CH 301, Surface Chemistry, Colloids and Phase Equilibria

Lecture 01

Chapter: Surface Chemistry

Topics
 Surface Chemistry
 Nature of Surfaces
 Surface active agents
 Surface free energy
 Wetting
 Contact angle
 Adsorption
 Application of Surface Chemistry

Nahida Akter , Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.

 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Surface Chemistry
Surface chemistry is referred to as the study of the phenomenon
occurring on the surfaces of substances. This is very applicable in
industries and day to day lives. In other words, surface chemistry deals
with all types of surface phenomenon. It occur at the interface of two
surfaces which can be solid-liquid, solid-gas, liquid-gas, etc.

There are various phenomena taking place on the surface of substances

and some of them are:

Solid Surface
 Adsorption Liquid drop Interface/
Boundary
 Heterogeneous Adsorption
 Catalysis
 Corrosion Solid
Bulk material
 Crystallization

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Nature of Surfaces
The atoms or molecules on a surface of a liquid or solid are subjected to
unbalanced forces due to their positions. A molecule in the interior of a solid
body or a liquid experiences an intermolecular force of equal magnitude in all
directions. The resultant force on this particular molecule is, therefore, zero.
But the condition of the molecules on the surface is different as they are pulled
downwards and sideways, but no forces act on them from above as shown in
Figure. As a result, there remains a residual field of force acting only on the
surface. These unbalanced forces on the surface molecules give rise to surface
tension in liquids.

“Surface tension is the tension of the

surface film of a liquid caused by the
attraction of the particles in the
surface layer by the bulk of the
liquid, which tends to minimise surface
area”.

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

In solids, due to rather fixed positions of the molecules or atoms, the exact
nature and magnitude of the unbalanced forces are different from those in
liquids, thus imparting some special properties to solid surfaces. The unsatisfied
combining capacities associated with surface atoms or molecules render them
particularly reactive towards any other material body, especially liquids and gases
when the latter happen to come near the field of force. At the first available
opportunity, these surface atoms molecules will try to satisfy the ‘unsaturation’
by ‘capturing’ other molecules or atoms.

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Surface Active Agent

Surface active agents, also known as tensides, amphiphiles or surfactants

(for short) is a general name for substances that tend to preferentially
accumulate at the boundary (i.e., interface) between two phases.

Surface-active compounds are characterized by having two distinct regions

in their chemical structure, one hydrophilic or water-loving region (usually
depicted with a circle) and the other hydrophobic or water-hating region
(usually depicted with a wiggly chain or a rectangular box). The existence
of such two regions in a molecule is known as amphipathy, and the molecules
are consequently often referred to as amphiphiles or amphipathic
molecules.

Schematic representation of surfactant

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Surface Free Energy

Surface energy quantifies the disruption of intermolecular bonds that occurs
when a surface is created. It is also called surface free energy or interfacial
free energy. In simple language, surface energy can be defined as the work per
unit area done by the force that creates the new surface.

The SI unit of Surface Energy is N/m.

Wetting
In the adhesive vocabulary, the term “wetting” refers to the ease with which an
adhesive can intimately contact and spread over a given substrate. There are a
variety of forces (ionic, static, polar, van der Waals etc.) acting between the
adhesive and the substrates that ensure good bonding. Good wetting provides a
larger area of contact where these forces may act. Consequently, good wetting
is crucial for good bond formation.

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

The degree of wetting of any given substrate can be attributed to the

critical surface energy of the substrate and the adhesive. As a general
rule, for good wetting, the critical surface energy of the substrate
should be higher than the critical surface energy of the adhesive.

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Contact Angle
A contact angle (also referred to as a wetting angle) is formed when a
drop of liquid is placed on a material surface. The surface tension of the
liquid and the attraction of the liquid to the surface causes the drop to
form a dome shape.
The contact angle is defined as the angle between a tangent to the liquid
surface and the solid surface at this point.

Theta (Θ) is the contact angle in the

illustration here. If the drop of liquid
spreads across a surface, the contact
angle becomes smaller.

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Adsorption on Surface Energy

Accumulation of species on higher concentration on the surface of a
substance due to intermolecular force is known as adsorption. For
Example, gases such as H2, O2, N2 adsorbs on the surface of activated
charcoal.

Types of Adsorption
Due to the force of interaction between adsorbate and adsorbent,
adsorption in surface chemistry is classified into two types;
1. Physical Adsorption or Physisorption
2. Chemical Adsorption or Chemisorption

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Difference
between Physical
and Chemical
adsorption

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Applications of Surface Chemistry

In a wider perspective, surface chemistry deals with the interaction of
surfaces of one system with that of the other system. Some phenomena
work on this principle such as:

 Catalysis
 Colloid Formation
 Electrode Reactions
 Chromatography
 Surface Chemistry has a major role in various chemical processes such as:

1) Enzymatic reactions at the biological interfaces found in the cell walls

and membranes.
2) In the electronics industry, they are used in the surface and interface of
microchips found in computers.
3) In automobile exhausts, the heterogeneous catalysts found in the
catalytic converter for cleaning emissions.

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.
 CH 301, Surface Chemistry, Colloids and Phase Equilibria

Nahida Akter , Assistant Professor, Dept. of Chemistry, University of Barishal, Barishal-8200, Bangladesh.