Surface Chemistry

JEE Syllabus
Adsorption- Physisorption and chemisorption and their characteristics, factors
affecting adsorption of gases on solids - Freundlich and Langmuir adsorption
11
CHAPTER
isotherms, adsorption from solutions. Catalysis - Homogeneous and
heterogeneous, activity and selectivity of solid catalysts, enzyme catalysis
and its mechanism. Colloidal state - distinction among true solutions, colloids
and suspensions, classification of colloids - lyophilic, lyophobic; multi
molecular, macromolecular and associated colloids (micelles), preparation
and properties of colloids - Tyndall effect, Brownian movement,
electrophoresis, dialysis, coagulation and flocculation; Emulsions and their
characteristics.

ADSORPTION THIS CHAPTER

The phenomenon of attracting and retaining the molecules of a substance on
INCLUDES
the surface of a liquid or a solid resulting into higher concentration of the molecules  Adsorption
on the surface is called adsorption  Adsorption isotherm
There are two types of adsorption
 Freundlich
(i) Physical adsorption
adsorption Isotherm
(ii) Chemical adsorption
 Langmuir adsorption
Physical adsorption Chemical adsorption isotherm
or or  Catalysis
Physisorption Chemisorption
 Hom ogeneous and
1. Enthalpy of adsorption usually 1. Enthalpy of adsorption is of Hetrogeneous catalysis
–1 –1
is of the order of –20 kJ mol the order of –200 kJ mol .
i.e. exothermic  Shape selective
2. Molecules of adsorbate and
catalysis by zeolites
2. Molecule of adsorbate and adsorbent are held by
adsorbent are held by Van der chemical bonds  Enzyme catalysis
Waal interaction  Colloids
3. It takes place relatively at
3. It usually takes place at low high temperature  Classification of colloids
temperature and decreases with
increasing temperature  Based on physical
state of dispersed
4. It is not very specific i.e. all 4. It is highly specific and take phase and dispersion
gases are adsorbed on all place when there is some medium
solids to some extent possibility of compound
formation between  Based on nature of
5. Multimolecular layers may be interaction between
adsorbate and adsorbent
formed on adsorbent
molecule. dispersed phase and
5. Usually monomolecular layer dispersion medium
is formed on the adsorbent.  Emulsions and its type

ADSORPTION ISOTHERM  Preparation of colloids

A relation or graph between x/m (x are number of moles of adsorbate and m  General properties of
is the mass of adsorbent) and the pressure (P) of the gas at a constant colloids
temperature is called adsorption isotherm.  Purifications of colloids
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A. Freundlich Adsorption Isotherm

Freundlich gave an equation x/m  KP1/n (n > 1) to explain the effect of pressure on amount of gas adsorbed
where K and n are parameters of the equations depending upon the nature of the gas and solid.

x
increases with increase in pressure. Since n > 1, so x/m does not increase, as rapidly as 'P'
m
1
log x/m = logK + log P (Taking log on both sides)
n

1
= n
pe
log x/m 

Slo

Intercept = log K

log P 
From this graph it is possible to find out value of K and n
B. Langmuir Adsorption Isotherm
Langmuir considered that adsorption to consist of the two opposing processes i.e. adsorption and desorption
both take place and dynamic equilibrium established between the above two processes. He also assumed
that the layer of the adsorbed gas was only one molecule thick i.e. unimolecular and for chemisorption.
The Langmuir adsorption isotherm is represented by the relation.

x ap
 where a and b are two Langmuir parameters.
m 1  bp

x a
 (At very high pressure 1 + bP 
~ bP)
m b

x
and = aP (At very low pressure 1 + bP  1)
m

x
So at high pressure of the gas remains constant and nature of graph is linear at very high pressure
m
x/m 

Pressure 
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In order to determine the parameters a and b, we may write

m 1  bP b 1
  
x aP a aP

m 1 1 b
A plot of against gives a straight line with slope and intercept equal to and respectively
x P a a

1
Slope = a
m
x
b
Intercept = a

1
P

CATALYSIS
The process of changing the rate of a chemical reaction by addition of a foreign substance (catalyst) is called
catalysis. The catalyst is specific in nature and change the rate of a particular reaction by providing an alternate
path of different activation energy. When catalyst increases the rate of reaction, it is called positive catalyst and
decreases the ratio of reaction is called negative catalyst.

MnO 2 (s)
Ex. 2KClO 3   2KCl(s)  3O 2 (g)

MnO2 (s) act as positive catalyst and phenomenon is known as positive catalysis

acetanilide (s)
2H2O 2 (l)     2H2 O (l)  O 2 (g)

Acetanilide (s) act as negative catalyst and process is known as negative catalysis.

