaction Quotient Q and Gibbs Energy G

At equilibrium, G = 0 and Q=K.


or,

Factors affecting equilibrium - Le Chatelier’s principle

Le Chatelier’s principle states that a change in any of the factors that determine the equilibrium conditions of
a system will cause the system to change in such a manner so as to reduce or to counter the effect of the
change.

 Effect of change in concentration

 The increase in concentration of one of the reactants for a reaction in equilibrium favours its forward reaction,
thereby shifting the equilibrium point more towards the products side and hence the value of K increases.
This increases the yield of the product(s) and vice-versa.
 The increase in concentration of one of the products for a reaction in equilibrium favours its backward
reaction, thereby shifting the equilibrium point more towards the reactants side and hence the value of K
decreases and vice-versa.

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 Effect of change of pressure
 This factor mainly affects the equilibrium point of the gaseous reactions.
 A pressure change obtained by changing the volume can affect the yield of products in case of a gaseous
reaction where the total number of moles of gaseous reactants and total number of moles of gaseous
products are different.
 For a gaseous reaction involving a decrease in the no. of moles from the reactants to the products, and
thereby decrease in volume in the forward direction, an increase in pressure favours forward reaction.
Hence equilibrium point shifts towards the products side and thus the value of K increases and vice-versa.

 Effect of change in temperature


 For an exothermic reaction in equilibrium, increase in temperature favours backward reaction. Hence
equilibrium point shifts towards the reactants side and thus the value of K decreases and vice-versa.
 For an endothermic reaction in equilibrium, increase in temperature favours forward reaction. Hence
equilibrium point shifts towards the products side and thus the value of K increases and vice-versa.

 Effect of catalyst
Presence of a catalyst does not affect the equilibrium point of a reaction. It increases/decreases the rate of
forward and backward reaction to the same extent by decreasing/increasing the activation energy of the
reaction. Hence the equilibrium point remains the same and the value of K remains unchanged. The presence
of catalyst however affects the time taken to reach the same equilibrium point as compared to the uncatalysed
reaction.

 Effect of addition of inert gas


If the volume is kept constant and an inert gas is added which does not take part in the reaction, the
equilibrium remains undisturbed. It is because the addition of an inert gas at constant volume does not
change the partial pressures or the molar concentrations of the substance involved in the reaction.

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