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Surface Tension

Surface tension, γ (alternatively T or σ) is defined as the ratio of the


surface force (F ) to the length (L) along which the force acts:
γ = F /L. That is, the amount of force exerted in the surface
perpendicular to a line of unit length.
In terms of energy, surface tension is the ratio of the change in the
energy of the liquid and the change in the surface area of the liquid
(that led to the change in energy). SI units: N m−1 or J m−2 .
Various intermolecular forces, such as van der Waals forces, draw
liquid particles/molecules together. The surface of the fluid tends to
shrink into the minimum surface area possible.
Surface tension depends mainly on:
the forces of attraction between the particles within the given liquid
the gas, solid, or liquid in contact with the liquid.
Note: An increase in temperature lowers the net force of attraction
among molecules and hence decreases surface tension.
PHY1104 – Properties of Matter Semester I 2023/2024 October 2023 1 / 36
Cohesion and Adhesion in Liquids
Cohesive forces: These are forces of attraction between molecules of the
same type. Liquids can, for example, be held in open containers because
cohesive forces hold the molecules together.
Adhesive forces: These are forces of attraction between molecules of
different types. Such forces cause liquid drops to cling to window panes. It
is also responsible for capillarity action.
Soap bubbles blown into the air maintain their shape because of the
attractive force between the molecules of the soap bubble.
Cohesive forces between molecules cause the surface of a liquid to contract
to the smallest possible surface area. This general effect is called surface
tension and arises because:
Molecules on the surface are pulled inward by cohesive forces, reducing
the surface area.
Molecules inside the liquid experience zero net force, since they have
neighbours on all sides.
Hence the surface of a liquid acts like a stretched elastic sheet. This
effectively explains surface tension effects.
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The molecular basis of surface tension
Surface tension is the tendency of fluid surfaces to shrink into the minimum
surface area possible.
At liquid–air interfaces, surface tension results from the greater attraction of liquid
molecules to each other (due to cohesion) than to the molecules in the air (due to
adhesion). The net effect is an inward force at its surface that causes the liquid to
behave as if its surface were covered with a stretched elastic membrane. Thus, the
surface comes under tension from the imbalanced forces. In other words,
– The interaction of a given molecule with its (nearest) neighbours leads
to a reduction of its potential energy, i.e., intermolecular forces act to
stabilise the system. Such forces give rise to cohesion among the
molecules of a liquid and to adsorption or adhesion between molecules
of that liquid and any bounding solid surface.
– In accordance with the principle that every system moves towards a
state of minimum potential energy, if free to do so, the surface of a
liquid shows a tendency to contract
– The smallest surface area for a given mass of water is that of a sphere.
– This explains the formation of spherical droplets of rain.

PHY1104 – Properties of Matter Semester I 2023/2024 October 2023 3 / 36


Due to the cohesive forces, a molecule is pulled equally in every
direction by neighbouring liquid molecules. The molecules inside bulk
of the liquid interact with their neighbouring molecules in all
directions, resulting in a net force of zero.
The molecules at the surface do not have the same molecules on all
sides of them and therefore are pulled inward.
This creates some internal pressure and forces liquid surfaces to
contract to the minimum area possible.
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In Summary:
A molecule inside the liquid will not experience a net force (Fnet = 0)
because the forces by the neighbouring molecules all cancel out.
A molecule on the surface of the liquid will experience a net inward
force since there will be no attractive force acting from above.
This inward net force causes the molecules on the surface to contract
and to resist being stretched or broken ⇒ the surface is under tension!
When an object is on the surface of the fluid, the surface under
tension will behave like an elastic membrane.
Thus, surface tension is a phenomenon in which the surface of a
liquid which is in contact with a gas, acts as a thin elastic sheet —
Only applies if the liquid surface is in contact with gas/air.
If the surface is between two liquids (such as water and oil), it is called
“interface tension”.
If the tension is between a liquid and a solid, it is often referred to as
“surface energy”. Other than in the interface, these are not different
from surface tension.
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Effects of surface tension
Several effects of surface tension can be seen with ordinary water:
Beading of rain water on a waxy surface, such as a leaf. Water adheres
weakly to wax and strongly to itself, so water clusters into drops.
Surface tension gives them their near-spherical shape, because a sphere
has the smallest possible surface area to volume ratio.
Formation of drops occurs when a mass of liquid is stretched.
Flotation of objects denser than water occurs when the object is
nonwettable and its weight is small enough to be borne by the forces
arising from surface tension (e.g a needle, some insects).
Separation of oil and water (in this case, water and liquid wax) is
caused by a tension in the surface between dissimilar liquids.