HOMOGENEOUS AND HETEROGENEOUS CATALYSIS

A reaction in which the catalyst and the reacting substances are present in the same phase, is called
homogeneous catalysis

NO (g)
Ex. 2SO 2 (g)  O 2 (g)   2SO 3 (g)

H (aq)
CH 3COOCH 3 (aq)  H 2O ( l)  
 CH3COOH(aq)  CH3OH(aq)

A reaction in which the catalyst is present in a phase different from that of the reacting substances is called
heterogeneous catalysis. All the reactions in this case occur at the surface of the catalyst

Finely
Ex. N2(g) + 3H2(g) 2NH3 (g)
divided Fe (s)

P(s)
2SO2 (g) + O2(g) 2SO3 (g)
or V2 O5(s)

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SHAPE SELECTIVE CATALYSIS BY ZEOLITES

Zeolites are the most important metal oxide or aluminosilicates catalysts. These catalysts are widely used
in the petrochemical industries for (i) cracking of hydrocarbons and (ii) for aromatisation. Zeolites are microporous
silicates having the general formula
Mx / n [( AlO2 ) x (SiO2 ) y ] . mH2O
Shape-selectivity is the most remarkable feature of zeolite catalysts. The reactions depend on the size of
the cavities (Cages) and pores (apertures) present on the surface of zeolite. The pore size varies between 260pm
and 760pm.
Hence depending upon the size of the reactant and product molecules, as compared to the size and the shape
of the cavities and the pores of the zeolite, the reactions can move in a specified manner.
A special catalyst, called ZSM-5, is used to convert alcohols such as methanol, ethanol directly to gasoline
or petrol.
ZSM 5
xCH 3OH   (CH 2 ) x  xH 2O
Methanol Catalyst Gasoline

Zeolites are also used in water softening.

ENZYME CATALYSIS
All biological reactions are catalysed by special catalysts called enzymes. Thus enzymes are defined by biogical
catalyst.
All biological reactions require a different kind of enzyme. Only small amount of enzymes can be highly efficient,
speed up the reaction by factors of upto 1020

Enzyme Reaction catalysed

(i) Invertase or sucrase Sucrose  Glucose + Fructose
(ii) Maltase Maltose  Glucose + Glucose
(iii) Lactase Lactase  Glucose + Galactose
(iv) L – Amylase Starch  n × Glucose
(v) Pepsin Proteins  L – Amino acid
(vi) Trypsin Proteins  L – Amino acid
(vii) Urease NH2CONH2 + H2O CO2 + 2NH3
Urea

COLLOIDS
Colloidal state of matter is a state in which the size of particles is such (10Å – 1000Å) that they can pass
through filter paper but not through animal or vegetable membrane.

CLASSIFICATION OF COLLOIDS
(i) Based on physical state of dispersed phase and dispersion medium–The physical state of dispersed
phase and dispersion medium may be solids, liquids or gases, eight types of colloidal system are possible.

Dispersed Phase Dispersion Medium Name Examples

Solid Solid Solid Sol Some coloured glasses, gem stones
Solid Liquid Sol Some paints, cell fuids, muddy water
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 foam Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather

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Note : A gas mixed with another gas form a homogeneous mixture and not a colloidal system
(hetrogeneous mixture).

(ii) Based on nature of interaction between dispersed phase and dispersion medium–
Divided into two types namely Lyophilic and Lyophobic Colloids

Lyophilic Sols Lyophobic Sols

1. Nature Reversible Irreversible

2. Preparation Prepared by direct mixing with liquid Cannot be prepared directly but by special
dispersion medium i.e. solvent loving method i.e. solvent hating
3. Stability Quite stable and not easily precipitated or Precipitated by adding small amount of
coagulated suitable electrolyte
4. Hydration Highly hydrated Not much hydrated
5. Nature & These sols are usually formed by the These are usually formed by the inorganic
substances organic substances like starch, gum, materials like metals, their sulphides etc.
proteins etc.
6. Viscosity Much higher than that of medium Almost same as that of medium
7. Surface Lower than that of dispersion medium Nearly same as that of dispersion medium
tension

EMULSIONS AND ITS TYPE

Emulsions are colloids in which both dispersed phase and dispersion medium are liquids and broadly classified
into two types
(i) Oil in water emulsion – In this type of emulsion oil act as dispersed phase and water act as dispersion
medium. Ex.– Milk, vanishing cream etc.
(ii) Water in oil emulsion – In this type of emulsion water act as dispersed phase and oil act as dispersion
medium.
Ex.– Cold cream, butter, cod liver oil etc.

PREPARATION OF COLLOIDS
Prepared by two types of methods
(a) Condensation method (b) Dispersion method
(a) Condensation method
Condensation Method

Physical Method
Chemical method
Double
As2O3 + 3H2S As2S3(sol) + 3H2O
decomposition

Exchange of solvent Excessive cooling Oxidation

SO2 + 2H2S 3S(sol) + 2H2O
When a true solution is mixed A sol of ice in CHCl3
with an excess of other solvent in Reduction
or ether by freezing 2AuCl3 + 3HCHO + 3H2O 2Au (sol)
which the solute is insoluble but the water in the +3HCOOH+6HCl
solvent is miscible. Ex– when a solvent Hydrolysis
solution of sulphur in alcohol is FeCl3 + 3H2O Fe(OH)3+3HCl (sol)
poured in excess of water sol of S
is obtained

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(b) Dispersion method

In this method large particles of the substance are broken into particles of colloidal dimensions in the
presence of dispersion medium and stabilised by adding some suitable stabilizer. Some methods given
below:

(i) Mechanical dispersion – In this method, the course suspension of the substance is brought into
a colloidal state in dispersion medium by grinding it in a colloidal mill, ball mill or ultrasonic
disintegrator.
+ Electrodes –
(ii) Electrical disintegration or Bredig's arc method
This process inv olves dispersion as well as
condensation colloidal sols of metals such as gold,
silver, platinum etc. can be prepared by this method.
Dispersion
Electric arc is struck between electrodes of metals Medium
immersed in the dispersion medium. The intense
Ice-Bath
heat produced vaporises the metal, which then
condenses to form particles of colloidal size.

(iii) Peptization – It is a process of converting the precipitate into colloidal sol by shaking it with
dispersion medium in the presence of a small amount of electrolyte (Peptising agent)
During peptization the precipitate adsorb one of the ion (cation or anion) which is common ion.
Ex – When freshly precipitated Fe(OH)3 is shaken with aqueous solution of FeCl3 (Peptizing agent)
it adsorbs Fe+3 ion (common ion) and there by breaks up into small sized particles.

Note : Lyophilic sols are quite stable and can be easily prepared by shaking the lyophilic material
with dispersion medium.
Ex – Colloidal sols of gelatin, gum, starch, egg, albumin etc.

GENERAL PROPERTIES OF COLLOIDS

(i) Colligative properties – Due to high average molecular masses of colloidal particles, mole fraction of
dispersed phase is very low and the value of colligative properties observed experimentally are very small.

(ii) Optical properties–Tyndall effect – Tyndall (1869) observed that if a strong beam of light is passed
through a colloidal sol placed in the dark place the path of the beam gets illuminated. This phenomenon
is called Tyndall effect, which is due to scattering of light by the colloidal particles. Tyndall effect not found
in true solution.

(iii) Mechanical properties–Brownian movement – Colloidal particles are found to be in continuous

zig–zag motion called Brownian movement, it arises because of the impact of the molecules of the
dispersion medium with the colloidal particles. + –
(iv) Electrical Properties-Electrophoresis. Electrode
The particles of colloids are electrically
charged and are positively or negatively
charge. The dispersion medium has an
Decrease the
equal and opposite charge making the
length of tube
system neutral as a whole. The Coagulated sol
particles
existance of charge is shown by the
phenomenon of electrophoresis. It
As2S3 sol
involves the movement of colloidal
(negatively charged)
particles either towards the cathode or
anode under the influence of electric
field.

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Positively charged collidal particles Negatively charged colloidal particles

Metal hydroxides [Fe(OH)3, Al(OH) 3, Ca(OH) 2, Metal, starch, clay, metal sulphides (As2S3,
Cr(OH) 3], Oxides (TiO2) haemoglobin, basic dye CdS), Acidic dye (congo red) etc.
(Methyl blue, Prussian blue) etc.

(v) Coagulation of colloids – The phenomenon of precipitation of a colloidal solution by the addition of excess
of an electrolyte is called coagulation or flocculation.
At lower concentration of electrolytes, the aggregation of particles is called flocculation that can be reversed
on shaking while at higher concentration of electrolyte coagulation takes place and the same cannot be
reversed simply by shaking.
Hardy–Schulze Rule
(i) The ions carrying charge opposite to that of sol particles are effective in causing the coagulation of
the sol
(ii) Coagulating power of an electrolyte is directly proportional to the fourth power of the valency of the
ions causing coagulation.
The minimum concentration of an electrolyte which is required to cause coagulation of a sol is known
as coagulation value and expressed in millimoles / litre.

PURIFICATION OF COLLOIDS
Following methods are used
(i) Dialysis – A bag made-up of parchment paper or cellophone membrane is filled with colloidal solution and
is then suspended in fresh water, the electrolyte particles passout leaving behind the colloidal sol
Movement of ions across the membrane can be expedited by applying electric potential through two
electrodes. This method is faster than simple dialysis and is known as electrodialysis
(ii) Ultrafiltration – In this method the colloidal solution is filtered through ultra-filters which allow to pass
electrolytes only.
(iii) Ultra–centrifugation – In this method colloidal sol is taken in a tube which is placed in an ultra-centrifuge.
On rotation of the tube with high speeds the colloidal particles settle down at the bottom of the tube and
the impurities remain in solution called the centrifugate. The settle colloidal particles are mixed with an
appropriate dispersing medium to regenerate the sol.



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