Surface Chemistry

Adsorption - Mechanism and Types

Adsorption

• Phenomenon of accumulation of molecules at the surface of a solid, which results into a higher
concentration at the surface than in the bulk

• The substance adsorbed is called adsorbate.

• The substance on which adsorption takes place is called adsorbent.

• The phenomenon of removing adsorbate from adsorbent is called desorption.

Distinction between Adsorption and Absorption

• Adsorptionis a surface phenomenon of accumulation of molecules of a substance at the surface

rather than in the bulk of a solid or liquid. In adsorption, the substance gets concentrated at the
surface only. It does not penetrate through the surface to the bulk of the solid or liquid. For
example, when we dip a chalk stick into an ink solution, only its surface becomes coloured. If we
break the chalk stick, it will be found to be white from inside.

• On the other hand, the process of absorption is a bulk phenomenon. In absorption, the absorbed
substance gets uniformly distributed throughout the bulk of the solid or liquid.

Mechanism of Adsorption

• All the forces acting between the particles inside the adsorbent are mutually balanced. However, on
the surface, the particles are not surrounded by atoms or molecules of their kind on all sides and
hence, they possess unbalanced or residual attractive forces. These forces of the adsorbent are
responsible for attracting the adsorbate particles on its surface.

• The extent of adsorption increases with the increase of surface area per unit mass of the adsorbent
at a given temperature and pressure.

• Adsorption is an exothermic process (ΔH = negative).

• It is accompanied by decrease in entropy of the system (ΔS = negative).

• Reason − When a gas is adsorbed, the freedom of movement of its molecules becomes restricted.

• Adsorption process is spontaneous in nature (ΔG = negative).

• When ΔG = 0, state of equilibrium is attained.

 Types of Adsorption

1. Physical adsorption or physisorption − When the accumulation of gas on the surface of a solid
occurs on account of weak van der Waal’s forces

2. Chemical adsorption or chemisorption − When the gas molecules or atoms are held to the
surface by chemical bonds

• Chemical bonds may be covalent or ionic.

3. Comparisons of physisorption and chemisorption are listed in the given table.

Physisorption Chemisorption

• Arises because of van der Waals forces • Arises because of chemical forces

• Not specific in nature • Highly specific in nature

• Reversible in nature • Irreversible in nature

• Depends on the nature of gas

• It also depends on the nature of gas. Gases which
• More easily liquefiable gases are adsorbed can react with adsorbent show chemisorption.
readily.

• Enthalpy of adsorption is low. • Enthalpy of adsorption is high.

• No appreciable activation energy is required.• Sometimes, high activation energy is required.

• Results into multi-molecular layers • Results into uni-molecular layer

• Low temperature is favourable for
• High temperature is favourable for adsorption. It
adsorption. It decreases with increase of
increases with the increase of temperature.
temperature.

• Increases with increase in surface area • Also increases with increase in surface area

Adsorption Isotherms, Adsorption from Solution Phase & Applications of Adsorption

Adsorption Isotherms

• The plots between the extent of adsorption against the pressure (P) of the gas at constant
temperature (T)

• Freundlich adsorption isotherm

• Freundlich adsorption isotherm gives an empirical relationship between the quantity of gas
adsorbed by a unit mass of solid adsorbent and pressure at a specific temperature.

• From the given plot it is clear that at pressure Ps, reaches the maximum value. Ps is called the
saturation pressure. Three cases arise from the graph.

• Case I: At low pressure

The plot is straight and sloping, indicating that the pressure is directly proportional to
 i.e., ∝P

• Case II: At high pressure

When pressure exceeds the saturated pressure, becomes independent of P values.

• Case III: At intermediate pressure

At intermediate pressure, depends on P raised to the powers between 0 and 1.

• This relationship is known as the Freundlich adsorption isotherm.

• On plotting the graph between log and log P, a straight line is obtained, with the slope equal

to and the intercept equal to log k.

 Adsorption from Solution Phase

The following observations have been made in the case of adsorption from solution phase.

• With the increase in temperature, the extent of adsorption decreases.

• With an increase in the surface area of the adsorbent, the extent of adsorption increases.

• The extent of adsorption depends on the concentration of the solute in solution, and on the nature
of the adsorbent and the adsorbate.

