SURFACE CHEMISTRY

It is the branch of chemistry that deals with the study of nature of surfaces and the different
processes taking place at the surface. The important surface phenomena are adsorption, corrosion,
electrode process, heterogeneous catalysis, dissolution etc.
ADSORPTION
It is the process of concentration or accumulation of a substance on the surface of another
substance.
Adsorbate: The substance which is adsorbed is called adsorbate.
Adsorbent: The substance whose surface on which adsorption takes place is called adsorbent. The
commonly used adsorbents are charcoal, silica gel, alumina gel, clay, colloids, and metals in finely
divided state etc.
* Adsorption is a surface phenomenon. Some examples of adsorption are:

1. Powdered charcoal adsorbs gases like H2, O2, CO, Cl2, NH3, and SO2 etc.

2. Silica gel adsorbs moisture

3. Animal charcoal adsorbs colouring material from sugar solutions
Desorption: The process of removal of an adsorbed substance from the surface of adsorbent is called
desorption. i.e. it is the reverse of adsorption.

 What is absorption?
Ans: It is the phenomenon in which a substance is uniformly distributed throughout the bulk, i.e. it
is the penetration of the substance through the surface into the bulk of the solid.
Eg: Water vapours are absorbed by anhydrous CaCl2.
 Distinguish between adsorption and absorption.
In adsorption, the substance is concentrated only at the surface while in absorption, the
substance is uniformly distributed throughout the bulk of the solid. So adsorption is a surface
phenomenon while absorption is a bulk phenomenon.
 Sorption.
If adsorption and absorption occur simultaneously, the process is called sorption.
Eg: When a chalk stick is dipped in ink, the surface retains the colour of the ink due to
adsorption of coloured molecules while the solvent of the ink goes deeper into the stick due to
absorption. On breaking the chalk stick, it is found to be white from inside.

 Mechanism of Adsorption (Why adsorption?)

- The surface particles of the adsorbent are not in the same environment as the particles inside
the bulk (inner part).
- Inside the adsorbent, all the forces are mutually balanced. But at the surface, there is always
some unbalanced or residual forces. These forces of the adsorbent are responsible for
adsorption.
 Define Enthalpy of adsorption (or Heat of adsorption?)
Adsorption is an exothermic process. i.e. some heat is always evolved during adsorption. The
amount of heat evolved when 1 mole of an adsorbate is adsorbed on the surface of an adsorbent
is called heat of adsorption.
Thermodynamic aspects of adsorption
Adsorption is an exothermic process. When a gas is adsorbed, the degree of freedom
(randomness) of its molecules decreases and hence the entropy decreases. i.e., ΔS becomes
negative. Adsorption is thus accompanied by decrease in enthalpy as well as decrease in entropy of
the system.
For a process to be spontaneous, ΔG must be negative. On the basis of equation, ΔG = ΔH – TΔS, ΔG
can be negative if ΔH >TΔS. As the adsorption proceeds, ΔH becomes less and less negative ultimately
ΔH becomes equal to TΔS and ΔG becomes zero. At this state equilibrium is attained.

 Why adsorption is exothermic?

When a gas is adsorbed, the degree of freedom (randomness) of its molecules decreases and hence
the entropy decreases. i.e., ΔS becomes negative. Adsorption is thus accompanied by decrease in
enthalpy (heat will evolve) as well as decrease in entropy of the system.
 Types of adsorption
Depending on the force of attraction between adsorbent and adsorbate, adsorption is of two
types – i) Physical adsorption or physisorption
ii) Chemical adsorption or chemisorption.
i) Physisorption
- If the force of attraction between adsorbent and adsorbate is weak van der Waals force, it is
called physical adsorption or physisorption.
- For physisorption, the heat of adsorption is low and it is not specific since the van der
Waals forces are universal. That is any substance can form van der Waals force with any surface.

ii) Chemical adsorption or chemisorption.

- In chemisorptions, the force of attraction between adsorbent and adsorbate is chemical bond.
- It is also called activated adsorption since it involves some activation energy.
- For chemisorption, the enthalpy of adsorption is high and it takes place at high temperature.
- It is highly specific in nature and it will occur only if there is some possibility of Chemical
bonding between adsorbent and adsorbate.

