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Q6.1(a):
A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature. The volume of the container is suddenly increased. a) What is the initial effect of the change on vapour pressure?

Solution :

Initial State Analysis

In a sealed container at constant temperature ($T$), the system exists in a dynamic equilibrium state described by the phase transition: $\text{Liquid}(l) \rightleftharpoons \text{Vapour}(g)$. According to the principles of phase equilibrium [Per the Clausius-Clapeyron relation], at a fixed temperature, the vapour pressure of a substance is constant and independent of the volume of the container, provided both phases (liquid and vapour) remain present.

Step 1: Analyzing the Effect of Sudden Volume Expansion

When the volume ($V$) of the container is suddenly increased to $V'$, the following processes occur:

  • The concentration of the vapour molecules ($n/V$) decreases instantaneously because the same number of gaseous moles ($n$) now occupy a larger volume [Per Boyle's Law: $P \propto 1/V$ at constant $T$].
  • As the gaseous molecules spread into the newly available volume, the rate of collisions per unit area on the surface of the liquid decreases.
  • Consequently, the pressure exerted by the vapour phase drops below its equilibrium vapour pressure ($P_{eq}$).

Step 2: Visual Representation of Pressure Change

Initial State (V) Expanded State (V') Liquid Liquid Lower P

Step 3: Logical Conclusion regarding Vapour Pressure

The initial effect is a decrease in the pressure of the vapour phase. This is because, at the instant of volume expansion, the number of moles of vapour per unit volume ($C = n/V$) decreases. Since the partial pressure of a gas is directly proportional to its molar concentration ($P = CRT$), an increase in $V$ at constant $T$ results in an immediate reduction in the observed vapour pressure [Per the Ideal Gas Law derivation].

Summary of Thermodynamic Response

While the system will eventually restore equilibrium by the evaporation of more liquid molecules until the original equilibrium pressure is re-established (Le Chatelier's Principle), the initial effect of the volume increase is a transient reduction in vapour pressure.

Final Solution: The initial effect of increasing the volume of the container is a decrease in the vapour pressure of the system.


More Questions from Class 11 Chemistry Equilibrium EXERCISES


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