SURFACE AND

INTERFACIAL TENSION
Understanding Surface and
Interfacial Properties
INTERFACES

When phases exist together, the boundary

between two of them is known as an interface.

The properties of the molecules forming the interface are often

sufficiently different from those in the bulk of each phase.

The term surface is used when referring to

either a gas–solid or a gas–liquid interface.
Introduction
• Every physical entity (cell, bacterium, colloid, granule, human) has an interface at its
boundary.
• Interfacial phenomena influence adsorption, drug penetration, emulsions,
suspensions, and lung function.
• This presentation explores types of interfaces, interfacial properties, and their
significance in pharmaceuticals.

Types of Interfaces
•Interfaces exist based on the state of
adjacent phases: 1. Gas-Liquid Surface (e.g., raindrop
surface)
2. Gas-Solid Surface (e.g., tabletop with air
above it)
3. Liquid-Liquid Interface (e.g., oil-water
system)
4. Liquid-Solid Interface (e.g., drug particle
in a suspension)
5. Solid-Solid Interface (e.g., adhesion in
L = Liquid, V = Vapor/Gas, S = Solid
layered tablets)
Surface vs. Interface
• Surface: Specific term for gas-liquid or gas-solid interactions.
• Interface: General term applicable to all phase boundaries (solid-solid, liquid-
liquid, etc.).
• Example: A raindrop's surface is a gas-liquid interface; a table’s surface is a gas-
solid interface.

Importance of Interfacial Phenomena in Pharmacy

• Drug Adsorption: Affects how drugs bind to solid excipients in dosage forms.
• Biological Membranes: Influences drug penetration and absorption.
• Emulsions: Determines formation and stability of oil-water mixtures.
• Suspensions: Controls dispersion of insoluble drug particles in liquids.
• Lung Function: Surface-active agents in alveoli facilitate efficient gas exchange.
• Drug Bioactivity: Surface properties affect therapeutic efficacy.
Surface and Interfacial Tension
• Interfacial Tension (γ): The energy required to maintain the interface between two
phases.
• Expressed as mN/m (millinewtons per meter).
• Surface Tension: A special case of interfacial tension when one phase is a gas.
• Influences droplet formation, wetting, spreading, and adsorption.

Furthermore, there are two important terms related to forces.

First, Cohesive forces are the intermolecular forces

which cause a tendency in liquids to resist separation.
These attractive forces exist between molecules of the
,same substance. While

Second, adhesive forces are the attractive forces

between unlike molecules. They are caused by forces
acting between two substances, such as mechanical
forces (sticking together) and electrostatic forces
(attraction due to opposing charges)
(A) A molecule in the surface
experiences a net attractive force
pointing toward the liquid interior,
because there are no molecules of
the liquid above the surface.

(B) A molecule within the bulk liquid is

surrounded on all sides by other
molecules, which attract it equally
in all directions, leading to a zero
net force.
• Interfacial tension: is the force per unit length existing at
the interface between two immiscible liquid phases and
has the unit of dynes/cm.
• ordinarily; it is less than surface tension because the
adhesive forces between liquid phases forming an
interface are greater than when a liquid and a gas phase
exist together.
• It follows that if two liquids are completely miscible; no
interfacial tension exists between them.
• Liquids exhibit cohesive forces between adjacent molecules.
• Molecules in bulk liquid experience uniform attraction in all directions.
• Molecules at the surface experience an inward pull due to unbalanced cohesive
forces.

Surface Tension
• Definition: The force per unit length applied parallel to the surface to counteract
the inward pull.
• Units: Dynes/cm (cgs system) or N/m (SI system).
• Effect: Causes the surface of a liquid to contract.

Interfacial Tension
• Definition: The force per unit length at the interface between two immiscible
liquid phases.
• Units: Dynes/cm, similar to surface tension.

