DEPARTMENT OF PHARMACEUTICS AND

PHARMACEUTICAL TECHNOLOGY

FEDERAL UNIVERSITY

OYE EKITI

PCT 302

SURFACE & INTERFACIAL PHENOMENA, SURFACE

ACTIVE AGENTS

OLUTAYO ADELEYE
Learning objectives:

 To describe interface and to list the classes of interface

 To explain interfacial and surface tension

 To explain the consequences of surface tension

 To describe the methods of determining surface tension

 To define surface active agents

 To list the classes of surface active agents

 To discuss the pharmaceutical application and medicinal importance of surface active

agents

 To describe micelle formation

 To identify the factors affecting solubilization

 To discuss pharmaceutical applications of solubilization

INTRODUCTION

Several types of interface can exist, depending on whether the two adjacent phases are in the

solid, liquid, or gaseous state. The boundary between any two faces is known as an Interface.

Every physical entity such as cells, bacteria, particles, granules, animals etc. possesses an

interface at its boundary with its surroundings.

There are considerable forces of attraction which exist within the molecules at the interface and

within the molecules in the bulk (e.g. liquid and solid system). However, the forces of attraction

which exist at the interface differ from the forces which exist within the bulk. Hence, the

properties of the molecules at the interface are often different from those in the bulk of each

phase.
At each zone of attraction within the bulk there are equal numbers of molecules exerting equal

forces from all directions since the molecules are surrounded by other molecules of the same

kind, thus the resultant force of attraction experienced by the molecules is zero. Molecules on the

surface have a part of the zone of attraction projecting above the surface into the vapor (gaseous)

phase; only some of their neighboring molecules are of the same kind. At this phase the numbers

of molecules are smaller relative to the molecules in the bulk. The forces of attraction exerted by

these molecules are relatively weak apart from their number [high attractive forces are exerted

from molecules of the same kind (cohesive force of attraction) and lower attractive forces from

molecules of the neighboring phase (adhesive force of attraction)]. As a result of these weak

forces and few numbers of molecules, the attractions which exist between the molecules at the

surface and the underlying bulk molecules are not balanced thereby making the surface

molecules to experience an inward pull (attraction) and also transference of molecules from the

bulk to the surface layer which requires the use of energy in order to overcome the inward

attraction resisting movement to the surface layer. This energy is known as the surface free

energy.
All systems will naturally react spontaneously in order to reach a state with the lowest total free

energy (from the law of thermodynamics). The methods by which systems decrease their total

free energies to a minimum give rise to the concept of interfacial phenomena.

This phenomenon is important in pharmacy and medicine because they are factors that affect

adsorption of drugs onto solid excipient in dosage forms, penetration of molecules through

biologic membranes, emulsion formation and stability, and the dispersion of insoluble particles

in liquid media to form suspensions. The activity of some drugs depends entirely on the surface

properties of such drugs.

CLASSIFICATION OF INTERFACES

A liquid interface involves the association of a liquid phase with a gaseous or another liquid

phase while the solid interface involves the association of a solid phase with gaseous, liquid or

another solid phase.

Phase Interfacial Tension Types and Examples of Interfaces

Gas–Gas No interface possible

Gas–liquid γLV Liquid surface, body of water exposed to

atmosphere. Aerosols, solutions

Gas–solid γSV Solid surface, table top. Aerosols

Liquid–liquid γLL Liquid–liquid interface, emulsion

Liquid–solid γLS, Liquid–solid interface, suspension

Solid–solid γSS Solid–solid interface, powder particles in

contact. Tablets
Note; the boundary between two phases is generally known as an Interface but when one of the

phases is a gas, the term surface is frequently used.

SURFACE AND INTERFACIAL TENSIONS

Free energy exists at the surface of a liquid-gas system. Molecules near the surface possess

excess energy as compared to the molecules in the bulk of the liquid. The system reacts

spontaneously to reduce the surface free energy in order to reach a state with the lowest total free

energy. The surface free energy is directly proportional to surface area so; one method by which

a system can reduce its surface free energy is by contracting the surface area of solids or liquids

within the system to a minimum. This is possible since the molecules at the surface are

continually moving into the bulk at a faster rate than molecules moving to the surface to replace

them. The number of molecules at this new surface reduces until the surface area reaches a

minimum which directly reduces the surface free energy also to a minimum. This contraction at

the surface gives rise to surface tension. The surface tension is the force pulling molecules at the

interface together leading to contraction at the surface (contractile force). It is defined as force

per unit length applied parallel to the surface

γ = F/2L

γ = surface tension, F = force, L = length

The unit of surface tension is Newton per meter (N/m) or dyne per centimeter (dyne/cm). The

surface tension is equivalent to surface free energy (Joules/metre2)

Interfacial tension on the other hand, is the force per unit length existing at the interface between

two immiscible liquid phases. Generally, interfacial tensions are less than surface tensions

because the adhesive forces between two liquid phases forming an interface are greater than
when liquid and gas phases exist together. If two liquids are completely miscible, it means no

interfacial tension exists between them. Oil and water do not mix because of interfacial tension.