Soap bubbles have very large surface areas with very little mass.
Bubbles in pure water are unstable. The addition of surfactants,
however, can have a stabilising effect on the bubbles — surfactants
reduce the surface tension of water by a factor of three or more.

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Surface tension of some liquids

Liquid σ or γ in N m−1
Water at 0 ◦ C 0.076
Water at 20 ◦ C 0.073
Water at 100 ◦ C 0.059
Soapy water (typical) 0.037
Mercury 0.465
Olive oil 0.032
Tissue fluids (typical) 0.050
Blood, whole at 37 ◦ C 0.058
Blood plasma at 37 ◦ C 0.073
Gold at 1070 ◦ C 1.000
Oxygen at -193 ◦ C 0.016
Helium at -269 ◦ C 0.00012

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Surface tension is the property of the surface of a liquid that allows it
to resist an external force, due to the cohesive nature of its molecules.
Due to surface tension, a needle or paper clip made of steel, which has
much higher density than water, can “float” on the surface of water
— The paper clip does not float but its weight (weight of the paper
clip) is rather supported by the surface of water.

Applications of surface tension

Clinical test for jaundice


Disinfectants
Soaps and detergents
Capillary rise

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Measuring Surface Tension: The Capillary rise method
The end of a capillary is immersed into the solution. The height at
which the solution reaches inside the capillary is related to the surface
tension by Equation 1.
If a tube is sufficiently narrow and the liquid adhesion to its walls is
sufficiently strong, surface tension can draw liquid up the tube in a
phenomenon known as capillary action.
The height to which the column is lifted is given by
2γ cos θ
h= , (1)
ρgr
where h is the height of rise of liquid in the capillary above the
reservoir level, γ is the liquid–air surface tension, ρ is the density of
the liquid, r is the radius of the capillary, g is the acceleration due to
gravity, and θ is the contact angle.
If θ > 90◦ , as with mercury in a glass container, the liquid will be
depressed rather than lifted.
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Measuring surface tension: Using a sliding wire device
The sliding wire device exerts a force to reduce the film’s surface area.
The force needed to hold the wire in place is
F = γL. (2)
Since there are two liquid surfaces attached to the wire, the force is
F = γ (2`) (3)
= 2γ` (4)
where ` is the length of the wire.
At equilibrium, the weight, mg , of the wire is balanced by the force
due to surface tension of the liquid.
mg
∴ γ= (5)
2`

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Some Examples
Surface tension is responsible for the shape of liquid droplets.
Although easily deformed, droplets of water tend to be pulled into a
spherical shape by the cohesive forces of the surface layer.
Surface tension is the reason why liquids form bubbles and droplets.
The inward surface tension force causes bubbles to be approximately
spherical and raises the pressure of the gas trapped inside relative to
atmospheric pressure outside. It can be shown that the excess
pressure P inside a spherical bubble is given by

P= , (6)
r
where r is the radius of the bubble. Thus the pressure inside a bubble
is greatest when the bubble is the smallest.
The excess pressure in a liquid drop is

P= . (7)
r
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Example 1 – Pressure inside a liquid drop
Consider a liquid drop of radius R. The force
due to surface tension is
F = γL = γ · 2πR (8)
At equilibrium, the force caused by tension is
equal to the force due to pressure inside the
liquid drop (Force = Pressure × Area).

