Ch.

- 2
Surface chemistry
Adsorption ::- The phenomenon of attracting and Retaining the molecules of substances the surface
of solid is known as adsorption.

The solid substance on the surface of which adsorption occurs is called as adsorbent.

The substances that get adsorbed on the solid surface is called as adsorbate.

W indow

Desorption::- The process of removal of adsorbed substance is called as

desorption.

Sorption ::- When adsorption and absorption occurs simultaneously,

then it is called as sorption.

Differences b/w adsorption and absorption::-

 Adsorption is a surface phenomenon, while absorption is bulk phenomenon.
 The process of adsorption is fast in the beginning and then slows down, while absorption occurs at
constant rate.
 In adsorption the concentration is higher on the surface then in the bulk, while in absorption
concentration is same everywhere.

Types of adsorption ::-

Depending upon the forces b/w adsorbate and adsorbent, adsorption may be classified as ::-

Physical Adsorption ::- When the particles of adsorbate are attached to the adsorbent by the physical
forces, then it is called as physical adsorption.
Characteristics ::-

 Low enthalpy ::- In physical adsorption there is only weak Vander wall forces, therefore they have
low enthalpy of adsorption ( 20 – 40 kj/mol.)
 Reversible in nature ::- Physical adsorption is generally reversible because there is no permanent
change occurs.
 Effect of temperature ::- On increasing the temperature the kinetic energy of adsorbate increases
and thus they can be easily desorbed.
 Lack of specificity ::- In physical adsorption there is only weak Vander wall forces which are not
specific in nature.
 Nature of Adsorbate ::- The extent of Physical Adsorption depends upon ease of liquefaction, i.e.,
The gas which is easily liquefied can be easily adsorbed.
 State of Adsorbate ::- The Physical Adsorption, no chemical reaction occurs and thus state of
adsorbate remains same.

Chemical Adsorption ::-

When the particles of adsorbate are held to the surface of adsorbent by chemical forces is called as
chemical adsorption.

Characteristics ::-

 High Enthalpy ::- In chemical adsorption there are the formation of strong chemical bond.
Thus, it has very high enthalpy of adsorption.
 Irreversible Nature ::- In chemical adsorption there is a formation of strong chemical bond
which are generally irreversible.
 Effect of Temperature ::- In chemical adsorption during the progress of reaction on increasing
temperature extent of adsorption increases but after the formation of compound on increasing the
temperature extent of adsorption decreases.
 High selectivity ::- In chemical adsorption chemical compounds are formed which are highly
selective in nature.
 State of adsorbate ::- In chemical adsorption there is a chemical reaction occurs and thus, state
of adsorbate changes.
 Adsorption Isotherm ::-
The relationship b/w the amount of the substance adsorbed by the adsorbent with pressure at
constant temperature is called as adsorption isotherm.

Const. Temp.

( x/m)

. P

Friendlich Adsorption isotherm ::-

(x/m)

Pressure

i. At low pressure

x/m α P’
ii. At high pressure

x/m α Po
 iv. At moderate pressure

x/m α P 1/n
x/m = KP 1/n
Note ::- x/m = KP 1/n

Taking log

ln x/m = ln KP 1/n

ln x/m = ln K + ln P 1/n

ln x/m = ln K + 1/n ln P

2.303log x/m = 2.303log K + 2.303/n logP

Log x/m = Log K + 1/n Log P

Factors affecting adsorption of gases on solids ::-

 Nature of gases ::- Higher the liquefaction Tendency of gases, grater will be the extent of
Adsorption.
 Nature of adsorbent ::- More active is the adsorbent greater will be the extent of adsorption.
 Surface area ::- Grater the active sites of the adsorbent, larger the extent of adsorption.
 Activation of adsorbent ::- Adsorbent can be activated in following ways ::-
i. By Rubbing
ii. By electroplating
iii. By heating
iv. By cutting it into several small pieces
 Effect of temperature ::-
 Adsorption Isobar ::-

(x/m)

(Physical Adsorption )

(x/m)

T
(Chemical adsorption)

Isoster ::-
The graph showing the variation of pressure with temperature for a given amount of adsorption is
called as Isoster.

T (x/m)
Catalysis ::- Catalyst are the substances which can alter the rate of chemical reaction without itself
undergoing any change and this phenomenon is called as Catalysis.

Depending upon the physical state of component Catalysis is can be divided into two types ::

 Homogeneous catalysis ::- When in a chemical reaction catalyst and reactant and the product are
in the same physical state called as Homogeneous catalysis.

SO(g) + ½ O2(g) SO2(g)

 Heterogeneous catalysis ::- When the catalyst and reactant and product are in the different
Physical state called as Heterogeneous catalysis.

CH2 = CH2 (g) + H2 (g) CH3 = CH3 (g)

Modern Adsorption Theory ::-

Modern Adsorption theory explain the catalytic property of chemical reaction and involve following
Steps ::

 Diffusion of reactant to the surface of the catalyst.

 Adsorption of the molecule of the reactant at the active sites.
 Occurrence of chemical reaction on the surface of catalyst through which intermediate compound is
formed.
 Desorption of the product molecules from the surface of the catalyst and thereby, making the surface
available for the reaction.

A B

A+B+

A B

A+B+
 Enzyme catalysis ::- Enzymes are biological catalyst produced by living cells which can
catalyze the biochemical reactions which occur in our body. Chemically enzymes are proteins with molar
mass 15000 to

C6H12O6 Zymase 2C2H5OH + 2CO2

NH2CONH2 + H2O Urea 2NH3 + CO2

Characteristics of Enzymes ::-

 Enzymes are highly efficient in nature i.e., Its very small amount can increase
the order of the reaction from 108 to 1020 times.
 Enzymes are highly specific in nature , almost every biochemical reaction is
controlled by its own enzyme.
 The activity of enzyme is maximum at a particular temperature and
concentration called as Optimum temperature and Optimum PH.
 Co – Enzymes are the substances which enhance the activity of enzyme.
 Lock And Key Model ::- According to the lock and key model “ the substrate have active
sites in such a specific manner that only a particular enzyme can fit into the slot. And this concept is similar t
lock and key function and is called as Lock and Key Model “ .

 Induced Fit Model ::- “ X-Ray Analysis and spectroscopic analysis observed that the
enzyme slight changes the shape when a substrate combine to it. And this model is known as Induced fit
model “ .

Mechanism ::-

E+S ↔ES ( fast )

ES → EP → E+P

Types of Solution ::-

Depending upon the size of the solute particles, solution may be classified into following types ::-
 True Solution ::- True solution is a homogeneous solution which contains small solute particles
having size less than 1nm .

Suspension ::- Suspension is heterogeneous mixture which contains small insoluble solute particle
having size more than 1000nm .

Colloidal Solution ::- Colloidal solution is a heterogeneous mixture which contains particles of
intermediate size i.e., in b/w 1nm to 1000nm .

Classification of colloids ::-

Classification on the basis of nature of interaction b/w dispersed phase and dispersion medium.

On the basis of the nature of interaction it may be divided into two types :::

Lyophobic colloids ::- These are the colloidal solution in which particles of dispersed phase have a great
affinity to combine with the dispersion medium called lyophobic colloids .

These solution are formed by difficulty and required some electrolyte for their
stability. Example :: Colloid of silver . gold, etc.

Classification on the basis of types of particle of dispersed phase.

Depending upon the type of particle of dispersed phase, colloid may be classified into three types.

Multi-molecular colloids ::- These are the true molecules having size less than 1nm but during
colloidal formation aggregate together to form colloidal dimension. Example :: colloid of Ag, Au, etc.

Macro-molecular Colloids ::- These are the big size molecule but during colloidal formation they
dissociate into colloidal dimension. Example :: Colloids of starch, cellulose, etc.

Associated colloids ::- These are the substances which when dissolved in medium behave as normal
electrolyte at low concentration but converted into colloidal dimension at higher concentration due to
formation of micelle.

The formation of micelle takes place above the particular temperature called craft
temperature and above a particular concentration called critical micellisation concentration.

Classification on the basis of physical state dispersed phase and dispersion medium.

Dispersed phase Dispersion medium Example

Solid Solid Alloy, Gem stone Colored glass
etc.
Liquid Solid Gel, Butter etc.
Gas Solid Rubber, foam etc.
Solid Liquid Paint
Solid Gas Smoke
Liquid Liquid Milk
Liquid Gas Fog
Gas Liquid Soap lather

 Preparation of colloids ::-

 By Peptization ::- The process of converting a freshly prepared precipitate into the
colloidal dimension by the addition of suitable
electrolyte is called as Peptization. And the electrolyte used in this process is called as
Peptizing agent.

Example::- Ag+

AgCl + AgNo3 → Ag+ AgCl Ag+

Ag+

Cl -

AgCl + HCl →Cl - AgCl Cl -

Cl -

Fixed first layer

NO3- Mobile Second Layer

Ag+

AgCl
Differences B/w Lyophobic And Lyophillic Colloids ::-

Lyophilic Colloids Lyophobic Colloids

 These are easily formed.  These are formed only by special method.

 Its particles are true molecules.  Its particles are the aggregate of many
particles.

 These are stable.  These are unstable and require some

stabilizing agent.

 These are un charged i.e., neutral.  Lyophobic Colloids are charged particles.

 These are reversible.  These are irreversible.

 These are not affected by the addition of any  These precipitate out when an electrolyte is
electrolyte. added to it.

 By electrical dispersion method ::-

 Bredig’s Arc method ::-
This method is used to prepare colloids of metal like Platinum, silver, gold etc.

The metal whose colloid is to be prepared is made as electrode immersed in

dispersion medium such as water which is kept cold by surrounding it with a freezing mixture.

When electric Arc is set up, high heat is generated which can vaporizes
the metal which are condensed immediately in the liquid and stabilized by previous addition of
electrolyte.

+ -

Water + alcohol
 Mechanical Dispersion Method ::- In this method, the substance is first grounded into small particles
and then mixed with dispersion medium to get a suspension. The suspension is then grinded in a Colloidal
Mill which consist of two metallic discs which are nearly touching each other. The particles in colloidal
dimension can pass through it.

By Chemical Reaction ::-

H2S + Br → 2HBr + S
Colloid

2H2 S + SO2 → 2H2O + 3S

Colloid

FeCl3 + 3HOH → Fe(OH)3 + 3HCl

Colloid

H2S + 2HNO3 → 2H2O + 2NO2 + S

Colloid

 Determination of Charge on colloids ::-

Electrophoresis ::- The Phenomenon of movement of colloidal particle under an applied
electrical field is called as Electrophoresis.
If the particle accumulate near the negative electrode. The charge on the particle
is positive. While if the colloidal particle are accumulated near the positive electrode then the charge on the
particle is negative.
 -Ve +ve

Electro osmosis ::-

-ve
+ve

When the movement of colloidal particles are prevented by semi permeable membrane and the molecules of
dispersion medium are allowed to move. Then this phenomenon is called as Electro osmosis.

Thus electro osmosis is the phenomenon of the movement of molecules of dispersion medium
under the influence of the electric field. Whereas colloidal particles are not allowed to move.

 Purification of Colloids ::-

 Ultra-centrifugation ::- In this method the colloidal solution is taken in a tube which is
placed in an ultra-centrifuge and on rotating the tube at high speed. The colloidal particles
settle down and easily separated and purified.
 Ultra-Filtration ::- The process of removing the impurities from the colloidal solution by
passing it through graded filter papers is called as Ultra-Filtration.
 Dialysis ::- The process of separating the particles of colloids from those of crystalloids by
the process of diffusion through semi-permeable membrane is called as Dialysis.

It is based upon the principle that colloidal particles cannot pass through the membrane
whereas the ions of the electrolyte can easily pass through it by the process of diffusion.

The ordinary process of dialysis is very slow therefore to make it fast an electric field is applied
called as electro dialysis.
  Coagulation or Flocculation ::- The phenomenon of precipitation of colloidal solution by
the addition of excess of an electrolyte is called as Coagulation or Flocculation.

Since the colloidal particles are charged particles therefore, when excess
of electrolyte is added, they attract the oppositely charged particles of electrolyte and gets
neutralized and this process is called as Coagulation.

 Hardy Schulze Rule ::- According to this Rule ::

i. The ions carrying the charge opposite to that of colloidal particle are responsible
for coagulation.
ii. Larger the charge on the electrolyte, greater will be its coagulating power and
smaller will be its coagulation value.

Protection of Colloids ::- The process of protecting the Lyophobic colloidal solution from
precipitation by the previous addition of some colloids called as Protection of colloids, And such colloids are
called as Protective colloids.

Gold number :- Gold Number is defined as the minimum amount of protective colloid( in milligram)
required to just prevent the Coagulation of 10 ml of a gold solution when 10% (1 ml ) of NaCl Solution is
added to it.