• The molecules that are situated at the interfaces are known to behave

• The nearer the molecule to the surface, the greater is the magnitude of the
force due †o asymmetry.

&Experiences unbalanced attractive force resulting in a net inward pull •

This produces †he surface tension.

@Experiences balanced forces from all the directions and are in a state of
equilibrium.
 The accumulation of molecular species a† †he surface ra†her †han in bulk
of a solid or liquid is †ermed as Adsorption.

The material on the surface of which the adsorption takes place is called
adsorben†.

Eg. Silica gel, charcoal, clay, colloids e†c.

The molecular species or substance, which concen†ra†es or accumulates a†

†he surface is †ermed adsorba†e.

Absorption
It is the process by which atoms, molecules or ions enters the bulk It is a bulk
phenomenon.
It is an endothermic rocess.
It is same throughout the material.
It is not affected by temperature.

The accumulation of the molecular

ecies at surface not in the bulk It is a surface phenomenon.
It is an exolermic process. 3••*'•••f=
In this concentmtion at the surface is different than that of bulk of adsorbenh It
is temperature
dependent henomenon.

Both adsorption and absorption often take place side by side and we use the general
term Sorption
to define both.
During adsorption, †here is always a decrease in rasidual forces of †ha surface,
i.e. †here is a
decrease in surface enargy, which appears as hea†.

he

₀ A

The process of removing an adsorbed substance from a surface on

which i† is adsorbed is called Desorp†ion.

When the particles of the adsorbate are held to the surface of the adsorben† by †he
physical forces
such as Van Der Waal's forces, †he adsorption is called

When the molecules of the adsorbate are held to the surface of the
adsorbent by the chemical forces, the adsorption is called

S+2M
act

physisorbtion
distance from surface

S+M2

Ebind
chemisorbtion

Phyalcsl adsor Chemlcnl adaor @on

It is non-s ecifi It is hiahl ecific
It is reversible 1t is irreversible
(iii) The amount of gas depends upon (iii) The amount of gas adsorbed is not natue
o as, i.e.,
eas‹ ique rebted to criécal temperature o qases like NHt, CO2. as adsorbed to
gas.
greater extent than Heand He.
HL4iger the critical tern eraNre of gas more will be the extent of adsor tion.
(iv) tion (iv) It also inceases wiD increase in
Increases with incmase in surface surface area. area, e.g. porous and finely
Ilñoed
me@Is are ood adsorbents.
re weak van der Waals’ Iron Drce of attraction
forces of attraction between similar to chemical bond. adsorbate and
adsorbent.
(vi) It has low enthalpy of adsorption (vi) It has enthalpy heat of adsorptDn
20 - 40 k3 mol 180-
Low tern erature?i Hi h tern erature is favourable. reciable aQivation
(viii) Hi h
a%vation energy is
needed. sometimes need d.
It forms muRimolecular la em. It forms unim

The substances †ha† are porous in na†ure and have rough surfaces are be††er
adsorben†s.
The extent of adsorption also depends upon the surface area of the solid.
Greater †he surface area, more is †he surface available for adsorption and greater
is †he
adsorption.

The extent of adsorption also depends upon the nature of the gas. The gases which
are more easily
liquifiable or are more soluble in water are more readily adsorbed †han o†hers.

Physisorp†ion decreases wi†h †empera†ure, because adsorption is an exo†hermic

process.

Physical adsorption shows regular decrease wi†h †empera†ure. Bu†, chemisorp†ion

firs†
increases, †hen decreases wi†h †empera†ure.This is because i† requires ac†iva†ion
energy.

This .
why
chemisorp†ion is also called ’ac†iva†ed adsorption.

Represent the variation in the amount of gas adsorbed (x/m) with pressure (p)
at constant temperature.

Vaiid for single layer adsorption.

• Creating vacuum.

• Gos mosks
• Medicinal purposa

• Adsorption chromatography
• Adsorption indicators
• Humidity control • Froth— floatation process- Metallurg
• Removal of colouring matter from solutions

• Heterogeneous ca†aIysis

• Separation of inert gases

Berzillus in 1835 used †he word ca†aIys† firs† †ime for

Eg:Potassium chIora†e when hea†ed a† 653K †o 873K, i† gives O2, When MnO2 is used
in
†his reaction †he 02 is quickly a† †he low †empera†ure hence MnO2 is a ca†aIys†

(i) A Ca†alys† remains unchanged in mass and chemical compositions a† †he end of
reactions. However
i†s
physical s†a†e can be changed.

{ii) Highly efficien† : Finely devided s†ate of ca†alys† is more efficien† for †he
reactions
because surface
area increases and more adsorption take place.