⇒ P · A = 2πRγ (9)

The cross-sectional area is given by A = πR 2 .


Therefore,
P · πR 2 = 2πRγ. (10)
∴ The excess pressure inside a liquid drop is:

P= . (11)
R
Example 2 – Pressure inside a soap bubble
Consider a soap bubble of radius R. The force due to surface tension is
F = γL.
Since air is trapped inside a soap bubble, the bubble consists of two thin
layers. This liquid layer is so thin that R + ∆R → R.
The length L through which the surface tension acts is therefore twice that
in a liquid drop of the same radius. Hence,
F = γL = γ · (4πR) ≡ 4πγR. (12)
At equilibrium, the force caused by tension is equal to the force due to
pressure inside the bubble (Force = Pressure × Area). Note that pressure
acts perpendicularly inside the surface but only the vertical components act
in the direction of surface tension.
The cross-sectional area is given by A = πR 2 . Therefore,
P · A = 4πRγ ⇒ P · πR 2 = 4πRγ. (13)
The excess pressure inside a bubble is therefore

P= . (14)
R
Surface Energy and Surface Tension
Consider a liquid whose surface tension is γ. If a force F acts
on the surface of the liquid through a distance `, then the force
due to surface tension is F = 2γ`.
If the area of the liquid surface has to be increased, work has to
be done against the force of surface tension.

The work done, dW to attain a small displacement, dx is


Z x
dW = F × dx = 2γ`dx ⇒ W = 2γ`dx
0

The work done to form a film is stored as potential energy in the surface and the amount
of this energy per unit area of this surface under isothermal condition is the “intrinsic
surface energy”. We thus obtain Z x
W = 2γ`dx
0
Since A = 2`x (area of both sides), then
W = 2γ`x = γA

W
∴ γ = (15)
A
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Due to surface tension, the pressure inside and outside a soap bubble will be
different. We need to calculate this pressure difference (using work done)
Consider an air bubble inside a liquid, say water.
Assuming the pressure difference is ∆P, then the work done, W to
increase the radius of this bubble from R to (R + ∆R) is given by:
W = F · ∆R = 4πR 2 ∆P · ∆R

(16)

Note that 4πR 2 is the area of a sphere (i.e., the bubble is assumed
to be spherical). Hence, the change in area is,
2
∆S = 4π (R + ∆R) − 4πR 2 = 8πR∆R (17)
From the definition of surface tension (in terms of work done and
surface area):
W 4πR 2 ∆P∆R
γ= =
∆S 8πR∆R


∴ ∆P = (18)
R
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For a soap bubble in air, there are two surfaces, and so,

 

∆P = 2
R


= (19)
R

1 Consider a soap film trapped between a frame and a wire of length 10 cm. If
the surface tension is given as 0.0049 N m−1 , calculate the mass of the wire
such that the wire remains in equilibrium. 100 mg
2 3. What will be the diameter of a water droplet, the pressure inside which is
0.05 N cm−2 greater than the outside pressure? 0.6 mm
3 A soap bubble is observed inside a bucket of water. If the pressure inside the
bubble is 0.075 N cm−2, calculate the diameter of the bubble. 8 × 10−4 m
(Where necessary, take the surface tension of water as 0.075 N/m).

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Example 3 – Radius of curvature when bubbles interact
Consider two bubbles with radii r1 , r2 and inside pressure P1 and P2 ,
respectively. Let P0 be the atmospheric pressure and assume r1 < r2 . The
excess pressure for each of the two bubbles is
4γ 4γ
P1 − P0 = and P2 − P0 = (20)
r1 r2

If the two bubbles are brought into contact and the radius of interface is R,
then

4γ 1 1 1
P1 − P2 = ⇒ − = . (21)
R r1 r2 R

r1 r2
∴ R= (22)
r2 − r1

Note: Bubbles of the same radius form an interface which is flat.