- A physisorption at low temperature may pass into chemisorption at high temperature.

For e.g. Hydrogen gas is first adsorbed on nickel by van der Waals force. But at high
temperature, the molecules of H2 dissociate to form H atoms and they are adsorbed
on the surface of Ni by chemical bond.

Both physisorption and chemisorption increases with increase in surface area of the
adsorbent. Surface area can be increased by powdering the adsorbent.
Distinction between physisorption and chemisorption

Properties Physisorption Chemisorption

1 Force of attraction Weak van der Waals force Strong chemical bond
2 Specificity Not specific in nature Highly specific
3 Reversibility Reversible Irreversible
4 Extend of adsorption Easily liquefiable gases (e.g. CO2, HCl, Gases which can react with the
and nature of gas NH3 etc) are easily adsorbed than adsorbent
show chemisorption
permanent gases (e.g. H2, N2, O2 etc)
5 Heat of adsorption Low (20-40 kJ/mol) High (80-240kJ/mol)
6 Temperature Low temperature is favourable. It High temperature is
decreases with increase in favourable. It increases
temperature with increase in temperature

7 Activation energy No appreciable activation energy is High activation energy is

needed required
8 Nature of layer Multimolecular layer of adsorption Only unimolecular layer of
occurs adsorption occurs

Adsorption Isotherms
The variation in the amount of gas adsorbed by the adsorbent with pressure at constant temperature
can be expressed by means of a graph called adsorption isotherm.
Freundlich adsorption isotherm:
Freundlich gave an empirical relationship between the quantity of gas adsorbed by unit mass of
solid adsorbent and pressure, at a particular temperature. The relationship can be expressed by the
following equation:
1/n
= k.P (where n > 1) where x Is the mass of the gas adsorbed,
m is the mass of the adsorbent,
k , n are constants which depend on
the nature of the adsorbent and the gas at a particular temperature.
The above relationship can be represented in the form of a graph as follows:
- From the graph it is clear that x/m (extend of adsorption) increases with pressure up to a certain
pressure called saturation pressure (Ps) and after that it becomes constant.
- If we take logarithm of the above equation, we get

log x/m = log k + 1/n log P

(This equation is of the form y = mx+c, equation for a straight line. So if we plot log x/m against
log P, we get a straight line, which verifies Freundlich isotherm. )

- The value of 1/n in Freundlich isotherm ranges from 0 to 1.

When 1/n = 0, x/m = a constant. i.e. the adsorption is independent of pressure.
When 1/n = 1, x/m = k.p, the adsorption varies linearly with pressure.
- Freundlich adsorption isotherm failed to explain adsorption at very high pressures.
-
Adsorption from solution
Certain solid adsorbents can adsorb solute particles from solution. This is known as adsorption from
solution.
E.g :
1) When a solution of acetic acid in water is shaken with charcoal, a part of the acid is adsorbed by the
charcoal and the concentration of the acid decreases in the solution.
2) Animal charcoal adsorbs colouring materials from sugar solution. So it is used for the purification of
sugar.
The important characteristics of adsorption from solution are:
(i) The extent of adsorption decreases with an increase in temperature.
(ii) The extent of adsorption increases with an increase of surface area of the adsorbent.
(iii) The extent of adsorption depends on the concentration of the solute and the nature of the
adsorbent and the adsorbate.

- Freundlich adsorption isotherm is applicable to adsorption from solution also. Here instead of
pressure, concentration of the solution is used.
1/n
i.e., x/m = k C
(where C is the equilibrium concentration).
On taking logarithm of the above equation, we have
log x/m = log k + 1/n log C

On plotting log x/m against log C, a straight line is obtained which verifies Freundlich isotherm.
Applications of adsorption
The important applications of adsorption are:

1) Production of high vacuum: For the complete evacuation of a vessel, activated charcoal is used.
2. Gas masks: The poisonous gases in coal mines can be removed by using gas masks containing
activated charcoal.
3) Control of humidity: Silica and aluminium gels are used as adsorbents for removing moisture and
controlling humidity.
4) Animal charcoal is used for the purification of cane sugar solution.
5) Adsorption finds application in heterogeneous catalysis.
6) A mixture of noble gases can be separated by adsorption on coconut charcoal at different
temperatures.
7) In curing diseases: A number of drugs are used to kill germs by getting adsorbed on them.
8) In froth floatation process for the purification of sulphide ores in metallurgy.
9) Adsorption indicators like eosin, fluorescein etc. are used in volumetric analysis.
10) Chromatographic analysis for the separation of a mixture is based on adsorption.