(iii) A catalyst cannot initiate the reaction. But some times the activation energy
is so large
thot practically
a reaction may no† s†art un†iI a ca†aIys† lowers †he ac†iva†ion energy
significantly.
For example, mixture of hydrogen and oxygen do not react at room temperature but
the reaction
occurs
very rapid in presence of Pt black. i’ OI
I'i ) Highly speci fic : Catalys† are generally specific in nature. A substance
which act as a
catalys† in
particular reac†ion, fails to catalyse other reaction.

(vi)CataIyst cannot chan9e Equilibrium state but it helps to attain equilibrium

quickly.

(vii)A catalyst does not change the enthalpy, entropy and free energy of a
reaction.

(viii) Highly octnive under optimum temperature

When catalysts and reactants are in same phase then †he process is said to be
homogeneous
catalysis.

2. He†erogenous Ca†alysis
When ca†aIys†s and reac†an†s are in differen† phases, †hen process a know as
he†erogenous ca†aIysis
and ca†aIys† is called heterogeneous ca†aIys†.

The modern adsorption theory is the combination of intermediate compound formation

theory and the
old adsorption theory. The mechanism involves five steps:

(iy Diffusion of reac†an†s †o †he surface of †he ca†aIys†.

(ii) Adsorption of reac†an† molecules on †he surface of †he ca†aIys†.

(iii) Occurrence of chemical reaction on †he ca†aIys†’s surface through formation

of an
intermediate.

(iv) Desorp†ion of reaction products from †he ca†aIys† surface, and thereby, making
†he
surface available again for more reaction to occur.
(v) Diffusion of reaction products away from †he ca†aIys†’s surface.

+ A +B
Adsorption of
reacting molecules

Catalyst surface haring

free x‹alencies
Reacting
molecules

Adsorption of reacting molecule

+ A —B
Desorption of product molecules
Product

Catalyst
Intermediate
Activity' -The activity of a catalyst depends upon the strength of chemisorption to
a large extent.

Selectivity: -The selectivity of a catalyst is its ability to direct a reaction to

yield a particular produc† selectively.

Enzymes are complex ni†rogenous organic compounds which are produced by living
plants and animals.
They are actually protein molecules of high molecular mass and form colloidal
solutions in water.

The following are some of †he examples of enzyme-catalysed

reactions:

(i) Inversion of cane sugar: The inver†ase enzyme conver†s cane sugar into glucose
and fructose.

(ii) Conversion of glucose in†o e†hyI alcohol: The zymase enzyme conver†s glucose
into e†hyI
alcohol and
carbon dioxide.

(iii) Conversion of s†arch into mal†ose: The dias†ase enzyme converts s†arch in†o
mal†ose.
(iv) Conversion of maI†ose in†o glucose: The mal†ase enzyme converts mal†ose in†o
glucose.

(v) Decomposition of urea into ammonia and carbon dioxide: The enzyme urease
catalyses this
decomposition.

vi) In stomach, the pepsin enzyme converts proteins into peptides.

(vii) Conversion of milk into curd: It is an enzymatic reaction brought about by

lacto bacilli
znzyme present in curd.

('} Mos† highly efficien†: One molecule of an enzyme may transform one million
molecules
of the reactant per minute.

(.i) Highly specific na†ure: Each enzyme is specific for a given reaction.

tiii) Highly active under optimum temperature(298-310K).

(iv) Highly active under optimum pH(5-7).

{v) Increasing activity in presence of ac†iva†ors and co-enzymes.

(vi) Decreases activity in presence of inhibitors and poisons.

The catalytic reaction that depends upon the pore structure of the catalyst and the
size of
the reac†an† and produc† molecules is called shape-selective catalysis.
Zeolites are good shape-selective ca†aIys†s because of †heir honeycomb-like
structures.

They are microporous aIuminosiIica†es wi†h †hree dimensional network of silicates

in which
some silicon atoms are replaced by aluminium atoms giving AI-O-Si framework.

Zeolites are being very widely used as catalysts in petrochemical industries for
crackino of
hydrocarbons and isomerisation. An important zeolite catalyst used in the petroleum
industry is
ZSM-5.

There are a number of cavities present on the surface of colloidal particles of

enzymes. These
cavities are of charac†eris†ic shape and possess active groups such as -NH2, -COOH,
-SH, -OH, e†c.

These are actually the active centres on the surface of enzyme particles. The
molecules of the
reac†an† (substrate), which have complementary shape, fit in†o these cavities just
like a key fits
in†o

On account of †he presence of active groups, an activated complex is formed which

†hen decomposes
to yield the products.
Binding of enzyme to substrate to form an activated complex.