Two soap bubbles connected with a tube

With the valve closed, two bubbles of different sizes are attached to each
end of a tube.
What happens after interconnecting the bubbles?
Since the excess pressure is inversely proportional to the radius of the
bubble, the surface forces produce a larger pressure in the smaller
bubble than in the larger one.
After connecting the insides of the bubbles, the air will start to flow
from the smaller one to the bigger one.
The bigger bubble will grow and the smaller one will shrink to a flat
membrane at the end of the connecting tube.
Above demonstrates the dependence of pressure below a curved surface of a
liquid on the radius of the surface.
The diameters of the bubbles will change (air will flow from one bubble to
the other) only if there is a higher pressure inside one of the bubbles than in
the other.
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The air will then flow from the bubble with higher pressure into the other
one with lower pressure (larger radius).
Recall:

The Laplace pressure inside a bubble is given as: LP = , where σ is
r
the surface tension of the liquid while r is the radius of the bubble.
Since Laplace pressure is inversely proportional to the bubble radius, the
pressure is higher inside the smaller bubble than in the larger bubble.
The air thus flows from the smaller bubble into the larger one.

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Surface Tension: Pressure Inside a Bubble

Question: Calculate the gauge pressure inside a soap bubble of radius 2 × 10−4 m.
Assume the surface tension for soapy water is 0.0370 N m−1 . Convert this
pressure to mm Hg.

Solution: Substituting r and γ into the equation P = r , we obtain

4γ 4 (0.037 N/m) 2
P= = = 740 N/m (23)
r 2 × 10−4
We use a conversion factor to get this into units of mm Hg:

2 1.00 mm Hg
P = 740 N/m 2 = 5.56 mm Hg. (24)
133 N/m

Discussion: Note that if a hole were to be made in the bubble, the air would be
forced out, the bubble would decrease in radius, and the pressure inside would
increase to atmospheric pressure (760 mm Hg). This is the standard pressure at
sea level (101325 Pa).
Capillary Action

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Capillary Action
One important phenomenon related to the relative strength of cohesive and
adhesive forces is capillary action.
Capillary action is the tendency of a liquid to be raised or suppressed in a
narrow tube (or capillary tube) due to the relative strength of cohesive and
adhesive forces.
If a capillary tube is placed vertically into a liquid, capillary action will raise
or suppress the liquid inside the tube depending on the combination of
substances.
The actual effect depends on the relative strength of the cohesive and
adhesive forces and, thus, the contact angle θ.
(i) If θ < 90◦ , the liquid will be raised;
(ii) If θ > 90◦ , the liquid will be suppressed.
Mercury, for example, has a very large surface tension and a large contact
angle with glass. When placed in a tube, the surface of a column of mercury
curves downwards.
The curved surface of a liquid in a tube is called a meniscus.
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The tendency of surface tension is always
to reduce the surface area.
Surface tension thus flattens the curved
liquid surface in a capillary tube.
This results in a downward force in mercury
and an upward force in water.
When a static quantity of liquid is in contact with an impermeable solid
surface, it generally rests so that there is a characteristic angle (measured in
the liquid) between the surface of the liquid and the surface of the solid.
This is the angle of contact, θ (see Figure 1).
When the angle of contact is acute, the liquid spreads out a little and
“wets” the surface. When the angle of contact is obtuse, the liquid
“bunches up”, and does not wet the surface.
Consider a liquid, L, (e.g. water) in contact with a solid, S, (e.g. glass) and
a gas, G, (e.g. air) as shown in Figure 1. The angle of contact is θ and the
surface tensions (energy per unit area) of the three interfaces (γLV , γSV ,
γSL ) are as shown.
When such a system is in equilibrium, we have either
γSV = γSL + γLV cos θ or γSL = γSV + γLV cos (180 − θ) . (25)
Hence, γSV − γSL
cos θ = . (26)
γLV
The angle of contact is acute (θ < 90◦ ) if γSV > γSL and is obtuse
(θ > 90◦ ) if γSV < γSL . That is, angle is obtuse if cos θ is negative.
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Surface tension occurs during a gas–liquid interface, but if that interface
comes in contact with a solid surface — such as the walls of a container, the
interface usually curves up or down near that surface. Such a concave or
convex surface shape is known as a meniscus.
A concave meniscus occurs when θ < 90◦ (θ is the contact angle).
A convex meniscus has a contact angle greater than 90◦ .
The surface tension between the liquid and air is usually greater than its
surface tension with the walls of a container. Where the two surfaces meet,
their geometry must be such that all forces balance.
Where the two surfaces meet, they form a contact angle, θ, which is the
angle the tangent to the surface makes with the solid surface. Note that the
contact angle, θ, is measured through the liquid.
Special contact angles:
For a water–silver interface where θ = 90◦ , the liquid–solid and the
solid–air surface tension difference is exactly zero.
A contact angle of 180◦ occurs when the liquid–solid and solid–air
surface tension difference is exactly equal to the liquid–air surface
tension. That is, γLV = γSL − γSV > 0 ⇒ θ = 180◦ .
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Figure 1: A liquid drop in a a wetting situation with contact angle θ < 90◦ (left-hand
panel), and a non-wetting situation with θ > 90◦ on a planar solid surface (right-hand
panel). γ is the interfacial tension between the phases indicated by the subscripts —
SV, SL, and LV stand for solid–vapour, solid–liquid, and liquid–vapour, respectively.

