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Q1.11:
Why do gases always tend to be less soluble in liquids as the temperature is raised?

Solution :

Theoretical Foundation: The Thermodynamics of Dissolution

The dissolution of a gas in a liquid is governed by the equilibrium process described as follows:

$\text{Gas} + \text{Solvent} \rightleftharpoons \text{Solution} + \text{Heat}$

[Per the principle of Le Chatelier’s Principle applied to dynamic equilibria]

Step 1: Identifying the Enthalpy of Solution ($\Delta_{sol}H$)

When a gas dissolves in a liquid, the process involves the transition of gas molecules into the liquid phase, which significantly restricts their motion. Consequently, the dissolution of gas in a liquid is almost invariably an exothermic process ($\Delta_{sol}H < 0$).

  • Entropy Change ($\Delta S$): The gas molecules move from a state of high disorder (gaseous state) to a more ordered state within the solvent. Thus, $\Delta S < 0$.
  • Gibbs Free Energy ($\Delta G$): For the process to be spontaneous, $\Delta G = \Delta H - T\Delta S$ must be negative.

Step 2: Applying Le Chatelier's Principle

Le Chatelier's Principle states that if a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to counteract the change.

Since the dissolution is exothermic (heat is a product), increasing the temperature ($T$) adds heat to the system. To counteract this, the system shifts the equilibrium in the direction that consumes the heat, which is the reverse direction:

$\text{Solution} + \text{Heat} \rightarrow \text{Gas} + \text{Solvent}$

[By Le Chatelier's Principle]

Step 3: Kinetic Energy Analysis

On a molecular level, raising the temperature increases the average kinetic energy of the dissolved gas molecules. These molecules gain sufficient energy to overcome the intermolecular forces of attraction between the solute and solvent (solute-solvent interactions) and escape the liquid phase back into the gas phase.

Visual Representation of Solubility Trends

Temperature ($T$) Solubility ($S$) $\text{Downward Trend}$

Summary of Factors

Factor Impact on Dissolved Gas
Increased Temperature Equilibrium shifts to the left (Reverse reaction)
Exothermic Nature Energy release is inhibited by external heat
Kinetic Energy Gas molecules escape the liquid matrix

Final Solution: The dissolution of gases in liquids is an exothermic process. According to Le Chatelier’s Principle, increasing the temperature provides thermal energy that shifts the equilibrium towards the gaseous phase, thereby decreasing the solubility of the gas in the liquid.


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