1

SURFACE CHEMISTRY RS
Adsorption: The phenomenon of accumulation of a substance at the surface rather than in
the bulk of a solid or liquid is known as adsorption.

Adsorbate: The substance accumulating at the surface of the solid during adsorption is
called adsorbate.

Adsorbent: The surface on which adsorption occurs is called adsorbent.

Sorption: Sometimes the adsorbate dissolves into adsorbent. Initially the adsorbate appears
on the surface of adsorbent and later passes into bulk of the adsorbent. Thus adsorption
changes into absorption. This is called sorption.

Desorption: The process of removing an adsorb substance from a surface of adsorbent is

called desorption.

Example of adsorption: When ammonia taken in a closed vessel containing finely divided
activated charcoal. The pressure of NH3 decreases. The decrease is due to adsorption of
NH3 on the surface of charcoal.

Cause of Adsorption: A particle (atom, molecule or ion) in the bulk of a liquid or solid is
equally attracted from all directions by neighbouring particles as a result net force of
attraction becomes zero. The particle at the surface is not uniformly surrounded and
attracted by neighbouring particles from one side. The unequal force of attraction acting
outward is called the residual force of attraction. This residual force of attraction attracts
the molecule, atom or ion which come in contact with its surface and decreases surface free
energy which is known as adsorption.

Change in enthalpy in an adsorption process: Adsorption is a spontaneous process at given

temperature and pressure therefore ∆ G must be negative. In adsorption the randomness of
the adsorbate molecule decreases, therefore ∆S is negative.

Now, ∆ G = ∆H - T∆S

And for the spontaneous process ∆G must be negative as T∆S is negative.

• ∆G can be negative only if ∆ H is negative and greater than T∆ S.

Therefore, adsorption is an exothermic process.

Physical adsorption:
In adsorption process, if adsorbate particle are held on the surface of adsorbent by vander
waal forces is known as physical adsorption>

Ex: adsorption of N2 gas on finely devided iron at low temperature.

2

Characteristics of physical adsorption:

i.It is non specific in nature therefore at particular temperature and pressure different gases
may be adsorb on the surface of any solid adsorbent.
 2

ii.It is reversible in nature.

iii.It depends on the nature of gas. Gases with higher critical temperature (easily liquefiable)
show physical adsorption to greater extent. As they possess a strong van der waals force of
attraction.
iv.The heat of adsorption is low (20-40 KJ/mol) in this case.
v.The extent of adsorption directly proportional to the surface area of the adsorbent. The
larger the surface area, greater the extent the physical adsorption.
vi.In physical adsorption more than 1 layer of molecule may be adsorbed on the the surface
of an adsorbent. So physical adsorption is a multilayer process.

Chemical Adsorption:
The adsorption process in which the adsorbate particles are held on the surface of
adsorbent by chemical force is known as chemical adsorption.

Ex: adsorption of H2 gas on the surface of metal like Ni and pt.

Characteristics of chemical adsorption:

i.Chemical adsorption is highly specific in nature. It occurs only when there is possibility of
formation of chemical bonds between adsorbent and adsorbate.
ii.It is irreversible.
iii.The heat of adsorption is high (go to 240 kJ/mol).
iv.The activation energy for chemical adsorption is very high. As they are involved in the
formation of chemical bonds.
v.The rate of chemical adsorption is low at low temperature. Since it requires high activation
energy. Therefore chemical adsorption favours moderate high temperature.
vi.Chemical adsorption increases with increasing the surface area of adsorbent.
viiChemical adsorption from unimolecular layers. Since chemical adsorption involves
formation of chemical bonds between adsorbate and adsorbent. Only mono layer is formed
on the surface of adsorbent.

Factor affecting the adsorption of gas by solid:

i Nature of gas: Under given condition of temperature and pressure easily liquefiable gases
(NH3, SO2, CO ) gases with higher critical temperature undergo physical adsorption to a
2

greater extent. While the gases that are not easily liquefiable that is Gases with lower
critical temperature undergo physical adsorption to a smaller extent.

