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Surface Energy and Surface Tension

As we have discussed that an extra energy is associated with surface of liquids, the creation of more surface (spreading of surface) keeping other things like volume fixed requires additional energy. To appreciate this, consider a horizontal liquid film ending in bar free to slide over parallel guides Fig (1).

Fig.(1): Stretching a film. (a) A film in equilibrium; (b) The film stretched an extra distance. 

Suppose that we move the bar by a small distance d as shown. Since the area of the surface increases, the system now has more energy, this means that some work has been done against an internal force. Let this internal force be F, the work done by the applied force is F.d = Fd. From conservation of energy, this is stored as additional energy in the film. If the surface energy of the film is S per unit area, the extra area is 2dl. A film has two sides and the liquid in between, so there are two surfaces and the extra energy is

S (2dl) = Fd                         (1) Or, 

S = $\frac{Fd}{2dl} = \frac{F}{2l}$                   (2)

This quantity S is the magnitude of surface tension. It is equal to the surface energy per unit area of the liquid interface and is also equal to the force per unit length exerted by the fluid on the movable bar.

So far we have talked about the surface of one liquid. More generally, we need to consider fluid surface in contact with other fluids or solid surfaces. The surface energy in that case depends on the materials on both sides of the surface. For example, if the molecules of the materials attract each other, surface energy is reduced while if they repel each other the surface energy is increased. Thus, more appropriately, the surface energy is the energy of the interface between two materials and depends on both of them.

We make the following observations from above: 

(i) Surface tension is a force per unit length (or surface energy per unit area) acting in the plane of the interface between the plane of the liquid and any other substance; it also is the extra energy that the molecules at the interface have as compared to molecules in the interior. 

Fig. (2)

(ii) At any point on the interface besides the boundary, we can draw a line and imagine equal and opposite surface tension forces S per unit length of the line acting perpendicular to the line, in the plane of the interface. The line is in equilibrium. To be more specific, imagine a line of atoms or molecules at the surface. The atoms to the left pull the line towards them; those to the right pull it towards them! This line of atoms is in equilibrium under tension. If the line really marks the end of the interface, as in Figure 2 (a) and (b) there is only the force S per unit length acting inwards.

Table 1 gives the surface tension of various liquids. The value of surface tension depends on temperature. Like viscosity, the surface tension of a liquid usually falls with temperature.

Table 1: Surface tension of some liquids at the temperatures indicated with the heats of the vaporisation

A fluid will stick to a solid surface if the surface energy between fluid and the solid is smaller than the sum of surface energies between solid-air, and fluid-air. Now there is attraction between the solid surface and the liquid. It can be directly measured experimentaly as schematically shown in Fig. 3. A flat vertical glass plate, below which a vessel of some liquid is kept, forms one arm of the balance. The plate is balanced by weights on the other side, with its horizontal edge just over water. The vessel is raised slightly till the liquid just touches the glass plate and pulls it down a little because of surface tension. Weights are added till the plate just clears water.

Fig.(3): Measuring Surface Tension.

Suppose the additional weight required is W. Then from Eq. 2 and the discussion given there, the surface tension of the liquid-air interface is 

$S_{la} = \frac{W}{2l} = \frac{mg}{2l}$               (3) 

where m is the extra mass and l is the length of the plate edge. The subscript (la) emphasises the fact that the liquid-air interface tension is involved.

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