Question:

A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature. The volume of the container is suddenly increased.
  1. What is the initial effect of the change on vapour pressure?
  2. How do rates of evaporation and condensation change initially?
  3. What happens when equilibrium is restored finally and what will be the final vapour pressure?

Updated On: Nov 10, 2023
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Solution and Explanation

(a) If the volume of the container is suddenly increased, then the vapour pressure would decrease initially. This is because the amount of vapour remains the same, but the volume increases suddenly. As a result, the same amount of vapour is distributed in a larger volume.


(b) Since the temperature is constant, the rate of evaporation also remains constant. When the volume of the container is increased, the density of the vapour phase decreases. As a result, the rate of collisions of the vapour particles also decreases. Hence, the rate of condensation decreases initially.


(c) When equilibrium is restored finally, the rate of evaporation becomes equal to the rate of condensation. In this case, only the volume changes while the temperature remains constant. The vapour pressure depends on temperature and not on volume. Hence, the final vapour pressure will be equal to the original vapour pressure of the system.

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Concepts Used:

Equilibrium

An equilibrium represents a state in a process when the observable properties such as color, temperature, pressure, concentration etc do not show any change.

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.

In the case of physical processes such as the melting of solid, dissolution of salt in water etc., the equilibrium is called physical equilibrium while the equilibrium associated with chemical reaction is known as chemical equilibrium.

Equilibrium in Chemical changes

The chemical equilibrium in a reversible reaction is the state at which both forward and backward reactions occur at the same speed.

The stage of the reversible reaction at which the concentration of the reactants and products do not change with time is called the equilibrium state.

Read More: Calculating Equilibrium Concentration

Types of Chemical Equilibrium

There are two types of chemical equilibrium:

  • Homogeneous Equilibrium
  • Heterogeneous Equilibrium

Homogenous Chemical Equilibrium

In this type, the reactants and the products of chemical equilibrium are all in the same phase. Homogenous equilibrium can be further divided into two types: Reactions in which the number of molecules of the products is equal to the number of molecules of the reactants. For example,

  • H2 (g) + I2 (g) ⇌ 2HI (g)
  • N2 (g) + O2 (g) ⇌ 2NO (g)

Reactions in which the number of molecules of the products is not equal to the total number of reactant molecules. For example,

  • 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
  • COCl2 (g) ⇌ CO (g) + Cl2 (g)

Heterogeneous Chemical Equilibrium

In this type, the reactants and the products of chemical equilibrium are present in different phases. A few examples of heterogeneous equilibrium are listed below.

  • CO2 (g) + C (s) ⇌ 2CO (g) 
  • CaCO3 (s) ⇌ CaO (s) + CO2 (g)

Thus, the different types of chemical equilibrium are based on the phase of the reactants and products.

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