Chemical adsorption is highly specific in nature. Chemical adsorption by solid surface occurs
only if there is a possibility of forming chemical bonds between adsorbate and adsorbent
particles.

ii.Nature of adsorbent: Adsorption depends on surface area of the adsorbent. Greater the
surface area of an adsorbent greater will be capacity for adsorption that is why A finely
divided adsorbent is a better adsorbent than in the form of lump.
iii. Temperature: Adsorption is an equilibrium process in which adsorption and desorption
both take place at same rate. Adsorption is an exothermic process which is favoured at
 3

lower temperature, this is applicable only for physical adsorption. For which the activation
energy is almost zero and adsorbent.
Since chemical adsorption has high activation energy. It increases rise in temperature but
also decreases when temperature is very high. At very high temperature thermal energy of
adsorb gas molecules on the surface of adsorbent increases and therefore rate of
desorption also increases.
The plot extent of adsorption (x/m) v/s temperature is known as
adsorption isobar.

, Pressure: In the adsorption of gas on the solid gas molecules are adsorbs on the surface
of solid and so the number of gas molecule decreases. Hence, the extent of adsorption
increases with increasing pressure at a constant temperature. The plot of the extent of
adsorption v/s pressure at constant temperature is called adsorption isotherm.

The extent of adsorption increases with increasing pressure both for physical and
chemical adsorption. After a certain pressure it reaches a maximum and no more adsorption
occurs if the pressure is further increased. The pressure at which adsorption occurs its
maximum value is called saturation pressure.

Q. What is Adsorption Isotherm? Describe freundlich adsorption isotherm.

Ans. The plot of the extent of adsorption vs pressure at constant temperature is called
adsorption isotherm.

Freundlich adsorption isotherm: Freundlich adsorption isotherm is,

x/m = k P1/n ...1 Where x is the amount of adsorbate on m gram of
adsorbent
at a pressure P where k and n are constant

taking both side log of equation 1

𝑋 1
log𝑚= 𝑛 logP + logK

Y = mX +C
 4

• As the plot of log x/m vs logP is a straight line freundlich adsorption is valid.
• This isotherm explains the behavior of adsorption approximately and 1/n can have
any value between 0 and 1.
• When 1/n = 0, x/m is constant which shows that adsorption is independent of
pressure.
• When 1/n = 1, x/m = Kp, i.e; x/m α P.

# The absorption varies directly with pressure.

Catalyst:
A catalyst is a substance which influences the rate of a chemical reaction without
itself undergoing any chemical change at the end of the reaction.

catalysis

Heterogeneous Homogeneous

Heterogeneous catalysis: When the catalyst is in a different phase from that of

reactant. The phenomena is known as Heterogeneous Catalyst.

Ex. i) hydrogenation of ethylene by Ni catalyst.

𝐻2/𝑁𝑖
CH = CH →
2 2 CH3-CH3

. ii) oxidation of ammonia to nitric oxide.

𝑝𝑡
4NH3 +5O2 → 4NO + 6H2O

Adsorption theory of heterogeneous catalysis:

i.Diffusion of reactant to the surface of catalyst.
ii.Adsorption of reactant molecule on the surface of catalyst.
iii.Chemical reaction take place on the surface of heated catalyst through formation of
intermediate.
iv.Desorption of product molecule from the surface of catalyst.
v.Diffusion of product away from the surface of catalyst.
 5

Characteristics of catalytic reaction:

I.Catalysts remain unchanged in mass and chemical composition at the end of the reaction.
II.A small amount of catalyst is generally needed to produce almost unlimited reaction.
III.A catalyst dose not initiate a reaction.
IV.A catalyst is more effective when it is finely divided.
V.A catalyst is specific in its action.
VI.Change of temperature changes the rate of a catalytic reach.
VII.A catalyst does not alter the final position of equilibrium. Although it decreases the tune
required to establish.
Activity of catalyst:
The ability of a catalyst to increase the rate of reaction is called catalytic activity.
It is also defined as the no. of moles of a reaction that react in the presence of a unit
mass of catalyst in unit tune is known as activity of catalyst.
Unit: Mol gm S
-1 -1

Selectivity of a catalyst:
The ability of a catalyst to follow a specific reaction mechanism and form a specific
product is known as the selectivity of a catalyst.

Catalytic promoter:
A substance which through itself is not a catalyst promotes the activity of catalyst
such a substance is called a promoter or an activator.

Molybdenum acts as a promoter for iron catalysts.

Classification of Catalysis :
i. Positive catalysis,
ii. Negative catalysis,
iii. Auto catalysis,
iv. Induced catalysis.
i. Positive catalysis : When the catalyst accelerates the speed of a chemical reaction, it is
known as a positive catalyst and the phenomenon is known as positive catalysis.
Examples :
2KClO3 → 2KCl + 3O2 in presence of Pt
2SO2 + O2 → 2SO3 in presence of Fe
ii. Negative catalysis : When the foreign substance retards the speed of a chemical
reaction, it is known as a negative catalyst and the phenomenon is known as negative
catalysis.
Examples :
 6

2H2O2 → 2H2O+ O2 in presence of H3PO4

4CHCl3 + 3O2 → 4COCl2 + 2Cl2 + 2H2O.
iii. Autocatalysis : When one reaction influences the speed of the other, which is not
possible under ordinary conditions, the phenomenon is known as induced catalysis.
Example : 2Na3AsO3 + O2 → 2Na3AsO4 (not possible) It is possible only when the
following reaction also occurs side by side.
Na2 SO3 +Na3AsO3 + O2 → Na2SO4+2Na3AsO4
Characteristics of catalytic reaction:
Enzyme catalysis: Enzymes are complex nitrogenous organic compounds which are
produced in the living cells of plants and animals; they are also called biochemical catalysts
because of their importance in the biochemical process.

Characteristics:

• Enzymes form a colloidal solution in water and hence they are a very active catalysis.
• Like inorganic catalysts they do not disturb the final step of equilibrium of a
reversible reaction.
• They are highly specific in nature.
• They are highly specific to temperature. Optimum temperature of their activity is
35 c to 40 c. They are deactivated at 70 c.
0 0 0

• Their activity is an increase in pressure of a sudden substance known as coenzyme.

• A small quantity of enzyme catalyst is sufficient for a large change.
Ex:

Mechanism of enzyme catalyst reaction:

The enzyme catalyst reaction takes place in 2steps

Step 1: Binding of enzyme to substrate to form an activated complex.

E + S → ES≠

Step 2: Decomposition of the activated complex to form the product.

ES≠ → E +P

This mechanism is also known as lock and key mechanism.

Shape selective catalyst: Catalytic action that depends on the structure of the pore of a
catalyst and size of the reactant and the product molecule s is known as shape selective
catalyst
Zeolites, due to its honeycomb like structure serve as an excellence shape selective
catalyst. They are microporous aluminosilicates with 3-D networks of silicates. The catalytic
process depends on the shape and size of the reactant product and the pores present in the
zeolites. Zeolite is extensively used as a catalyst in the petrochemical industry for cracking of
hydrocarbons and isomerism.
ZSM – 5 is an important zeolite catalyst which produces petrol or gasoline by dehydration of
alcohol.
 7

COLLOIDAL STATE OF MATTER

Colloidal solution: It is a heterogeneous system therefore consisting of two phases-
dispersed phase and dispersion medium. The diameter of the particle ranges from 1 to 100
km. This particle does not settle down under the force of gravity on long standing.

Ex: glue, starch, albumin, gelatin, soap solution etc.

Disperse phase: The phase of colloid particles is called the dispersion phase. This is like a
solute in the solution.

Dispersion medium: The medium in which dispersed particles are dispersed is called
dispersion medium. This is like a solvent in true solution.

Crystalloids: The substance whose aqueous solution can pass the semipermeable
membrane are called crystalloids.

Comparison between true solution colloidal solution and suspension:

True solution Colloidal solution Suspension

Homogeneous Heterogeneous Heterogeneous
Particle are not visible even Particle are not visible to Particles are visible under
under ultramicroscope naked eyes but can be seen ordinary microscope also
through ultramicroscope sometimes through naked eyes
Can pass through both filter Can pass through filter Cannot pass through a filter
paper and parchment paper paper but cannot pass paper or parchment paper
through parchment paper
These solution are Colloidal particles are Particle as well as solution are
electrically neutral either positively or electrically neutral.
negatively charged
Dose not show Tyndall Shows Tyndall effect These solution do not exhibit
effect the electrical property
Particle size ≤ 10 cm
-8
Particle size 10 – 10 cm
-7 -5
Particle size >10 cm
-5

