Surface Chemistry

“The branch of physical chemistry, which

deals the nature of surfaces and also with
the chemical and physical processes which
takes place on the surfaces, is called
surface chemistry”.
In surface chemistry, we study the
phenomenon of adsorption, catalysis and
colloidal properties.
 The word "adsorption" was coined in 1881 by German physicist
Heinrich Kayser (1853-1940)
Interface: The boundary b/w two or more phases
Adsorbate: It is the substance which is adsorbed at the surface of
another substance.
 Examples are: gases, dyes etc.
Adsorbent: It is the substance which adsorbs the other substance at
its surface.
 Examples are: activated charcoal, bone charcoal, alumina, silica
gel, kaolin.
 In pharmacy, activated charcoal is considered to be the most
effective single agent available as an emergency decontaminant in
the gastrointestinal tract. It is used after a person swallows almost
any toxic drug or chemical.
 Adsorption
adsorption is the adhesion or sticking together of
molecules of gas, liquid, or dissolved solid to the surface
of solid or sometime liquid. This process creates a film of
the adsorbate on the surface of the adsorbent.
 The phenomenon of attracting and retaining the
molecules of a substance on the surface of a liquid or
solid resulting in to higher concentration of the
molecules on the surface is called adsorption.
Absorption: is the passage of one substance into or
through the bulk of another medium and saturate the
whole medium and form solution.

Causes of adsorption:
 Unbalanced forces of attraction or free valencies which
is present at the solid or liquid surface, have the property
to attract and retain the molecules of a gas or a dissolved
substance on to their surfaces with which they come in
contact.
Example: Ammonia gas placed in contact with charcoal
gets adsorbed on the charcoal whereas ammonia gas
placed in contact with water gets absorbed into water,
Adsorption is a surface phenomenon while
absorption involves the whole volume of the
material.
Adsorbed substance is loosely held and can be
reversed easily
while absorbed substance is comparatively
difficult to remove.
Cotton in water(absorption)
Ordinary paper in water or coating on backside
of mirror(adsorption).
Adsorption Absorption
It is a surface phenomenon. It concerns with the whole mass of the
absorbent.

In it, the substance is only retained on It implies that a substance is uniformly

the surface and does not go into the bulk distributed, through the body of the solid
or interior of the solid or liquid. or liquid.

In it the concentration of the adsorbed In it the concentration is low.

molecules is always greater at the free
phase.

It is rapid in the beginning and slows It occurs at the uniform rate

down near the equilibrium.

Examples : (i) Water vapours adsorbed by Examples : (i) Water vapours absorbed by
silica gel. anhydrous CaCl2
(ii) NH3 is adsorbed by charcoal. (ii) NH3 is absorbed in water forming
NH4OH
Silica gel
Silica gel is a chemically inert, nontoxic, polar and
dimensionally stable (< 400 °C or 750 °F) amorphous
form of SiO2. It is prepared by the reaction between
sodium silicate and acetic acid, which is followed by a
series of after-treatment processes. These after
treatment methods results in various pore size
distributions.
Silica is used for drying of process air (e.g. oxygen,
natural gas) and adsorption of heavy (polar)
hydrocarbons from natural gas.
 Surface Energy
An explanation of why material accumulates at the
interface is based on the excess energy associated
with particles at interfaces. For example, in the case
of pure water and air, the water molecules at the air-
water interface have higher energy than water
molecules in the interior of the water phase. The
reason that these surface molecules have higher
energy is that, unlike the interior molecules, they
have an unbalanced force component (on the airside
of the molecule).
These surface molecules have additional energy
to balance the forces. It takes energy to put
molecules on the surface. This excess energy is
called surface tension. Since it takes energy to
create interfacial surfaces, the system will try
to minimize the total interfacial surface area.
Hence we see spherical droplet, meniscus etc
d
Surface process bulk process
 Physical adsorption or physiosorption:
Vander Waals attraction between adsorbate and
adsorbent or that type of adsorption in which
the adsorbate and adsorbent are held together
by Vander Waals forces (weak intermolecular
attraction) is called Physical adsorption . The
attraction is not fixed to a specific site and the
adsorbate is relatively free to move on the
surface. This is relatively weak, reversible,
adsorption capable of multilayer adsorption.
Chemical adsorption or
chemosorption: That type of adsorption
in which the adsorbate and adsorbent are
held together by strong chemical bonding.
This interaction is much stronger than
physiosorption. As chemical bonding is
strong so the Adsorbed molecules are not
free to move on the surface. It is
irreversible process and typically a
monolayer is formed.
 Types of Adsorption Modes