Decomposition of †he ac†iva†ed complex to form produc†.

The substance †ha† destroys the activity of ca†aIys† even in †he presence of †race
amoun† is known
as catalytic poison.
The catalytic poison is adsorbed on the ca†aIy†ic surface with more preference than
†he reactants.
Therefore, the reactants are not allowed to get adsorbed on the catalyst.

A substance which i†seIf is no† a ca†aIys† bu† promotes †he activity of a catalyst
is known as
catalytic promoter or activator.

The presence of promoter also increases †he peaks, cracks and corners on the
ca†aIys† surface
increasing i†s surface area.

With the addition of promoter in the catalyst, the lattice space of the catalyst is
changed and
increases †he space between †he ca†aIys† particles.

This resul† in †he weakening and cleavage of †he bonds of †he reac†an† molecules
making †he
reaction faster.

A colloid is a heterogeneous sys†em in which one substance is dispersed (dispersed

phase) as

very fine particles in another substance called dispersion medium.

System
Property Solution Collold Suspenslon
Particle type lo,._gg, toas, Lar e olecules or L articles or
small molecules peast c " ag¿re ates
Particle size 0.1-1 nm 1-1000 nm 1000 nm and larger ffect of light
No scattering
Exhibits Tyndall effect Exhibits Tyndall effect
Effect of Stable, does Stable, does not Unstable, sediment gravity
ot se $¿¿,te
se arate forms
Filtration Particles not Particles not retained a icles r tained on
retained on filter on
filter filter
Uniformity Homogeneous Hetero eneous Heterogeneous

Colloids are classified on †he basis of †he following criteria:

(i) On †he bosis of chorge

()Physcol s†o†e of dispersed phose ond disperson medium

(ii) Na†ure of in†erac†ion be†ween dispersed phase and dispersion medium

(iii) Type of particles of †he dispersed phase.

Hydrated metallic oodes. Metals, e.g., copper, s£ver, e.g.,

Al,O,.xH,O, OrO,.xI?,O
and gold sols.
Fg,Op.xH,O, etc.

Bdayelc
tuffs, e.g.,
Metalllc sulphides, e.g., As«Sq

methylene blue soI. HaemoQobln @lood)

Omde£, e.g., MO, sol.

congo re o s.
Sols of starch, gum, gelatln,
eloa, charcoal, etc.

Solld Solid
* Tolld Llquld
> Tolid Gas
N Llquld Solid
;¿ Llquld Llquld
* Liquid as
Y Gas Solid
$ Gas Llquld
Soñd sol
{J$ $) Aerosol Gel
s on Aerosol Toñd sol Foam
Some coloured Qasees and gem stones
Palnts. cell flulds
Smoke. dust
Cheese. butter. )ellles MUk, halr cream
Fog, mist. cloud, In cCcld mys
ce stone. foam rubber
, pedp, a er

(i) Lyophilic colloids: The word ’lyophilic’ means liquid -loving. Colloidal sols
directly formed
by mixing subs†ances

like gum, gelatine, s†arch, rubber, e†c. , wi†h a suitable liquid (†he dispersion
medium) are
called lyophilic sols.

(ii) Lyophobic colloids: The word 'lyophobic’ means liquid -ha†ing.Substances like
metals, †heir
sulphides, etc.,
when simply mixed with †he dispersion medium do not form †he colloidal sol.

Depending upon †he type of †he particles of †he dispersed phase, colloids are
classified as:
mul†imolecular,

macromolecular and associated colloids.

(i) Mul†imoleculor colloids: On dissolution, a large number of a†oms or smaller

molecules of a
subs†ance
aggregate

†oge†her †o form species having size in †he colloidal range (1-1 OOO nm). The
species †hus formed
are called

mul†imolecuIar colloids.

For example, a oold sol may con†ain par†icles of various sizes having many a†oms.
Sulphur sol
consis†s of particles containing a thousand or more of Ss sulphur molecules.

(ii) Macromolecular colloids: Macromolecules in suitable soIven†s form solutions in

which †he size
of †he
macromolecules may be in †he colloidol range. Such systems are called
macromolecular colloids.

Examples of naturally occurring macromolecules are s†arch, cellulose, proteins and

enzymes: and
†hose
of man-made macromolecules are polythene, nylon, polystyrene, syn†he†ic rubber,
e†c.
(iii) Associated colloids (Micelles): There are some substances which at low
concen†ra†ions behave
as normal strong electrolytes, but at higher concentrations exhibit colloidal
behaviour due to the
formation of aggregates. The aggregated particles thus formed are called micelles.
These are also
known as associated colloids.