• Can be approximately described by Freundlich’s equation by using the concentration (C) of the
solution instead of pressure

• On plotting the graph between log and log C, a straight line is obtained, with the slope equal

to and the intercept equal to log k.

Applications of Adsorption

• Production of high vacuum: The traces of air can be adsorbed by charcoal from a vessel evacuated
by a vacuum pump, to give a very high vacuum

• Gas mask: Used for breathing in coal mines, to adsorb poisonous gas
• Silica and aluminium gels are used as adsorbents for controlling humidity.

• A number of drugs are used for killing germs; the drugs get adsorbed on the germs.

• Used in heterogeneous catalysis

• Used in chromatographic analysis: It is based on the phenomenon of adsorption; finds a number of

applications in analytical and industrial fields

Catalysis

• Catalysts alter the rate of a chemical reaction, and remain chemically and quantitatively
unchanged after the reaction.

• Promoters enhance the activity of a catalyst.

• Poisons decrease the activity of a catalyst.

• Homogeneous catalysis − When the reactants and the catalyst are in the same phase

• Heterogeneous catalysis −When the reactants and the catalyst are in different phases

Adsorption Theory of Heterogeneous Catalysis

This theory explains the mechanism of heterogeneous catalysis. The mechanism involves the
following steps:

• Diffusion of reactants to the surface of the catalyst

• Adsorption of the reactant molecules on the surface of the catalyst

• Occurrence of chemical reaction on the catalyst’s surface through the formation of an intermediate

• Desorption of reaction products from the catalyst surface (making the surface available for more
reactions to occur)

• Diffusion of reaction products away from the surface of the catalyst

The adsorption of reacting molecules, formation of intermediate and desorption of products are
shown in the given figure.
 Important Features of Solid Catalysts

• Activity − Depends upon the strength of chemisorption to a large extent

• Selectivity − Ability to direct a reaction to yield a particular product

Shape-Selective Catalysis

• The catalytic reaction that depends upon the pore structure of the catalyst and the size of the
reactant and product molecules

• Zeolites are good shape-selective catalysts

Reason: They have honeycomb-like structures.

Enzyme Catalysis

• Enzymes −Complex nitrogenous compounds which are produced by living plants and animals

• They catalyse numerous reactions in the bodies of animal and plants to maintain the life processes.

• Example:

Inversion of cane sugar into glucose and fructose by enzyme invertase

Conversion of glucose into ethyl alcohol by enzyme zymase

• The given table lists some enzymatic reactions.

Enzyme Source Enzymatic reaction

 Invertase Yeast Sucrose → Glucose and fructose

Zymase Yeast Glucose → Ethyl alcohol and carbon dioxide

Diastase Malt Starch → Maltose

Maltase Yeast Maltose → Glucose

Urease Soyabean Urea → Ammonia and carbon dioxide

Pepsin Stomach Proteins → Peptides

• Characteristics of Enzyme Catalysis

• Highly efficient

• Highly specific in nature

• Highly active under optimum temperature

• Highly active under optimum pH

• Increase in activity in the presence of activators and co-enzymes

• Influenced by inhibitors and poisons

• Mechanism of Enzyme Catalysis

Steps involved are −

• Binding of enzyme to substrate to form an activated complex

E + S → ES#
• Decomposition of the activated complex to form products

ES# → E + P

The given figure represents the mechanism of an enzyme-catalysed reaction.

Catalysts in Industry

Some of the important catalytic processes are listed in the given table.

- Process Catalyst

Haber’s process for the

Finely divided iron, molybdenum as promoter; conditions:
1. manufacture of ammonia
200 bar pressure and 723−773K temperature
N2(g) + 3H2(g) → 2NH3(g)

Ostwald’s process for the

manufacture of nitric acid

4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

2. Platinised asbestos; temperature 573K
2NO(g) + O2(g) → 2NO2(g)

4NO2(g) + 2H2O(l) + O2(g) →

4HNO3(aq)
 Contact process for the
manufacture of sulphuric acid

2SO2(g) + O2(g) → 2SO3(g)

Platinised asbestos or vanadium pentoxide (V2O5);
3.
temperature 673−723K
SO3(g) + H2SO4(aq) →
H2S2O7(l) (oleum)

H2S2O7(l) + H2O(l) → 2H2SO4(aq)

Colloids - Classification and Preparation

Colloid

• Heterogeneous system

• Intermediate between true solutions and suspensions

• The range of diameters of colloidal particles is between 1 and 1000 nm.

• Consists of two phases − dispersed phase and dispersion medium

Classification of Colloids

Colloids are classified depending upon the following three criteria:

• Physical state of dispersed phase and dispersion medium

• Nature of interaction between dispersed phase and dispersion medium

• Type of particles of the dispersed phase

Depending Upon the physical state of Dispersed Phase and Dispersion Medium

Dispersed phase Dispersion medium Type of colloid Example

Solid Solid Solid sol Gem stones, some

coloured glasses
 Solid Liquid Sol Paints, cell fluids

Solid Gas Aerosol Smoke, dust

Liquid Solid Gel Cheese, butter,

jellies

Liquid Liquid Emulsion Milk, hair cream

Liquid Gas Aerosol Fog, mist, cloud

Gas Solid Solid sol Pumice stone, foam,

rubber

Gas Liquid Foam Froth, soap lather

Differences Between True Solution, Colloid and Suspension

S.No. True solution Colloid Suspension
1. Homogeneous Heterogeneous Heterogeneous
Particles are either
Particles are
single
Particles are ions aggregates of
2. macromolecules or
or molecules. molecules or
aggregates of
atoms.
molecules or atoms.
Particle size varies Particle size varies
Particle size is
3. between 0.1 nm to between 1 nm to
larger than 103 nm.
1 nm. 103 nm.
The particles do The particles do not The particles settle
4.
not settle. settle. out.
The particles do The particles The particles do
5.
not scatter light. scatter light. not scatter light.
 It does not exhibit It exhibits It does not exhibit
properties like properties like properties like
6. electrophoresis, Brownian electrophoresis,
Brownian movement, Brownian
movement, etc. electrophoresis etc. movement, etc.

Depending Upon the Nature of Interaction between Dispersed Phase and Dispersion
Medium

• Lyophilic colloids (solvent attracting)

• Also called reversible sols

• Quite stable and cannot be easily coagulated

• Lyophobic colloids (solvent repelling)

• Also called irreversible sols

• Unstable and can be easily coagulated

Depending Upon the Type of Particles of the Dispersed Phase

• Multi-molecular colloids − Species having size in the colloidal range

(diameter < 1 nm)

• Macromolecular colloids − Macromolecules (such as starch, cellulose, proteins, enzymes, etc.) in

suitable solvents form solutions in which the size of the macromolecules may be in the colloidal
range.

• Associated colloids (Micelles) − Some substances at low concentration behave as normal

electrolytes, but at higher concentrations exhibit colloidal behaviour due to formation of
aggregates. The aggregated particles are called micelles and are also known as associated colloids.

• The temperature above which the formation of micelles takes place is called Kraft temperature
(Tk).

• The concentration above which the formation of micelles takes place is called critical micelle
concentration (CMC).

Preparation of Colloids

• Chemical method − Can be prepared by chemical reactions leading to the formation of molecules,
which then aggregate leading to the formation of sols
• Electrical disintegration or Bredig’s Arc method − It involves dispersion as well as
condensation. Colloidal sols of metals such as gold, silver, platinum, etc. can be prepared by this
method.

• Peptisation − Process of converting a precipitate into colloidal sol by shaking it with dispersion
medium in presence of small amount of electrolyte (peptising agent)

Purification of Colloidal Solutions & Properties of Colloidal Solutions

Purification of Colloidal Solutions

• Reduction of the amount of impurities to a requisite minimum

• Dialysis

• It is the process of removing a dissolved substance by diffusion through a suitable membrane.

• The apparatus used for this purpose is called dialyser.

• The colloidal solution is placed in a bag of suitable membrane while pure water is taken outside.

• The molecules and ions diffuse through the membrane into the outer water and pure colloidal
solution is left behind.

• Electro-dialysis
• The process of dialysis is quite slow and can be made faster by applying an electric field.

• When the electric field is applied, the ions present in the colloidal solution migrate out to the
oppositely charged electrodes.

• Ultra-filtration

• It is the process of separating the colloidal particles from the solvent, and the soluble solutes
present in the colloidal solution, by specially prepared filters.

• The filters are permeable to all substances, except the colloidal particles.

• It is a slow process and to speed it up, pressure or suction is applied.

