Surface Chemistry

Adsorption: Introduction

Surface chemistry is the branch of chemistry that deals with the phenomenon occurring on
the surface or interface, that is, at the boundary separating two bulk phases.

Adsorption is the phenomenon of attracting and retaining molecules of a substance on the

surface of a liquid or solid.

The substance on which adsorption takes place is called the adsorbent, while the substance
that gets adsorbed is called the adsorbate.

The reverse process, that is, the removal of the adsorbed substance from the surface, is
called desorption.

Adsorption of a gas on the surface of a metal is called occlusion.

Adsorption is accompanied by a decrease in enthalpy and a decrease in entropy.

When adsorption and absorption occur simultaneously, it is called sorption.

Adsorption: Types

Physical adsorption or physisorption is the phenomenon that occurs when gas molecules or
atoms accumulate on the surface of a solid by the van der Waals forces.
Chemical adsorption or chemisorptions is the phenomenon when gas atoms or molecules
are held to the surface of a solid by chemical bonds.

Physical adsorption is non-specific in nature, but chemisorptions is highly specific in

nature.

Both physical and chemical adsorption depend upon the nature of the adsorbate.

Physical adsorption is reversible, but chemical adsorption is not.

The enthalpy of physical adsorption is 20 to 40 kJ/mol, and the enthalpy of chemical

adsorption is 80 to 240 kJ/mol.

Very little activation energy is required for physical adsorption, but high activation energy
is required for chemisorption.

Physical adsorption is multi-molecular, while chemisorptions is unimolecular.

Physical and chemical adsorption increase with an increase in the surface area of the
adsorbent.

Adsorption: Isotherms

At a constant temperature, a graph between the amount of the gas adsorbed per gram of
the adsorbent and the equilibrium pressure, or the equilibrium concentration of the
adsorbate, is called the adsorption isotherm.

The Freundlich adsorption isotherm for gases is represented by

1/n
=

The Freundlich adsorption isotherm for solutions is represented by

1/n
=

For solutions, the extent of adsorption:

• Decreases with an increase in temperature
• Increases with an increase in the surface area of the adsorbent
• Increases with an increase in the concentration of the solute

The nature of the adsorbate and the adsorbent govern the extent of adsorption.

Adsorption: Applications

Adsorption finds extensive applications both in research and in industry. Some

applications are:

• Production in high vacuum

• Gas masks
• Clarification of sugar
• Chromatographic analysis
• Heterogeneous catalysis
• Adsorption indicators
• Humidity control
• Separation of inert gases
• Froth floatation process
• Curing diseases.

Catalysis: Types and Adsorption Theory

A catalyst is a substance that alters the speed of a chemical reaction without itself being
consumed in the process, and this phenomenon is known as “catalysis”.

The substance that enhances the activity of the catalyst is called a “catalytic promoter”.

The substance that lowers the activity of the catalyst is called a “catalytic poison”.

A reaction where the catalyst and the reactants are in the same phase is called
“homogeneous catalysis”.

A reaction where the catalyst involved in the reaction in a different phase than that of the
reactants is known as “heterogeneous catalysis”.

Catalysts: Features and Shape Selective Catalysis

The activity of a catalyst is defined as its capacity to increase the speed of a chemical
reaction.

Te selectivity of a catalyst is its ability to direct the reaction to form particular products, to
the exclusion of others.

A catalytic reaction that depends upon the structure of the pores of the catalyst and the size
of the reactant and product molecules is called shape-selective catalysis.

Zeolites are microporous crystalline solids with well-defined honeycomb-like structures.

Zeolites have a three-dimensional network of silicates in which some silicon atoms are
replaced by aluminium atoms, giving an aluminium-oxygen-silicon framework.

Zeolites are efficient shape-selective catalysts.

Catalysts: Enzyme Catalysis and Catalysts in Industry

Enzymes are bio-chemical catalysts.

Enzymes are highly efficient catalysts, they speed up reactions by lowering activation
energy.

Every enzyme catalyses only one chemical reaction. It is highly specific.

The optimum temperature range for enzymatic activity is 298 K to 310 K.

The optimum pH value lies between 5 and 7.

Enzyme activity increases in the presence of certain substances known as Co-enzymes.

The activities of enzymes are slowed down by some substances known as Inhibitors or
Poisons.

The mechanism of an enzyme catalyst is a two-step process.

• Formation of the enzyme-substrate complex.

• Dissociation of the enzyme-substrate complex to form the products.

Some common Industrial Processes using the phenomenon of Surface Catalysis are:

• Haber’s process for the manufacture of Ammonia.

• Ostwald’s process for the manufacture of Nitric acid.
• Contact process for the manufacture of Sulphuric acid.