.
 THE COLLOIDAL STATE
 Based on particle size solutions are classified into three True solution, Suspension and colloids.
 In a true solution, - The size of the particles is < 1nm.
- The particles do not settle down under the influence of gravity
- They cannot be filtered by a filter paper.
- A true solution is homogeneous and transparent.
 In a suspension - the size of the particles is > 1000nm.
- The particles settle down under the influence of gravity
- They can be filtered by an ordinary filter paper.
- It is heterogeneous and opaque.

 Colloid is an intermediate state between true solution and suspension.

- In colloids, the particle size is in between 1 nm and 1000nm.
- The particles do not settle down under the influence of gravity.
- They cannot be filtered by ordinary filter paper, but can be filtered by
ultra-filters.
- They are heterogeneous and translucent.
- Colloids are heterogeneous systems containing two phases – dispersed phase and dispersion
medium.
Dispersed phase: The substance which is dispersed (distributed) is called dispersed phase.
Dispersion medium: The medium in which the particles are dispersed is called dispersion medium.
e.g.: In starch solution, starch is the dispersed phase and water is the dispersion medium.

Classification colloids
1. Based on the physical state of dispersed phase and the dispersion medium
Depending upon physical state of the dispersed phase and the dispersion medium, there are eight
types of colloidal systems. A gas mixed with another gas forms a homogeneous mixture and hence
is not a colloidal system. The different types colloidal dispersion are:

Dispersed Phase Dispersion Type of colloid Examples

medium
Solid Solid Solid Sol Some coloured glasses and gem
stones
Solid Liquid Sol Paints, Cell fluids

Solid Gas Aerosol of solid Smoke, dust

Liquid Solid Gel Cheese, butter, jellies

Liquid Liquid Emulsion Milk, hair cream, cod liver oil
Liquid Gas Aerosol of liquid Fog, mist, cloud, insecticide sprays

Gas Solid Solid foam Pumice stone, foam rubber

Gas Liquid Foam Froth, whipped cream, soap lather
 2. Based on the dispersion medium, colloids are classified as follows:

Dispersion medium Name of colloid

Air Aerosol
Water Hydrosol
Alcohol Alcosol
Benzene benzosol

3. Based on the attraction between the dispersed phase and the dispersion medium
- Two types: lyophilic (solvent loving) and lyophobic (solvent hating).
Lyophilic Sol : If the force of attraction between dispersed phase and dispersion medium is
strong, it is called lyophilic sol
e.g. gum, gelatin, starch, rubber etc in suitable dispersion medium.
Lyophobic Sol : If the force of attraction between dispersed phase and dispersion medium is
weak, it is called lyophobic sol.

e.g. Arsenic sulphide (As2S3) sol, sulphur sol and metal sols like gold sol, silver sol etc.

 Differences between lyophilic and lyophobic sols

Properties Lyophilic sol Lyophobic sol

Force of attraction Strong Weak Weak
Can be easily prepared by mixing the Some special methods are used
Preparation dispersed phase with the dispersion for the preparation
medium

Reversibility Reversible (i.e. they can be easily irreversible

separated and remixed)

Stability Self-stabilized Less stable and requires some

stabilizing agent
Coagulation large amount of electrolyte is required for Only small amount of
coagulation electrolyte is required.

4. Based on the nature of particles:

Based on this, colloids are of three types – Multimolecular colloids, Macro molecular colloids and
associated colloids.
1. Multimolecular colloids:
They contain an aggregate of atoms or molecules having dimension < 1nm. These particles are
bind together by weak van der Waal’s force of attraction and form particles of colloidal dimension.
e.g. Arsenic sulphide (As2S3) sol, sulpher sol and metal sols like gold sol, silver sol etc.
2. Macromolecular colloids:
Macromolecules (Polymers) in suitable solvents form solutions in which the size of the particle
is in the colloidal range. Such systems are called macromolecular colloids. These colloids are quite
stable and resemble true solutions in many properties.