Physical adsorption or
physisorption
Bonding between molecules and
surface is by weak van der Waals
forces.

Chemical bond is formed between

molecules and surface.
Chemical adsorption or
chemisorption
Factors effecting the adsorption:
1.Pressure: pressure has direct relation with adsorption it is expected that
extent of adsorption increases with increase in pressure and decrease in
pressure causes desorption.
2.Stirring: Normally with agitation the adsorption decreases.
3.Affinity between adsorbent and adsorbate:
4.Temperature: Adsorption is an Exothermic process so in case of
physical adsorption as the temp increase physical adsorption decrease
because vanderwaal’s forces are strong at low temperatures. However,
the chemisorption first increases with rise in temperature and then starts
decreasing.
5.Surface area: Adsorption being a surface phenomenon, the extent of
adsorption depends upon the surface area. Increase in the surface area
of the adsorbent, increases the total amount of gas adsorbed. Thus finely
divided metals (nickel, platinum) and porous substances (Charcoal,
silica gel) provides large surface area and are best solid adsorbents.
6.Nature of adsorbate (Gas): The amount of gas adsorbed by a solid
depends upon the nature of gas. In general, more easily liquefiable a
gas is (i.e. higher its critical temperature), the more readily will it be
adsorbed. Thus 1gm of activated charcoal adsorbs 380 ml of sulphur
dioxide (critical temperature 157°C), 16 ml of methane (critical
temperature –83°C) and 4.5 ml of hydrogen (critical temperature –
240°C). This is valid for physical adsorption only.
 Since Chemical Adsorption is Specific in nature, it
occurs only if the gas can form a chemical bond with the solid.
7.pH : On changing PH if adsorbent ionized than solution form so no
adsorption occurs.
If on changing PH the adsorbent is unionized than solution do not form
and adsorption occurs.
8. Concentration of adsorbate: Direct relation i.e. greater the
concentration of adsorbate greater will be adsorption
Pharmaceutical Application:
Decolourization: charcoal is also used as decolorizing agent
because it has capacity to remove dye (color) from preparation
by the process of adsorption.
Activated charcoal: Most commonly used antidote in
accidental poisoning. It adsorb poisons and toxic substances
through mechanism of adsorption.
Gasmasks: The gas mask is a mask used to protect the wearer
from inhaling airborne pollutants and toxic gases. Airborne
toxic materials may be gaseous (for example the chlorine gas
used in World War I) or particulate (such as many
biological agents developed for weapons such as bacteria,
viruses and toxins).charcoal(activated carbon) is also used is
gas masks to adsorb the airborne pollutants and toxic gases.
Desiccation: The removal of moisture from solid, liquid or gas is
called desiccation. Most commonly silica gel is used for
desiccation. silica gel remove moisture through adsorption
mechanism.
Removal of pyrogens: Through adsorption process pyrogens
(endotoxin) can be removed from preparations. For example
polymer of an aziridine compound is used to adsorb pyrogens from
preparations
Emulsification: the stability of emulsion also depends on the
adsorption process, because greater the adsorption of emulsifying
agents at the interface greater will be stability.
Drugs: like kaolin and pectin(anti-diarrheal) acts through
adsorption mechanism.
Solid-liquid chromatography: