Surface Chemistry

BY : NIKHIL CHHONKAR
• Adsorption Surface chemistry:

The branch of chemistry which deals with the phenomenon that occur
at the surfaces or interfaces. This phenomenon is usually studied with
the help of adsorption and colloidal state.
• Adsorption
Adsorption: The accumulation of molecular species at the surface
rather than in the bulk of a solid or liquid is termed adsorption. The
surface that adsorbs is known as adsorbent whereas the one that gets
adsorbed is known as adsorbate. For example: Silica and aluminium
gels are used to adsorb moisture to reduce humidity.
• Types of adsorption:

• Physisorption: It is also known as physical adsorption. When the gas is

accumulated on the surface of the solid on account of weak van der
Waal’s forces, it is known as physical adsorption or physisorption.

• Chemisorption: It is also known as chemical adsorption. When the gas

molecules or atoms are held to the solid surface by chemical bonds, it
is known as chemical adsorption or chemisorptions.
• Desorption:

• It is a process of removing an adsorbed substance from the surface of

an adsorbent. In absorption, the substance is uniformly distributed
throughout the bulk of the solid. For example: Chalk stick dipped in
ink.

• Sorption: When adsorption and absorption takes place

simultaneously, it is called sorption. For example: Cotton dipped in
ink.
• Enthalpy of adsorption: Adsorption generally occurs with the
release of energy and is exothermic in nature. The enthalpy change
for the adsorption of one mole of an adsorbate on the surface of
adsorbent is called enthalpy or heat of adsorption.
• Difference between Adsorption and Absorption:
• Factors affecting adsorption of gases on solids:
• Nature of gas
• Nature of adsorbent
• Specific area of the solid
• Pressure of the gas
• Effect of temperature
• Activation of adsorbent
• Freundlich Adsorption Isotherm: It gives the relationship
between the quantity of gas adsorbed by unit mass of solid adsorbent
and pressure at a constant temperature. It is represented by a
mathematical equation,
•Applications of adsorption:
• In the preparation of gas masks using activated charcoal.
• Froth floatation method used for concentration of sulphide ores.
• Silica gel is used to remove moisture.
• Ion exchange method used to soften water.
• Adsorption chromatography is used to purify and separate pigments, hormones etc.
• Charcoal powder can remove coloured impurities from sugar.
• Charcoal is used for making high vacuum.
• The cleaning action of soaps and detergents.
• In heterogeneous catalysis. In curing diseases.
• Catalysis

Catalysis: Catalyst is a substance that is used to increase the rate of the

reaction without changing itself and this process is known as catalysis.
For example,

The catalyst remains unchanged with respect to mass and composition.

Catalyst does not affect H, S. G and equilibrium constant k.
• Promoters:

Those substances which increase the activity of the catalysts are called
promoters. For example, Mo is promoter whereas Fe is catalyst in
Haber’s process.
• Poisons or Inhibitors:

Substances which destroy the activity of the catalyst by their presence

are known as poisons or inhibitors. For example, Arsenic acts as
catalytic poison in the manufacturing of sulphuric acid by contact
process.
• Types of catalysis:

Homogeneous Catalysis: A catalytic process where the reactants and the

catalyst are in the same phase (i.e. liquid or gas). For example, Catalytic
oxidation of SO2 to SO3 in presence of NO is an example of Homogeneous
catalysis.

Heterogeneous Catalysis: A catalytic process where the reactants and the

catalyst are in different phase. For example, Hydrogenation of vegetable
oils in the presence of finely divided nickel as catalyst.
• Adsorption theory of Heterogeneous Catalysis:

• According to modern adsorption theory, there are free valencies on the surface of
solid catalyst and mechanism involves following five steps:

• Diffusion of reactants to the surface of the catalyst.

• Adsorption of reactant molecules on the surface of the catalyst.
• Occurrence of a chemical reaction forming an intermediate on the surface.
• Desorption of the product molecules from the surface.
• Diffusion of product molecules away from the surface of the catalyst.
• Important features of solid catalysts:

• Activity: It is the ability of catalyst to increase the rate of reaction.