If θ > 90◦ (a convex meniscus), resulting in a negative liquid-solid surface


tension, the liquid level will go down compared to the surrounding level, as
opposed to rising in relation to it.
Mercury is suppressed in a glass tube because its contact angle is greater
than 90◦ (θ ≈ 140◦ ). Surface tension exerts a downward force as it flattens
the mercury, suppressing it in the tube.
Water is raised in a glass tube because its contact angle is nearly 0◦ .
Surface tension therefore exerts an upward force when it flattens the surface
to reduce its area.
Mercury kept in a container into
which a narrow tube is inserted lowers
its level inside the tube relative to the
level in the rest of the container.

In a similar situation, water rises in the tube so that the water level in the tube is
above the water level in the rest of the container. This phenomenon is due to the
large contact angle of mercury with glass (θ ≈ 140◦ ) and the smaller contact angle
of water with glass (θ ≈ 0◦ ).
Adhesion and Capillary Action
Recall: Forces of attraction acting between the molecules of same type are
called cohesive forces. Forces acting between the molecules of different types
are called adhesive forces.
The balance between the cohesion of the liquid and its adhesion to the
material of the container determines the degree of wetting, the contact
angle and the shape of meniscus.
When cohesion dominates, the wetting is low and the meniscus is
convex at a vertical wall (e.g., mercury in a glass container).
When adhesion dominates, the wetting is high and the similar meniscus
is concave (e.g. for water in a glass).
This explains why water beads up on a waxed car but does not on bare
paint. Because the adhesive forces between water and wax are much smaller
than those between water and paint.
Adhesion and cohesion forces cause water to rise in glass tubes and in soil
pores. The adhesion causes the rise in a capillary, and the cohesion makes
all the water molecules follow the upward pull.
The concave curvature indicates the presence of a pressure below the water
surface being smaller than the surrounding normal, atmospheric pressure.
Water forms beads on the waxed surface
because the cohesive forces responsible for
surface tension are larger than the adhesive
forces, which tend to flatten the drop.
Water beads on bare paint are flattened
considerably because the adhesive forces
between water and paint are strong, overcoming
surface tension.
The water beads on wax (which are not
flattened) are due to the greater force of
attraction between the water molecules than
between the water molecules and the surface.
— On the surface without wax the force of
attraction between the water molecules and
paint is greater. Hence the flattening (and
consequently, wetting).
Capillary Rise

Consider a liquid in a container, in which a narrow tube (or capillary tube)


of radius r is placed.
The vertical displacement h that will take place within the capillary is given
by the following equation:
2γ cos θ
h= , (27)
ρgr

h is the height of the liquid drawn up the capillary tube


γ is the liquid–gas surface tension
θ is the contact angle
ρ is the density of the liquid
g is the acceleration due to gravity
r is the radius of the capillary tube