Comparison with Surface Tension:

• Usually lower than surface tension because adhesive forces between two
liquid phases are stronger than between a liquid and gas.
• If two liquids are completely miscible, no interfacial tension exists.
• Surface tension can be demonstrated using a three-
sided wire frame with a movable bar.
• A soap film forms over the area enclosed by the frame.
• When a force (e.g., a hanging mass) is applied to the bar,
the film stretches.
• When the force is removed, the film contracts due to
surface tension.

Surface Tension Equation

• Surface tension (γ) is determined by the force needed to break the
film (fb).

• The soap film has two liquid-gas interfaces (above and below the
plane).
• The total length of the liquid-gas interface is twice the bar length
(2L).
Surface Tension
Concept of Surface Free Energy
• In a bulk liquid, molecules are surrounded by others in all directions, resulting in
balanced forces.
• At the surface, molecules lack neighboring molecules on one side, leading to
unbalanced cohesive forces.
• To move a molecule from the bulk to the surface, work must be done to overcome
surface tension.
• This extra potential energy at the surface is known as surface-free energy.

Surface Free Energy and Surface Area

• More surface area → More molecules at the surface → Higher surface free
energy.
• Liquids tend to minimize surface energy by adopting shapes with the smallest
surface area per unit volume (e.g., spherical droplets).
• Breaking a liquid into smaller droplets (e.g., a spray) increases its surface free
energy.
Work Done to Increase Surface Area
When a movable bar is used to stretch a soap film in a wireframe:
• Force (f) is required to increase the surface area.
• The work (dW) done to extend the surface by a small distance (ds) is:
dW = f × ds
• From Equation (1): f = γ × 2L
• Substituting this into the work equation: dW = γ × 2L × ds
• Since 2L×ds represents the increase in surface area (dA), we get:
dW = γdA

Equation for Surface Free Energy

For a finite (measurable) change in surface area, we integrate the above
equation: W=γΔA where:
• W = Work done (Surface free energy increase) in ergs.
• γ = Surface tension in dynes/cm (or N/m in SI units).
• ΔA = Increase in surface area (cm²).
 Thermodynamic Interpretation of Surface Tension (γ)
Surface tension is not just a mechanical concept (force per unit length) but also
has a thermodynamic basis. Let's break this down step by step.

Surface Tension as Work Done per Unit Area

From Equation (2):
W=γΔA
• W = Work done (ergs or Joules)
• γ = Surface tension (dynes/cm or N/m)
• ΔA = Increase in surface area (cm² or m²)
This means surface tension is the work required to increase the surface area
by one unit.

Thermodynamic Definition of Surface Tension

• From thermodynamics, at constant temperature (T) and pressure (P), surface tension
can be related to Gibbs free energy (G).
• Equation (3):
• This equation states that surface tension (γ) is the rate of change of Gibbs free
energy (G) with respect to surface area (A), at constant temperature and pressure.
• Gibbs free energy (G) is a thermodynamic function that is independent of the path
taken, unlike mechanical work (WWW).
• This means that surface tension can be analyzed using thermodynamic principles.

Surface Enthalpy and Surface Entropy

From thermodynamics, the relationship between Gibbs free energy (G), Enthalpy (H),
and Entropy (S) is:
G = H−TS
where:
For a surface, this can be rewritten as:
γ=Hs−TSs (Equation 4) γat=the
Surface tension; Hs​= Surface enthalpy (energy stored
surface); Ss​= Surface entropy (disorder at the
surface); T = Absolute temperature (Kelvin)
Implications:
• At higher temperatures (T), the entropic term (TSs​) increases → This means surface
tension decreases because more thermal energy disrupts molecular cohesion at the
surface.
• At lower temperatures, surface tension is higher because entropy is lower.
 Mechanical Interpretation: Surface tension is the force per unit length that keeps
the surface intact.
 Thermodynamic Interpretation: Surface tension is also Gibbs free energy per unit
area.
 Equation (4) shows that surface tension depends on enthalpy and entropy:
• Higher temperature → Lower surface tension (increased molecular motion
reduces cohesive forces).
• Lower temperature → Higher surface tension (stronger intermolecular
attraction).
 Determination of Surface Tension

1. Capillary rise method

2. DuNouy Ring method

3. Drop weight (Stalagmometer) method

4. Maximum bubble pressure method

5. Sessile drop method

 Capillary Rise Method
 When a capillary tube is placed in a liquid, the liquid rises up the tube
a certain distance. By measuring this rise, it is possible to determine
the surface tension of the liquid.
 It is not possible to obtain interfacial tensions using this method.
Capillary Rise Method
 Cohesive force is the force existing between like molecules in the surface of a
liquid
 Adhesive force is the force existing between unlike molecules, such as that
between a liquid and the wall of a glass capillary tube
 When the force of Adhesion is greater than the cohesion, the liquid is said to
wet the capillary wall, spreading over it, and rising in the tube.

If a capillary tube of inside radius = r immersed in a liquid that wets its

surface, the liquid continues to rise in the tube due to the surface tension,
until the upward movement is just balanced by the downward force of gravity
due to the weight of the liquid.
Force Decomposition:
• At the interface between the liquid and the capillary wall, surface tension acts along
the liquid surface.
• This tension force makes an angle θ with the capillary wall.
• The total force per unit length due to surface tension at any point on the
circumference is γ.
• This force has two components:
• Horizontal component: γsinθ (does not contribute to upward motion).
• Vertical component: γcosθ (pulls the liquid up).

Thus, the effective force pulling the liquid up

along the capillary wall is:
a=
γcosθ
 Capillary Rise Method
 The upward component of the force resulting from the surface tension of
the liquid at any point on the circumference is given by:

a = γcos Ө
 Thus, the total upward force around the inside circumference of the tube
is
2πrγcosӨ
o Where, Ө = the contact angle between the surface of
the liquid and the capillary wall
o 2 π r = the inside circumference of the capillary.
o For water the angle Ө is insignificant, i.e. the liquid
wets the capillary wall so that cos Ө = unity
Role of the Contact Angle (θ)
The contact angle θ determines how much of the surface
tension force is effective in pulling the liquid upward:
• If θ = 0° (Perfectly Wetting, e.g., Water on Glass)
• cos⁡0° = 1
• The entire surface tension force contributes to
upward pull, resulting in maximum capillary rise.
• If θ = 90° (Neutral Wetting, e.g., Water on Teflon)
• cos⁡90° = 0
• There is no vertical component, and no capillary rise
occurs.
• If θ > 90° (Non-wetting, e.g., Mercury on Glass)
• cos⁡θ is negative → Liquid is pulled downward,
leading to capillary depression instead of rise.
Capillary Rise Method
The downward force of gravity
(mass x acceleration) is given by
πr2h(ρ – ρo)g
Where:
πr2 = the cross-sectional area +w
h = the height of the liquid column to the lowest point of the meniscus
(ρ – ρ o) = the difference in the density of the liquid p and its vapor
g = the acceleration of gravity
w = the weight of the upper part of the meniscus.

At maximum height, the opposing forces are in equilibrium

2πrγ cos Ө = π r2h(ρ – ρo)g + w

ρ°, θ, and w can usually be disregarded

Hence, the surface tension can be calculated.

2πrγ = πr2hρg γ=rhρg/2

Why is the Vapor Density (ρo​) Considered?

The key reason the vapor density is included in the equation is that the liquid column
does not exist in a vacuum—it is surrounded by its own vapor.
The liquid column is influenced by the density difference between the liquid and its
vapor
1. The buoyant force (due to the displaced vapor) reduces the effective weight of
the liquid column.
2. The effective downward gravitational force is not just ρg but (ρ−ρo)g since the
liquid is surrounded by vapor, which provides a small opposing force.
• The net weight of the liquid column is given by:
• Weight = (Mass of liquid column - Mass of displaced vapor)×g
• Mass of liquid column = πr2hρ
• Mass of displaced vapor = πr2hρo​

• Effective weight = πr2h(ρ−ρo)g

• If the vapor had zero density (ρo=0), then the term simplifies to πr2hρg, which is the
usual hydrostatic pressure of the liquid.
Mid Sem Syllabus