Rarely show brownian Show brownian movement Show brownian movement in

movement some cases
These solution do not show These solution show all These solution do not show
electrophoresis,electro these properties electrophoresis,electro osmosis
osmosis
 8

Classification of colloids

Dispersed Dispersion Name of examples

phase medium colloid
Solid Solid Solid solColoured glass,glass, ruby
Solid Liquid sol Paints,ink,milk of magnesia,gold sol,
silver sol
Solid Gas Solid aerosol Smoke, dust strome
Liquid Solid Gels Jellies, cheese,curd,
Liquid Liquid Emulsion Milk, cod liver oil
Liquid Gas Liquid aerosol Mist,fog, cloud
Gas Solid Solid foam Pumice stone,rubber,cake
Gas Liquid Foam Soap lather, soda water
SOL: It is the colloidal system in which the disperse phase is solid and the dispersion
medium is liquid.
Ex: gold sol, sulphur sol.
SOL

Hydro sol Alcosol Benzosol Aerosol

Dispersion Dispersion Dispersion Dispersion
medium is medium is medium is medium is air
water alcohol benzene Ex: smoke,fog
Ex : gold sol

Classification of colloid based on attraction between disperse phase and

dispersion medium:

Colloid

Lyophilic colloid Lyophobic colloid

The colloidal solution in which the The colloidal solution in which particles
particles of the dispersed phase have of the dispersed phase have little affinity
strong affinity for the dispersion medium for the dispersion medium is known as
is known as lyophilic colloid. lyophobic colloid

Ex: Gum,starch,geletine Ex:Gold sol, silver sol ,sulphur sol

 9

Difference between lyophilic and lyophobic colloid:

Lyophilic colloid Lyophobic colloid
Organic compounds are used in dispersed Inorganic compounds are used in dispersed
phase phase
Viscosity is greater than dispersion medium Viscosity is same as the dispersion medium
Surface tension is less than dispersion Surface tension is same as the dispersion
medium medium
It is more stable and reversible nature It is less stable and irreversible nature
It is easily prepared It cannot be easily prepared
It cannot be coagulate easily It is easily coagulate

Classification of colloid on the basis of nature of disperse phase:

Colloid

Multimolecular colloid Macromolecular colloid Associated colloid

Multimolecular colloid: This colloid consists of particles that are large aggregates of atoms
or molecules. The atom and molecule are held together by weak vanderwall force of
attraction. These are lyophobic colloids.

Ex: A sulpher sol contains thousands of S sulphur molecules.

8

A gold sol may have particles of various sizes having many atoms.

Macromolecular colloid: There are many substances whose individual molecules have a
very large size with colloidal dimension. Such large molecules are called macromolecules.
When these substances form a colloid they are called Macromolecular colloids.

Ex: Natural starch, cellulose, protein, vitamin.

Synthesis macro macro macromolecular colloid are ploy ethylene, nylon etc.

Associated colloid: There are certain substances which at low concentration behave like
normal strong electrolytes but at higher concentration behave as a colloidal solution due to
the formation of aggregated particles. Such colloids are associated colloids and aggregated
particles known as miscalls.

Ex: soap and detergent.

 10

Definition of CMC (critical micelle concentration):

In case of the solution of a substance capable of forming micelle there is a minimum
concentration of the solution above which micellization began. This is called critical micelle
concentration.

Craft Temperature:
The minimum temperature above which micellization began is known as Kraft
Temperature.

Type of emulsion: Emulsion

Oil in water type of emulsion. Water in oil type of emulsion.

Ex: milk Ex: butter,cod liver oil ,cold
cream

Emulsifier or Emulsifying agent

The substance that is added during the preparation of an emulsion to increase the stability
of the emulsion to increase the stability of the emulsion is known as emulsifier or
emulsifying agent.

Ex: soap or detergent, sulphonic acid having a large hydrocarbon tail acts as an emulsifier.

Surface active agents:

A substance which when added to a liquid preferentially gets absorbed on the
surface of the liquid and reduces its surface tension to a large extent, is called a surfactant
or surface active agent.

surface active agent

Anionic surface active Cationic surface active agent. Non inorganic surface active
Ex : Cetyl trimethyl agent
agent ammonium chloride Ex: alkyl polyethylene oxide
Ex: sodium stearate

Preparation of lyophobic colloids:

Peptisation: The conversion of a freshly formed precipitate into a sol by addition of a small
amount of an electrolyte is called peptisation.

# The electrolyte used for this purpose is called peptizing agent.

 11

Cause of Peptisation:
During peptisation, the precipitate selectively absorbs one of the ions of the
electrolyte, which is common with the precipitate. This develops a positive or negative
charge on the particles of the precipitate. Mutual repulsion between the like charged
particles results in splitting of the particles into smaller particles of colloidal dimension.

For example, when FeCl solution is added to freshly prepared Fe(OH)3 Fe3+ ions are
3
+

selectively adsorbed by the precipitate and eventually forms Fe(OH)3 sol.

Example of peptisation:
i.A freshly precipitated sodium hydroxide Fe(OH)3 is mixed with a water and small quantity
of FeCl3. A brown colour ferric hydroxide sol is obtained.
Here, FeCl3 is a peptizing agent.
ii.A freshly prepared precipitated Al(OH)3 is mixed with water and a small quantity of dil.
HCl, produces Al(OH)3 sol.
Here, dil. HCl is a peptizing agent.

Dialysis:
The process of removal of crystalloid from colloid by means diffusion through
parchment paper is known as dialysis or cellophane membrane.

Electro dialysis:
Dialysis in which the movement of ions is added by an electric field applied across a
semi permeable membrane is known as electro dialysis.

Application of dialysis:
i.In the human body kidney work as a dialyser. Blood is a colloidal solution. Harmful
substances produced during physiological activities, the blood gets contaminated and the
impure blood passes through the kidney and gets purified due to removal of impurities by
dialysis.
ii.Artificial kidney or haemodialysis, work on the principle of dialysis. Blood flows through the
inner tube of the two concentric tubes made of cellophane. While water flows in the
annular space in between the tubes. As a result the non-colloidal impurities pass through
the cellophane membrane into the stream of water in the annular space.
Tyndall effect
When a beam of light is allowed to pass through a colloidal solution placed in a dark
room. Scattering of light by colloidal particles occurs. Illuminated path of light can be
visualized from a direction at right angle to the incident light. This phenomenon is known
as a Tyndall effect.
The illuminated beam or cone formed by the scattered light inside the colloidal solution
is called a Tyndall beam or cone.
 12

Conditions for Tyndall effect:

i.There is a negligible difference between the diameter of a dispersed particle and
wavelength of the light used.
ii.There is a large difference between the refractive indices of the dispersed phase and
dispersion medium.

Electrophoresis:
The preferential movement of a colloidal particle under the influence of an applied
electric field is called electrophoresis.

Cataphoresis and anaphoresis:

The movement of a positive sol towards the cathode is known as cataphoresis.
Ex: [Fe(OH)3sol] ferric oxide sol.
The movement of negative sol towards the anode is known as anaphoresis.
Ex: (As S )sol arsenious sulphide sol.
2 3

Electro-osmosis:
The movement of a dispersion medium towards a certain electrode through a semi
permeable membrane at the influence of an applied electric field is known as electro
osmosis.
Protective colloid:
The prevention of coagulation of lyophobic sol by addition of some lyophilic colloid.
This is known as prevention of colloid and the lyophilic colloid is known as protective colloid.

Gold Number: The number of milligrams of a protective colloid that must be added to 10mL,
of a standard gold sol (0.0053 to 0.0058%) so as to just prevent the coagulation of the sol
(i.e., to prevent the colour change from red to blue) on addition of 1mi, of 10% NaCI
solution is called the gold number of that protective colloid.
Therefore, a small amount of a protective colloid with a small value of gold number is
sufficient to prevent the change in colour of a gold sol. This means that smaller the value of
gold number of a lyophilic sol, greater is its protecting power.

Coagulation: The precipitation of the dispersed phase of the colloid by the addition of a
suitable electrolyte is called coagulation, and the substance in presence of which
coagulation occurs is called the coagulating agent.

Hardy-Schulze rule:
( i)Ions carrying an electrical charge opposite to that of the particles of a colloid are
responsible for bringing about the coagulation of the colloid.
(ii)Greater the electrical charge of the oppositely charged ion, greater is its coagulating
power.
 13

Coagulating power of an electrolyte varies directly with the valency of the ion causing
coagulation. ln the coagulation of negatively charged colloids, the order of coagulating
efficiency of different cation is
Al3+ > Mg2+ >Na+ and for the coagulation of positive ly charged colloids, the effectiveness of
the anions are in the order, [Fe(CN)]4- ,PO43- SO42-

Example: (i)For the coagulation of As2S3 sol, AlCl3 is much more effective than NaCI. The
particles of As2S3 sol are negatively charged. So the particles of this sol will be neutralised by
the positively charged ions (here, Na+ or Al3+ ). As the charge on Al3+ is greater than Na+
,AlCl3 is more effective in the coagulation of As2S3 sol.
(ii)In the coagulation of Fe(OH)3 sol, Na2SO4 is more effective than NaCI. The particles of
Fe(OH)3 sol are positively charged and hence, they are neutralised by the negative ions
(here, Cl- and SO42- ). As the charge on SO42- is greater thanCl- , Na2SO4 is more efficient than
NaCI in coagulating Fe(OH)3 sol.

Coagulation or Flocculation Value: The minimum amount of electrolyte (in millimoles) that
must be added to one litre of a colloidal solution leading to complete coagulation is called
coagulation or flocculation value. It is generally expressed in millimoles/ litre.

Applications of colloid chemistry

Food stuff:
Most of our food-stuffs like milk, butter and creams are colloids. In milk, fat is dispersed in
water. In ice cream, cream is dispersed in ice. In fried egg, albumen is coagulated by heating
with oil, preparation of boiled rice from raw rice or food from potatoes involves the
coagulation of starch.
Medicine:
Medicines in colloidal state are much more effective as they are easily absorbed by the
body. Example: Antimony colloid: specific medicine for black-fever,
Angier's emulsion: used in cough and cold, Milk of magnesia: used in stomach trouble,
Silver colloid: used as eye lotion.
Purification of water:
Impurities in water such as mud, soil and other silicon materials exist in colloidal form.
Addition of alum, [K2SO4 ,Al2(SO4)3.24H2O] precipitates the negatively charged colloidal
impurities by neutralising them with Al3+ and K+ ions. Coagulated contaminants settle down
at the bottom and pure water is obtained by filtration.
Formation of delta:
River water is a colloidal solution which contains clay dispersed in water. When turbid water
mixes With sea Formation water at the mouth of the river, different salts present in sea
water coagulate the Impurities of river water. These coagulated Impurities accumulate at
the confluence in course of time, forming the delta.
Cleansing action of soap :
Most of the dust or dirt sticks to the grease or oily sub-stance present on clothes. As grease
is not wetted by' water, it cannot be cleaned by water alone. The addition of soap or
 14

detergent lowers the interfacial tension between water and grease and causes
emulsification of grease in water.

Clotting of blood :
Blood is a colloidal solution of albumin (negatively charged) particles. We use alum to stop
bleeding in minor wounds. The positive ions such as Al3+ , K+ present in alum coagulate the
negatively charged colloidal particles resulting in clotting of blood.

Haemo-dialyser:
The process of artificial dialysis for the purification of blood is employed in the case of
persons suffering from kidney failure. The apparatus with the help of which artificial dialysis
is conducted, is known as haemo-dialyser.
Cottrell precipitator :
The removal of smoke and dust from air by electrophoresis is done in the Cottrell
precipitator. The air from a furnace is passed between metal electrodes maintained at a
high potential difference (about 50,000 volts). The particles are discharged and deposited as
precipitates on the oppositely charged electrodes, from which they are mechanically
scrapped off.
Rubber Industry :
Rubber is obtained by coagulation of latex, obtained from rubber trees. In rubber plating,
the negatively charged particles of rubber (latex) are deposited on wires or handles of
various tools by electrophoresis.
Artificial rain :
When air saturated with water vapour comes in contact with the charged dust particles
floating in air, it forms a colloid which we call cloud. To cause artificial rain, oppositely
charged sand particles are sprayed over the clouds by aeroplane. Consequently, the charge
on the colloidal water particles is neutralised which coagulate to form bigger water drops,
causing artificial rain.
Blue colour of the sky:
Light from sun when passes through air, is scattered by the suspended particles in air. This
fact is an example of Tyndal effect. As the wavelength of blue light is very small, it is
scattered to a great extent. This makes sky appear blue to our eyes.