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Q.State Raoult’s law for a solution containing volatile components. Write two characteristics of the solution which obeys Raoult’s law at all concentrations.

CBSECBSE Class XII Board 2019Subjective· 2mImportance★★★★★
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Raoult's law for volatile components states that each component's partial vapour pressure equals its mole fraction times its pure vapour pressure; ideal solutions obeying it show zero enthalpy of mixing and zero volume change on mixing.

Understanding Raoult's Law for Volatile Components

When both components of a binary solution can evaporate—meaning both are volatile—each contributes to the total vapour pressure above the solution. Raoult's law quantifies this contribution by relating the partial pressure of each component to how much of it is present in the liquid phase.

The central idea is simple: if a component makes up, say, 30% of the solution by mole fraction, it will exert roughly 30% of the vapour pressure it would exert if it were pure. This linear relationship holds exactly for ideal solutions.

For a solution containing volatile components A and B:

pA=xA pA0andpB=xB pB0p_A = x_A \, p_A^0 \quad \text{and} \quad p_B = x_B \, p_B^0

where pAp_A and pBp_B are the partial vapour pressures, xAx_A and xBx_B are the mole fractions in the liquid phase, and pA0p_A^0 and pB0p_B^0 are the vapour pressures of the pure components at the same temperature.

The total vapour pressure is then:

ptotal=pA+pB=xA pA0+xB pB0p_{\text{total}} = p_A + p_B = x_A \, p_A^0 + x_B \, p_B^0

Since xA+xB=1x_A + x_B = 1 for a binary solution, this can also be written as:

ptotal=pA0+(pB0−pA0)xBp_{\text{total}} = p_A^0 + (p_B^0 - p_A^0) x_B

This shows that total pressure varies linearly with composition.

Characteristics of Ideal Solutions

A solution that obeys Raoult's law at all concentrations—across the entire composition range from pure A to pure B—is called an ideal solution. Such behaviour arises when the intermolecular forces between unlike molecules (A–B interactions) are essentially identical to those between like molecules (A–A and B–B interactions).

Two fundamental thermodynamic characteristics define these ideal solutions:

1. Enthalpy of Mixing is Zero (ΔmixH=0\Delta_{\text{mix}} H = 0)

When you mix the components, no heat is absorbed or released. The A–B interactions in the solution are energetically equivalent to the A–A and B–B interactions in the pure liquids, so breaking old bonds and forming new ones costs no net energy. The mixing process is purely entropy-driven. …

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