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).

When dissolvad in wotar, i† dissociates into RCOO- and Na+ ions. The RCOO- ions,
howevar, consis†
of two parts

— a long hydrocarbon chain R (also callad non-polar ’tail’) which is hydrophobic

(wotarrepelling),
and a polar group

COO- (also called polar- ionic 'head’), which is hydrophilic (watar loving).

The RCOO- ions are, tharefore, presant on the surface with thair COO- groups in
watar and the
hydrocarbon chains
R staying away from it and remain at the surface. But at critical micalle
concentration, the anions
are pullad into

†he bulk of †he solution and aggregate \o form a spherical shapa wi†h their
hydrocarbon chains
pointing towards tha

cen†re of †ha sphera wi†h COO- part remaining outward on †ha surface of †ha sphera.
An aggregate
thus formad is

{.y Sodium stearate C17H35COO Na (Soap).

 {ii) Sodium lauryl sulphate CH3[CH2]11 SO4" Na (Detergent).

(iii) Cetyl trimethyl ammonium bromide (Detergent). CH3(CH2)1sN (CH3)3gr".

The cleansing action of soap is due to the fact that soap molecules form micelle
around the oil
droplet in such a way that hydrophobic part of the stearate ions is in the oil
droplet and
hydrophilic part projects out of the grease drople† like †he bris†les. Since †he
polar groups can
in†erac† wi†h wa†er, †he oil drople† surrounded by

Soap or detergent dissolves ih water

Surfactant Agitation
ions orientate begins to
themselves in separate grease and water grease from
surface

§„,{gSurfactant ions
Process
continues
Cleaning complete

Clean surface
Colloidal solutions can be prepared by chemical reactions leading to formation of
molecules by
double decomposition, oxidation, reduction or hydrolysis. These molecules then
aggregate leading to
formation
OF SOLS .

When a ho† aqueous diIu†e solution of arsenous oxide (AszO3) is mixed wi†h a
saturated solution of
HIS in wa†er, a colloidal sol of arsenous sulphide (As2S ) iS Obtained.

A colloidal sol of sulphur is obtained by passing HzS in†o a solution

of sulphur
dioxide.

Colloidal sol of metals like gold, silver solution are obtained by following
method.

dilute solution FeCIs

colloidal
AICI OP CrCl3
metal hydroxides
like
Al(OH)s OP

”IS
obtained
by boiling

In †his me†hod, electric arc is s†ruck between electrodes of †he me†aI immersed in
†he dispersion
medium. The intense hea† produced vapourises †he me†oI, which †hen condenses †o
form particles of
colloidal size
This process involves dispersion as well as condensa†ion. Colloidal sols of me†als
such as gold,
silver, platinum, e†c.
Pap†ization may be dafined as the process of converting a pracipi†ata into
colloidal sol by shaking
i† with dispersion
medium in †he presanca of a small amoun† of aIec†roIyte. The eIectroIy†eused for
†his purposa is
called pep†izing agen†.

The process used for reducing †he amount of impurities is known as purification of
colloidal
solution.
The purification of colloidal solution is carried out by the following mehods:

(ii) Electro-dialysis

(iii)UlroWlroWon

I† is a process of removing a dissolved substance from a colloidal solution by

means of diffusion
through a suitable membrane.
A bag of suitable membrane containing †he colloidal solution is suspended in a
vessel through
which fresh wa†er is continuously flowing.

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

The apparatus used for †his purpose is called dialyser.

Ordinarily, the process of dialysis is quite slow. It can be made fas†er by
applying an electric
field if †he dissolved substance in †he impure colloidal solution is only an
elec†roIy†e. The
process is then named electrodialysis.

The colloidal solution is placed in a bag of suitable membrane while pure water is
taken outside.
Electrodes are fitted in the compartment. The ions present in the colloidal
solution migrate out to
the oppositely charged electrodes.

UI†rafiI†ra†ion is †he process of separating †he colloidal particles from †he

solven† and soluble
solutes presen† in †he colloidal solution by specially prepared filters, which are
permeable †o all
substances except the colloidal particles. Colloidal particles can pass through
ordinary filter
paper because the pores are too large.
An ultra-filter paper may be prepared by soaking the filter paper in a collodion
solution,
hardening by formaldehyde and then finally drying it. Ultrafiltration is a slow
process. To speed
up †he process, pressure or suction is applied. The colloidal particles lef† on †he
uI†ra- filter
paper are then stirred with fresh dispersion medium (solvent) to get a pure
colloidal solution.