Colloids: Classification – Physical State and Nature of Interactions

In a colloidal solution, the particle size ranges from 10-9 to 10-6 metres.

Depending upon the physical state of the dispersed phase and the dispersion medium, eight
types of colloidal systems are possible.

If water is the dispersion medium, then the sol is called an aquasol or a hydrosol.

When alcohol is the dispersion medium, it is called an alcosol.

Depending upon the affinity of the dispersed phase for the dispersion medium, colloidal
systems are classified into lyophilic and lyophobic sols.

Starch, gum and gelatin form lyophilic colloids.

Arsenic sulphide, ferric hydroxide, gold and other metals form lyophobic colloids.

Lyophilic colloids are reversible colloids, but lyophobic colloids are not.
Colloids: Classification – Type of Particles

Depending upon how the different substances that form a colloidal solution acquire the
required particle size, they are classified as multimolecular, macromolecular and
associated colloids.

The formation of micelle takes place above a certain concentration, called critical micelle
concentration.

Micelle are generally formed by specific types of molecules that have both lyophilic as
well aslyophobic ends.

The cleansing action of soaps is based upon its tendency to undergo micelle formation.

Molecules having lyophilic and lyophobic ends are called as surface-active molecules or
surfactant molecules.

Soaps act as an emulsifier and helps in the stabilisation of an emulsion.

Colloids: Preparation and Purification

Lyophobic sols are prepared by special methods since they have no affinity for the solvent.

In the condensation method, the smaller particles of the dispersed phase aggregate to form
larger particles of colloidal dimensions.

Colloidal sols are obtained by double decomposition, oxidation, reduction and hydrolysis.

The Bredig’s arc method is commonly used to prepare colloidal solutions of metals like
platinum, silver and gold.

Peptisation is defined as the process of converting a freshly prepared precipitate into

colloidal form by adding a small amount of a suitable electrolyte.
Dialysis is defined as the process of removing a dissolved substance from a colloidal
solution by means of diffusion through a suitable membrane.

Ultra-filtration is defined as the process of separating the colloidal particles from the
solvent and the soluble solutes from the colloidal solution by specially prepared filters.

Colloids: Properties of Colloidal Solutions – I

At a given concentration, the value of any colligative property of a colloidal solution is of

a small order as compared to the value shown by a true solution.

The osmotic property of colloidal solutions is used to determine the average molecular
masses of colloidal particles.

The scattering of light by colloidal particles is called the Tyndall effect.

The Tyndall effect confirms the heterogeneous nature of colloidal solutions.

The size, shape and nature of the particles determine the colour of a colloidal solution.

The continuous zigzag movement of colloidal particles in a dispersion medium is called

Brownian movement.

Brownian movement is responsible for the stability of colloidal solutions.

Colloids: Properties of Colloidal Solutions – II

The particles of a colloidal solution have a positive or a negative electrical charge.

There are three reasons for the presence of the electrical charge on colloidal particles:

• Electron capture by the colloidal particles during electro-dispersion of metals.

• Preferential adsorption of ions from the solution.
• The formation of an electrical double layer.

The difference in potential between the oppositely charged fixed and diffused layers is
called “Electro Kinetic Potential” or “Zeta Potential”.

The movement of colloidal particles towards a particular electrode under the influence of
an electrical field is called electrophoresis.

Electro-osmosis is the movement of the dispersion medium under the influence of an

electrical field when the movement of the colloidal particles is prevented by a suitable
membrane.

The setting of colloidal particles is called coagulation or precipitation of the sol.

The Hardy-Schulze rule: The greater the valence of the flocculating ion, the greater is its
power to cause precipitation.

The process of protecting lyophobic colloids from coagulation is called protection of

colloids.

Emulsions

An emulsion may be defined as a colloidal dispersion of two immiscible or partially

immiscible liquids, in which one liquid acts as the dispersion medium and the other as the
dispersed phase.

Emulsions are of two types – oil in water and water in oil.

In oil in water type of emulsions, oil acts as the dispersed phase and water as the
dispersion medium.

In water in oil type of emulsions, water acts as the dispersed phase and oil as the
dispersion medium.

Substances that stabilise an emulsion are called emulsifiers.

Colloids Around us

Colloidal solutions are all around us, in the form of food, medicines, paints, inks,
photographic products, blood, river or sea water, and so on.

The neutralization of the charge on colloidal particles by suitable methods forms the basis
for:

• The Cottrell Precipitator

• The Clotting of Blood
• The Purification of Water
• The Tanning of Leather
• Artificial Rain
• The Formation of a Delta
• Sewage Disposal
• The Production of Rubber