• Selectivity: It is the ability of a catalyst to direct the reaction in such a
way, that we get a desired product.
• Shape-selective catalysis by zeolites:

• It is the catalytic reaction that depends upon the pore structure of

the catalyst and the size of the reactant and product molecules.
Zeolites are shape selective catalyst having honey comb structures.
Zeolite catalyst, ZSM-5 is used in petroleum industry to convert
alcohols into gasoline by dehydration.
• Enzyme Catalysis:

Enzymes are complex nitrogenous organic compounds produced by

living plant and animals which are basically protein molecules but with
high molecular mass and form colloidal solution in water.

In enzyme catalysis, specific biochemical reactions occur.For example,

decomposition of urea into ammonia and carbon dioxide.
The enzyme urease catalyses this
decomposition.
• Characteristics of enzymes:

• Enzymes are very active catalysts as they form a colloidal solution in water.

• Like inorganic catalyst they cannot disturb the final state of equilibrium of a reversible
reaction.

• They are highly specific in nature.

• They have an optimum temperature range between 25C–35C and get deactivated at 70C.
Hence, they are highly specific to temperature.

• A small quantity of enzyme is sufficient for a large change.

• They are destroyed by UV rays.
• Their efficiency is decreased in the presence of electrolytes.
• Co-enzymes: Certain substances, which can
increase the activity of enzymes are known as
Coenzymes.
• Colloids

• Colloids: A colloid is a heterogeneous system in which one substance is dispersed

(dispersed phase dp) as very fine particles in another substance called dispersion
medium(dm). The size of colloidal particles is in the range 1-100nm.

• Colloidal solution: Colloidal solutions, or colloidal suspensions, are nothing but a

mixture in which the substances are regularly suspended in a fluid. It is a
heterogeneous system in which a very tiny and small material is spread out
uniformly all through another substance called dispersion medium. For example,
glue, ink, water etc.
• Dispersed phase: It is a component present in small proportion like
solute in solution.

• Dispersion medium: The medium in which the colloidal particles are

dispersed is called dispersion medium.

• Crystalloids: The substances whose aqueous solution can pass

through a semi-permeable membrane are called crystalloids.
• Classification based on nature of interaction between :

• Lyophillic Colloids: Lyophillic means “liquid loving”, thus, lyophillic colloids are
colloids mixed with suitable liquid with high force of attraction between the
colloids and the solvent. They are also known as intrinsic colloids. For example,
gelatin, starch, etc.

• Lyophobic Colloids: Lyophobic means “liquid hating”, thus, lyophobic colloids

consists of the phases which do not interact with each other. Their solution can
only be prepared by special methods. They are also known as extrinsic colloids.
For example, metals and their sulphides.
• Classification based on the type of particles of the dispersal phase:

• Multimolecular Colloids: When a large number of dispersed particles (having diameter

less than 1nm) combine together in a dispersion medium to form aggregates of many
molecules, it is known as multimolecular colloids. For example, sulphur sol, gold sol etc.

• Macromolecular Colloids: When certain substances form large molecules whose

dimensions are comparable to those of colloidal particles, they are known as
macromolecules. When such substances are dispersed in suitable medium, the resulting
colloidal solution is known as macromolecular solution. For example, Polythene, nylon
etc.
• Associated Colloids (Micelles):
Micelles: Those colloids which behave as normal strong
electrolytes at low concentrations, show colloidal properties
at higher concentration due to the formation of aggregated
particles of colloidal dimensions. Such compounds are also
referred to as associated colloids
• Mechanism of micelles formation:
• Molecules having lyophillic as well as lyophobic ends generally form micelles.
Such types of molecules are known as surface active molecule.
Soap is sodium or potassium salt of a higher fatty acid and may be represented as
RCOONA+.
• When dissolved in water, it breaks down into RCOO– and NA+ ions. However,
it contains two parts:-> a long hydrocarbon chain R which is hydrophobic and a
polar group COO–, which is hydrophilic.
• The RCOO– ions are present on the surface with their COO– groups in water and
the hydrocarbon chains R staying away from it and remains at the surface. At the
critical micelle concentration, the anions are pulled into the bulk of the solution
and aggregate to form a spherical shape with their hydrocarbon chains pointing
towards the centre of the sphere whereas, the COO– part remaining outward on
the surface of the sphere. The result of this is known as ‘ionic micelle’.
• Preparation of colloidal solution: Colloidal solutions can be
prepared by following methods:

• Mechanical dispersion: A suspension of coarsely ground particles prepared in dispersion

medium is fed into a colloidal mill and speed of rotation is adjusted so as to get the
particles of colloidal size.

• Electrical disintegration or Bredig’s Arc method: This process involves dispersion as well
as condensation. In this method, two rods of the metal (Au, Cu, Pt, Ag) are immersed in
cold and a direct electric arc is struck between them. This results in the formation of
vapours of metal which in turn condense to form particles of colloidal size.
• Bredig’s Arc method
• Double decomposition: This method is used to prepare colloids from inorganic salts.
• Exchange of solvent: There are a few substances that form true solution in one solvent but forms
colloidal solution in another due to lower solubility. For example, sulphur dissolved in alcohol
forms colloidal solution in water
• Peptization: When precipitates are passed into a colloidal solution in presence of an electrolyte, it
is known as peptization. The electrolyte used is known as peptizing agent.
• Purification methods of colloidal solutions: Colloidal solution
can be purified by following methods:

• Dialysis: In dialysis, a dissolved substance is removed from a colloidal

solution by means of diffusion through a suitable membrane. The
membrane used is usually a parchment paper or cellophane membrane.

• Ultrafiltration: The process of separating colloidal particles by specially

prepared filter papers whose pores is reduced by dipping it in a solution
made up of 4% of nitrocellulose in mixture of alcohol and ether.
• Electrodialysis: This method is faster than simple dialysis because in this
method, movement of ions across the membrane can be quickened by applying
electric potential through two electrodes.
• Properties of colloids:

• Brownian movement: The haphazard movement of colloidal particles

is known as Brownian movement. The movement of particles is
observed under a powerful microscope.

• Electrophoresis: When electricity is passed through a colloidal

solution, the colloidal particles move towards one of the electrodes.
This phenomenon is called electrophoresis.
• Tyndall effect: Scattering of light by colloidal particles is called Tyndall
effect.
• Hardy-Schulze rules:
• Opposite charged ions are effective for coagulation.
• The coagulating power of electrolyte increases with increase in charge
on the ions used for coagulation. For example,  for negatively
charged colloids.
• Coagulation value is the inverse of coagulating power, i.e. lower the
coagulation value, higher will be coagulating power.
• Electrokinetic Potential or Zeta Potential:

• The potential difference between the fixed layer and diffused layer of
opposite charges is called zeta potential.
• Coagulation: It is a process by which a liquid changes into a solid or
semi-solid state.
• Coagulating value: The minimum concentration of an electrolyte
which is required to cause the coagulation is known as coagulating
value.
• Emulsions: They are the type of colloidal system where the dispersed
phase and the dispersion medium both are liquids. There are two
types of emulsions:

• Oil in water: In this type of emulsion, oil is the dispersed phase and
water is the dispersion medium. For example, milk.

• Water in oil: In this type of emulsion, water is the dispersed phase

and oil is the dispersion medium. For example, butter.
• Emulsification: It is a process of preparing an emulsion.

• Emulsifying agent: It is a substance used in emulsification, to stabilize

the emulsion. For example, soap and detergents.

• Demulsification: The process of decomposing an emulsion into it’s

constituent liquids is called demulsification. It is carried out by
centrifugation, freezing, boiling or chemical methods which destroy
the emulsifying agent.
• Applications of colloids:
• Sewage disposal
• Purification of drinking water
• Smoke precipitation
• Medicines
• Tanning
• Rubber industry