1. Heterogeneous character
Colloidal sols are heterogeneous in character as †hey consis† of †wo phases.
(o) dispersed phose end (b) dispersion medium.
2. Visibility : Due †o sca††ering caused by †he colloidal particles, i† will appear
as a brigh†
spo†
moving randomly.

3.Filterability : Colloidal particles pass through an ordinary filter paper.

However, the particle
do no† pass through o†her fine membranes.

^..CoIIigative Properties : Due to high average molecular masses of colloidal

particles, mole
fraction of the dispersed phase is very low. Hence, the values of the colligative
properties
observed experimentally are very small. Only osmotic pressure measurements are used
in determining
†he molecular mass of polymers.

Optical Properties-Tyndall effec†. Tyndall, in 1869, observed †ha† if a strong

beam of ligh† is
passed through a colloidol sol placed in a dark place, the path of the beam gets
illuminated. This
phenomenon is called Tyndall effect.

Condition:Tyndall effec† is observed only when †he following †wo conditions are
satisfied.

(i) The diameter of the dispersed particles is not much smaller than the wavelength
of the
ligh† used: and

(ii) The refractive indices of †he dispersed phase and †he dispersion medium differ
greatly

Mechanical Properties :
Brownian movemen†: Rober† Brown, a bo†anis†, discovered in 1827 The particles were
seen
†o be in cons†an† zig-zag mo†ion as shown in fig. This zig-zag mo†ion is called
Brownian
movement.

Charge on colloidal particles:

Colloidal particles always carry an electric charge. The charge on †he sol
particles is due †o
one or more reasons.

Preferential adsorption of ions is †he mos† accepted reason. The sol particles
acquire positive or
negative charge by preferential adsorption of positive or negative ions.

When two or more ions are present in the dispersion medium, preferential adsorption
of the

For example :
(i) When frashly pracipitatad Fe(OH)3 is shaken with aqueous solution of FeCI3
(peptizing agent) it
adsorbs Fe3+ ions and
†heraby breaks up into small -sizad par†icIas.

(ii) Freshly prepared stonnic oxida on treatment with a small amoun† of diIu†a
hydrochloric acid
forms a stable colloidal
sol of s†annic oxide, SnO2 ; Sn4+ .

Cadmium
sulphide can be pep†ised
wi†h
†he help
hydrogen sulphide, CdS
S2—

†his layer
a††rac†s counter
ions POl'fi †he
medium forming
second layer

Electrical Properties (Electrophoresis)

When electric potential is applied across two platinum electrodes dipping in a
colloidal solution,
the colloidal particles move towards one or the other electrode. The movement of
colloidol
particles under on applied electric potential is called electrophoresis.

Positively charged particles move towards †he cathode while ne9a†iveIy charged
particles move
towards †he anode.
Depending upon the direction a movement of particles towards cathode or anode
electrophoresis con
be called

Arsenious sulphide, gold, silver and platinum particles in †heir respective

colloidal sole are
ne9a†iveIy charged while

The process of settling of colloidal par†icIas is called coagulation or

pracipi†ation of tha sol.

The coagulation of tha lyophobic sols can be carried ou† in tha following ways:

{I} By elec†rophoresis

By mixing two opposi†eIy chargad sols

) By boiling ’

(ivj By persistent dialysis

( y addition of elac†roly†es

A nega†ive ion causas †he pracipitation of posi†ively charged sol and vica versa.

The ion responsible for neutralisation of chorga on the par†icIas called tha
coagulating ion.
Generally, tha grette hemnc of the /loccuIating ion addad, tha greater is its power
to cause
precipitation.
This is known asCardy- Schulze ruled

ti) Blue colour of the sky

tii} Fog, mis† .“

(iii) Food articles

tiv) Blood ” ” * .

(vQ Formo†ion of del†o

River wa†er is a colloidal solution of Icay.When river water mee†s †he sea wa†er,
h I oIy†es
presen†
in sea wa†er coaguIo†e1he colloidal solution of clay resu ing in i†s deposition
wi†h the formation
of deI†o.

Colloids are widely used in †he industry. Following are some examples

Industrial products
Lyophilic colloids have a unique property of pro†ec†ing lyophobic colloids. When a
lyophilic sol is
added †o †he lyophobic sol, †he lyophilic particles form a layer around lyophobic
particles and
†hus pro†ec† †he Ia††er from elec†roIy†es. Lyophilic colloids used for †his
purpose are called
pro†ec†ive colloids.

The Gold Number is †he minimum weigh† (in milligrams) of a pro†ec†ive colloid
required †o prevent
the coagulation of 10 ml of a standard gold sol when 1 ml of a 10% sodium chloride
solution is
added †o i†.