It can only be made miscible by the introduction of an agent that has affinity for both oil and

water. This agent is called surface active agent. This agent acts the interface by reducing the

interfacial tension thus, allowing oil and water to mix.

CONSEQUENCES OF SURFACE TENSION

 Floating

Small objects like paper clip, razor blade with gravitational force smaller than the surface tension

will "float" on the surface of a liquid without becoming partly submerged as long as the object

cannot break the surface tension. The surface under tension is behaving like an elastic

membrane.

 Spherical shape of liquid drop

The spherical shape of liquid drops is as a of result surface tension. The liquid tends to decrease

the surface area, since the sphere has minimum surface area for particular volume of the liquid,

thus liquid drops are spherical in shape.

For example, water droplets are formed due to water molecules trying to interact with each other.

If the water forms a flat surface there are more molecules that need to interact with the air instead

of with each other. Formation of water drop makes the water molecules to interact more with

each other on the inside. This pulls the water molecules together because the outside surface has

a strong surface tension which keeps the drop in place.

 Wetting of solids
The degree and extent of wetting of a solid by a liquid is usually expressed in terms of the

contact angle (θ). Hence, the contact angle measures the tendency of a liquid to wet a solid

surface. A smaller θ will result in a greater contact between the solid and the liquid resulting in a

greater wetting ability of the solid by the liquid.

Contact angle =0o Complete wetting or spreading

Contact angle 0o - 90o Partial wetting

Contact angle 90o - 180o Non wetting

Contact angle =180o Perfectly non wetting

If the force of adhesion is greater than the force of cohesion, liquid wets the surface of the solid

(or spread on another liquid), but when the force of adhesion is less than force of cohesion, the

liquid refuses the surface. The word wettability is used between liquids and solids and

spreadability between liquid and liquid.

Pharmaceutical applications such as suspensions require fine solid particles to be immersed and

dispersed in a liquid vehicle. The solid particles have to be wetted for it to be dispersed in the

liquid. The nature of the solid particle will determine its wetting ability whether it can be

dispersed in a liquid. If it is has poor wetting ability surface active agent is required to increase

the extent of wetting.

 Meniscus formation

The shape of the fluid surface in a glass tube is known as the meniscus which is influenced by

surface tension. The contact angle can be used to explain these shapes (meniscus). For a liquid

such as water that wets glass, the meniscus is concave while a liquid such as mercury that does

not wet glass exhibits a meniscus that is convex.

Capillary action is the ability of a liquid to flow in narrow spaces without the assistance of, and

in opposition to, external forces such as gravity. When a capillary tube is placed in a liquid that

wets the tube, the liquid generally rises up the tube a certain distance due to surface tension. The

liquid will continue to rise in the tube until the weight of the liquid as it moves upward balances

the downward force of gravity. This occurs when the intermolecular attractive forces between the

liquid and the solid surrounding surfaces (adhesive forces) are stronger than the cohesive forces

within the liquid. If the diameter of the tube is sufficiently small, then the liquid is lifted. Note

that the height to which the liquid is lifted is inversely proportional to the radius of the tube,

which explains why the phenomenon is more pronounced for smaller tubes.

The pressure immediately below the meniscus is less than the pressure immediately above it. The

difference in these pressures will be significant and appreciable if the radius of curvature of the

meniscus inside the tube is small. On the other hand, if the radius of curvature of a container is

large, pressure difference is negligible. The difference in pressures below and above the

meniscus is the driving force which causes liquid to rise up the capillary tube. By measuring rise

in a capillary, it is possible to determine the surface tension of liquids but it is not possible to

determine interfacial tensions using the capillary rise method.

Adsorption is a process where a molecule (adsorbate) binds to the surface of a substrate

(adsorbent). It is a surface phenomenon, in which molecules only stick to the surface of the

substrate unlike absorption, in which molecules penetrate into the bulk of the substrate. For

example, water is absorbed by a sponge. Adsorption can takes place between a gas and a solid or

a liquid and a solid as well as between a liquid and another liquid. Adsorption occurs as a result

of adhesion of molecules at the interface.

MEASUREMENT OF SURFACE AND INTERFACIAL TENSIONS

The following are some of the several methods that can be used to obtain surface and interfacial

tensions.

Capillary Rise Method

Ring Method (Du Nuoy tensiometer)

Drop weight method

Wilhelmy plate methods

Bubble pressure
Oscillating drop

The choice of a particular method often depends on;

 Type of tension to be determined (whether surface or interfacial tension)

 The accuracy and convenience desired

 The size of sample available

 Effect of time on surface tension is to be studied.