Properties of Colloidal Solutions

• Colligative properties

• Osmotic pressure, lowering in vapour pressure, depression in freezing point and elevation in
boiling point

• The values of these properties are of a small order as compared to the values shown by true
solutions at the same concentrations.

• Tyndall effect

• It is due to the fact that colloidal particles scatter light in all directions in space.

• The scattering of light illuminates the path of the beam of light.

• Colour

• Depends on the wavelength of the light scattered by the dispersed particles

• Wavelength of light depends on the size and nature of the particles.

• Brownian movement
• Zig-zag movement of colloidal particles

• Smaller the size and lesser the viscosity, faster is the motion.

• Charge on colloidal particles

• Colloidal particles carry an electric charge.

• May either positive or negative

• The given table lists some common sols with the nature of charge on their particles.

Positively charged sols Negatively charged sols

Hydrated metallic oxides

Metals (e.g., copper, silver, gold sols)
(e.g., Al2O3.xH2O, CrO3.xH2O, Fe2O3.xH2O)

Metallic sulphides (e.g., As2S3,

Basic dye stuffs (e.g., methylene blue sol)
Sb2S3, CdS sols)

Acid dye stuffs (e.g., eosin,

Haemoglobin (blood)
congo red sols)

Oxides (e.g., TiO2 sol) Sols of starch, gum, gelatin, clay, charcoal, etc.

• Electrophoresis

• Movement of colloidal particles under applied electric potential

• Electro osmosis: Movement of dispersion medium through the membrane, in an applied electric
field

• Coagulation or precipitation
 Process of settling of colloidal particles

Ways to Carry Out Coagulation of Sol

• By electrophoresis

• By mixing two oppositely charged sols

• By boiling

• By persistent dialysis

• By addition of electrolytes

Hardy−Schulze rule

The greater the valence of the flocculating ion added, the greater is its power to cause precipitation.

Emulsions & Applications of Colloids

Emulsions

• Colloidal systems in which both the dispersed phase and the dispersion medium are liquids

• There are two types −

• Oil dispersed in water (O/W type)

• Water dispersed in oil (W/O type)

• Emulsifying agent: The third component used for stabilising an emulsion

• Emulsification:Process of making an emulsion

Preparation of Emulsion

• It is prepared by shaking vigorously the mixture of two immiscible liquids.

• A small amount of an emulsifying agent or an emulsifier is added to the emulsion during its
preparation to prevent its breaking as the two immiscible liquids are unstable and separate out in
two layers on standing.
• The emulsifier forms a protective layer around the dispersed phase which prevents the particles
from coming closer to one another, thereby undergoing coagulation.

Properties of Emulsion
• The particles of disperse phase in emulsions are globules which are larger in size than the particles
of disperse phase in sols.
• The globules migrate under the application of an electric field as they are negatively charged.
• On addition of electrolytes containing divalent or trivalent particles, the globules coagulate.
• The globules show Tyndall effect and Brownian motion.

Breaking of Emulsion

• Heating, freezing and centrifugation can be employed to separate the two liquids in emulsions.
• Addition of electrolytes in large quantities causes coagulation of dispersed phase particles.
• Any chemical species capable of causing chemical destruction of the emulsifier results in
separation of the two liquids.

Colloids around Us

• Blue colour of the sky: Dust particles along with water suspended in air scatter blue light.

• Food particles such as milk, butter, fruit juices are all colloids.

• Fog,mist and rain are also colloids.

• Blood:A colloidal solution of an albuminoid substance

• River water: A colloidal solution of clay

• Fertile soils are colloidal in nature, in which humus acts as a protective colloid.

Applications of Colloids

• Purification of drinking water: Water obtained from natural resources often contains suspended
impurities. Alum is added to coagulate the suspended impurities.

• Medicines :Most medicines are colloidal in nature. Example: Milk of magnesia(an emulsion)

• In the cleansing action of soaps and detergents

• Photographic plates or films are prepared by coating an emulsion of the light sensitive AgBr in
gelatin, over glass plates or celluloid films.

• Paints, inks, rubber, graphite lubricants, etc., are all colloidal solutions.

• Rubber industry: Rubber is obtained by the coagulation of latex, which is a colloidal solution of
rubber particles.

• Electrical precipitation of smoke:

• Smoke is a colloidal solution of solid particles (carbon, dust, arsenic compounds, etc.).

• Smoke can be electrically precipitated by using the Cottrell precipitator.