Example: solutions of starch, cellulose, proteins, enzymes, polythene, nylon, polystyrene, synthetic
rubber, etc. in suitable dispersion medium.
 3. Associated colloids:
- These are substances which behave as normal strong electrolytes at low concentrations, but as
colloids at higher concentrations. The colloidal behaviour is because of the formation of
aggregates. They are also called micelles.
- The formation of micelles takes place only above a particular temperature called Kraft
temperature (Tk) and above a particular concentration called critical micelle concentration (CMC).
- Surface active agents such as soaps and synthetic detergents are examples for micelles. These
colloids have both lyophobic and lyophilic parts.

Mechanism of micelle formation

An example for micelle is soap solution. Soap is sodium or potassium salt of a higher fatty acid and
– + – +
may be represented as RCOO Na . When dissolved in water, it dissociates into RCOO and Na
–
ions. The RCOO ions consist of two parts — a long hydrocarbon chain R (also called non-polar ‘tail’)
–
which is hydrophobic (water repelling), and a polar group COO (also called polar-ionic ‘head’), which
is hydrophilic (water loving)

– –
The RCOO ions are present on the surface with their COO groups in water and the hydrocarbon
chains (R) at the surface. But at critical micelle concentration, the anions are pulled into the bulk
of the solution and aggregate to form a spherical shape. Thus a micelle is formed.

Cleansing action of soaps

The cleansing action of soap is due to micelle formation. The soap molecules form micelle around
the oil droplet in such a way that hydrophobic part is in the oil droplet and hydrophilic part projects
out. Since the polar groups (hydrophilic end) can interact with water, the oil droplets are pulled in
water and removed from the dirty surface. Thus soap helps in emulsification and washing away of oils
and fats.
 Preparation of colloids
Some of the methods used for the preparation of colloids are:
a) Chemical methods:
Colloidal solutions can be prepared by chemical reactions like oxidation, reduction, double
decomposition, hydrolysis etc.
1. Oxidation: Sulphur sol can be prepared by passing H2S gas through an aqueous solution of
sulphur dioxide.

2. Reduction: Sols of metals like silver, gold and platinum are obtained by the reduction of their
salts with reducing agents like formaldehyde, stannous chloride etc.

3. Hydrolysis: Ferric hydroxide sol is obtained when concentrated solution of ferric chloride is
added drop-wise to hot water.

4. Double decomposition: A colloidal solution of arsenic sulphide is formed by passing H2S through
a dilute solution of arsenious oxide in water.

b) Electrical disintegration (Bredig’s arc method):

- This method is used for the preparation of metal sols like Ag, Au, Pt etc.
- The metal whose sol is to be prepared is taken in the form of two rods and it is kept in suitable
dispersion medium containing small amount of electrolyte. The whole arrangement is kept in an ice
bath. When high voltage is passed through the metal, the intense heat produced vapourises the
metal, which then condensed to form particles of colloidal dimension.

c) Peptization:
- The process of conversion of a freshly prepared precipitate into a colloidal sol by shaking it with
suitable dispersion medium in the presence of small amount of electrolyte is called peptization.
- The electrolyte added is called peptizing agent.
- During peptization, the precipitate adsorbs one of the ions of the electrolyte on its surface and
forms a positive or negative charge on it. Thus the particles of the precipitate break up into
smaller particles of the colloidal size.
 Purification of colloids
The colloidal solution prepared contains excess amount of electrolyte and some other soluble
impurities. Even though small amount of electrolyte is required for the stability of colloid, large
amount may cause precipitation. The process of reducing the concentration of electrolyte and other
impurities is known as purification of colloids.
- Some methods used for purification are:
1. Dialysis: It is the process of removing dissolved substances from a colloidal solution by means of
diffusion through a semi-permeable membrane. Here the sol particles are taken in a parchment
or cellophane bag and it is suspended in a running stream of water. The impurities are diffused
through the membrane and the sol particles are left behind. These particles are then suspended
in suitable dispersion medium so as to get a colloidal dispersion.
- The speed of dialysis can be increased by using hot water instead of cold water. Then the
process is known as hot water dialysis.
- The speed of dialysis can also be increased by dipping two electrodes and passing electricity.
Then the process is known as electrodialysis.

2. Ultrafiltration: It is the process of separating the colloidal particles from the impurities by using a
special type of filter paper called ultrafilters or ultra-filter paper. It is prepared by dipping ordinary
filter paper in collodion solution (a 4% solution of nitrocellulose in a mixture of alcohol and ether).
When colloidal particles are filtered using ultrafilters, the sol particles are retained on the
filterpaper while the impurities and the electrolyte are passed through it. When these sol particles
are suspended in suitable dispersion medium, we get a colloidal solution.

 Properties of colloids

1. Colligative properties:
In colloids, the number of particles are very small compared to that of true solution. So the
values of colligative properties such as relative lowering of vapour pressure, elevation of boiling
point, depression of freezing point and osmotic pressure are small compared to that of true
solution.
2. Tyndall effect:
When a light beam is passed through a colloidal solution, we can see the path of the light beam.
This phenomenon is known as Tyndall effect. It is due to the scattering of light beam by the colloidal
particles. The visible path is called tyndall cone.

Tyndall effect is observed only when the following conditions are satisfied:
(i) The diameter of the dispersed particles is much larger than the wavelength of the light used.
(ii) The refractive indices of the dispersed phase and the dispersion medium differ greatly in
magnitude.
True solutions do not show tyndall effect since the size of particles are very small so
that they cannot scatter the light beam.

- Thus tyndall effect is used to distinguish a colloidal solution from a true solution.
Ultramicroscope used to see the colloidal particles works on the principle of tyndall effect.
3. Brownian movement
- In colloids, the particles of dispersion medium are in a state of continuous zig-zag motion.
This motion was first observed by Robert Brown and it is known as Brownian movement.

- It is independent of the nature of the colloidal particles but depends on the size of the particles
and viscosity of the solution. Smaller the size and lesser the viscosity of the medium, faster is the
motion.
- Brownian movement is due to the unbalanced bombardment of particles of the dispersed phase
by the particles of dispersion medium. It is responsible for the stability of colloids.

4. Charge on colloidal particles:

Colloidal particles always carry an electric charge. For a given colloidal solution, the nature of the
charge is the same on all the particles.
Positively charged sol Negatively charged sol

Hydrated metallic oxides like Fe2O3.xH2O, Metal sols (e.g. Cu sol, Ag sol, Au sol)
Al2O3.xH2O, and CrO3.xH2O etc.
Basic dyes (e.g. methylene blue) Metallic sulphides (e.g. As2S3, CdS etc)

Haemoglobin in blood Acid dyes (e.g. eosin, Congo red etc.)

Metal oxides (TiO2) Sols of starch, gum, gelatin, clay, charcoal etc.

Reason for the charge on colloidal particles: The charge on the sol particles is mainly due to
preferential adsorption of ions from solution. When 2 or more ions are present in the dispersion
medium, preferential adsorption of the ion common to the colloidal particle takes place.
e.g.
- When AgNO3 is added to KI, AgI is precipitated, which adsorbs iodide ions from the dispersion
medium and thus get a negative charge.
AgNO3+ KI → AgI + KNO3
+
- But when KI is added to AgNO3, the precipitated AgI adsorbs Ag ions from the solution and thus
get a positive charge.
- Helmholtz electrical double layer: Due to the positive or negative charge in the sol particles, they
attract the counter ions (opposite ions) from the medium. Thus a double layer of opposite charges
is formed. This is known as Helmholtz electrical double layer.
- The layer in which the ions are directly adsorbed to the sol particles is termed as fixed layer. The
second layer is mobile and is termed as diffused layer.

- Electrokinetic potential or zeta potential

Due to the opposite charges on the fixed and diffused layers, there arises a potential difference
between these layers. This potential difference between the fixed layer and the diffused layer of
opposite charges is called the electrokinetic potential or zeta potential.
 The presence of similar charges on colloidal particles leads to repulsion between the
particles and prevent them from coagulation when they come closer. So the charge on
the sol particles is mainly responsible for the stability of colloidal solution.

5. Electrophoresis:
Since colloidal particles carry charge, they move under the influence of an electric field. This
movement of colloidal particles is called electrophoresis. The positively charged sol particles move
towards cathode (cataphoresis) and the negatively charged particles move towards the anode
(anaphoresis).

Electro-osmosis.

If the movement of the sol particles is prevented by some suitable method, the particles of
dispersion medium itself move under the presence of electric field. This migration is termed as
electro-osmosis.
6. Coagulation (precipitation or flocculation)
The process of settling of colloidal particles is called coagulation or precipitation of the sol. This can
be done by different ways:
i) By electrophoresis
ii) By mixing two oppositely charged sols
iii) By continuous dialysis
iv) By boiling
v) By the addition of electrolyte
When an electrolyte is added to the sol, the ions carrying opposite charge to that of the sol neutralize
the charge and causes precipitation. The ion of the electrolyte which causes the precipitation is called
the coagulating ion or the flocculating ion.
- A negatively charged ion causes the precipitation of positively charged sol and vice versa.

Hardy – Schulze rule

Generally, the greater the valency of the coagulating ion, the greater will be the coagulating power.
This is known as Hardy – Schulze rule.

Thus for the coagulation of a negative sol like As2S3, the flocculating power of the + ve ions is of the
3+ 2+ +
order: Al > Ba > Na

Similarly for a +ve sol like ferric hydroxide, the flocculating power of the counter ion is of the order:
4- 3- 2- -
[Fe(CN)6] > PO4 > SO4 > Cl

Coagulating value: The minimum concentration of an electrolyte in millimoles per litre required for
the coagulation of a sol within 2 hours is called coagulating value. The smaller the coagulating value,
the higher will be the coagulation power.
  Protection of colloids
- Lyophilic sols are self-stabilized, while lyophobic sols require some stabilizing agents. For this
purpose, some lyophilic sols are added to lyophobic sols. These lyophilic sols are called protective
colloids.
- When a lyophilic sol is added to a lyophobic sol, the lyophilic particles form a layer around
lyophobic particles and thus protect them from electrolytes.
 Applications of Colloids
1. Formation of Delta:
Deltas are formed at the river mouth. This is because river water is a negatively charged colloid
of sand particles. When this water enters into sea, the positive ions present in sea water coagulate
the colloidal solution of sand and so the particles settle down. This will result in the formation of
delta.
2. Electrical precipitation of smoke (Cottrell precipitation):
Smoke is a colloidal solution of carbon, arsenic compounds, dust particles etc. in air. The smoke
before coming out of the chimney is passed through a chamber (Cottrell precipitator) containing
plates having a charge opposite to that of smoke particles. Thus neutralization of charges occurs
and the particles settle down and pure air flows out of the chimney.
3. Purification of drinking water:
The water obtained from natural sources often contains suspended impurities. In order to
coagulate these impurities, alum is added to water. The positive ions present in alum neutralize the
suspended impurities and hence get purified.
4. Medicines:
Most of the medicines are colloidal in nature. This is because they have large surface area and
are therefore easily assimilated. For example, argyrol is a silver sol used as an eye lotion.
Colloidal antimony is used in curing kalaazar. Colloidal gold is used for intramuscular injection.
5. Tanning:
Animal hides are colloidal in nature. When a hide, which has positively charged particles, is soaked
in tannin (which contains negatively charged colloidal particles) mutual coagulation takes place.
This results in the hardening of leather. This process is termed as tanning.
6. Photographic plates and films:
Photographic plates or films are prepared by coating an emulsion of the light sensitive silver
bromidein gelatin over glass plates or celluloid films.
7. Rubber industry:
Rubber latex is a colloidal solution of rubber particles which are negatively charged. Rubber is
obtained by coagulation of the latex.
8. Food articles:
Milk, butter, halwa, ice creams, fruit juices, etc., are all colloids in nature.
9. Blood: (Negative colloid)
Blood is a colloidal solution of an albuminoid substance. When alum and ferric chloride (FeCl 3)
solution are added to blood, then coagulation of particles take place which results in clotting of
blood.
10. Industrial products:
Paints, inks, synthetic plastics, rubber, graphite lubricants, cement, etc., are all colloidal in nature.

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