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Q9.2(c):
Explain why (c) Surface tension of a liquid is independent of the area of the surface

Solution :

1. Theoretical Foundation: Molecular Interaction

Surface tension ($\gamma$) is defined as the force per unit length acting in the plane of the interface between the liquid and another medium (gas or solid). At the microscopic level, molecules in the bulk of a liquid are surrounded by other molecules on all sides, resulting in a net intermolecular force of zero [Per the concept of Central Force fields].

Conversely, molecules at the surface experience a net inward force because there are no liquid molecules above them to provide a counter-balancing upward attraction. This causes the surface layer to behave like a stretched elastic membrane [Per the Molecular Theory of Surface Tension].

2. Definition of Surface Tension as Energy Density

Surface tension can also be defined in terms of work ($W$) done to increase the surface area ($A$) of a liquid film by an amount ($dA$):

$\gamma = \frac{dW}{dA}$

In this thermodynamic definition, $\gamma$ is equivalent to the surface free energy per unit area. Crucially, the internal energy of a liquid surface depends solely on the density of molecules at the surface and the strength of the intermolecular bonds, neither of which changes as the surface area expands, provided the temperature remains constant.

3. Logical Derivation of Independence

To understand why $\gamma$ is independent of area, we analyze the work required for an expansion:

  • Step A: Imagine a liquid film of area $A$. The total surface energy $U$ is given by $U = \gamma A$.
  • Step B: If we increase the area by $dA$, the work done $dW$ is equal to the increase in surface energy: $dW = \gamma \cdot dA$.
  • Step C: The value of $\gamma$ is determined by the cohesive forces between molecules. Since these forces are short-ranged (effective only up to a few molecular diameters, typically $\approx 10^{-9} \, \text{m}$), the environment of a surface molecule does not change as the area increases.
  • Step D: Because the arrangement and density of molecules at the surface remain uniform regardless of whether the surface is $1 \, \text{cm}^2$ or $100 \, \text{cm}^2$, the force per unit length ($\gamma$) must remain constant.

4. Visualizing Surface Energy Stability

Bulk Molecules (Net force = 0) Inward force (Cohesion)

5. Conclusion

Surface tension is an intensive property of the liquid. Much like density or boiling point, it depends on the nature of the substance and the temperature, not on the total quantity or the macroscopic dimensions (area) of the fluid body. Expanding the surface area simply requires bringing more molecules from the bulk to the surface; it does not change the energy state or the cohesive environment of the individual molecules already participating in the surface layer.

Final Solution: Surface tension is an intensive property derived from the cohesive molecular forces of the liquid; since the local environment of a surface molecule remains identical regardless of the total surface area, the force per unit length remains constant.


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