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Assume the liquid rises to a height, h and the contact angle
is θ. The net vertical force (acting upwards) due to surface
tension is
Fnet = γ cos θ · L (28)
= γ cos θ · (2πr ) (29)

At equilibrium, this vertical force is equal to the weight of


the liquid in the bore. If m is the mass of the liquid,

γ cos θ · (2πr ) = mg (30)


2

2πr γ cos θ = ρπr h g (31)
2γ cos θ
∴ h = . (32)
ρgr

Note that the height, h, is directly proportional to the surface tension γ,


which is its direct cause. h is also inversely proportional to the tube radius, r
and the density, ρ, of the liquid
The smaller the radius r , the higher the liquid can be raised.
Also a larger density means a greater mass in the same volume.
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When a capillary tube is plunged into a volume of wetting liquid, the liquid
rises inside the tube under the effect of capillary forces.
The height reached by the liquid is inversely proportional to both the radius
of the tube and density, ρ, of the liquid.
A denser fluid in the same tube rises to a smaller height, all other factors
being the same.
The height reached by the liquid is negligible for large-radius tubes.

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Question: Calculate the radius of a capillary tube that would raise a liquid 100 m,
assuming that liquid has a density of 1050 kg m−3 , its contact angle is zero, and
its surface tension is 0.0728 N m−1 .

Solution: The height to which a liquid will rise as a result of capillary action is
given by
2γ cos θ
h= , (33)
ρgr

and every quantity is known except for r .

Solving for r by substituting known values produces

2γ cos θ 2 × 0.0728 × cos (0)


r = =
ρgh 1050 × 9.8 × 100

= 1.41 × 10−7 m.

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Now consider rise of a liquid such as water in two different capillary tubes of
radii r1 and r2 . If the water rises to heights h1 and h2 as shown in the Figure
below, show that r1 h1 = r2 h2 .

Let γ1 and γ2 be the surface tension in capillaries 1


and 2, respectively. Let the corresponding contact
angles be θ1 and θ2 .

r1 h1 ρ1 g r2 h2 ρ2 g
⇒ γ1 = and γ2 = (34)
2 cos θ1 2 cos θ2

Since the liquid in the two capillary tubes is the same, γ1 = γ2 .

r1 h1 ρ1 g rhρg
⇒ = 2 2 2 (35)
2 cos θ1 2 cos θ2

Also, ρ1 = ρ2 and θ1 = θ2

⇒ r1 h1 = r2 h2 . (36)
Summary
Angle of Contact:
Angle of contact, for a solid and a liquid is defined as the angle
between tangent to the liquid surface drawn at the point of contact
and the solid surface inside the liquid.
The angle of contact of a liquid surface on a solid surface depends on
the nature of the liquid and the solid.
Case I: When θ < 90◦ : The liquid surface curves up towards the solid
surface. This happens when the forces of cohesion between two liquid
molecules is less than the forces of adhesion between the liquid and the solid.
If such a liquid is poured into a solid tube, it will have a concave meniscus.
For example, a glass rod dipped in water, or water inside a glass tube.
Case II: When θ > 90◦ : The liquid surfaces in contact with the solid
surface get curved downward. In this case the cohesive forces are greater
than the adhesive forces. In such cases, solids do not get “wet”. When such
liquids are put into a solid tube, a convex meniscus is obtained. An example
is a glass rod dipped in mercury or mercury within a solid glass tube.

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NOTE:

While water wets glass, there are some surfaces made of material whose
surfaces water does not adhere to.
When carefully poured on a surface made of a substance to which
water does not adhere (wax is such a substance), it behaves like
mercury on glass.
Hence, if water is poured onto a smooth, flat, horizontal wax surface,
say a waxed sheet of glass, it will behave similarly to mercury poured
onto glass.

Definitions:

Surfactants – substances which reduce surface tension.


Meniscus – surface curvature formed by a liquid in a container.

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