(5403) Sheet Surface Chemistry Theory e

Surface Chemistry
INTRODUCTION :
Surface chemistry is that branch of chemistry which deals with study of the phenomena occuring at the
surface or interface, i.e. at the boundary separating two bulk phases. In this chapter our main emphasis will
be on three important topics related to surface chemistry, viz., adsorption, colloids and emulsions.
 Adsorption : The phenomenon of attracting and retaining the molecules of a substance on the surface
of a liquid or a solid resulting into a higher concentration of the molecules on the surface is called adsorption.
As a result of adsorption, there is a decrease of surface energy. The process of removal of an adsorbed
substance from the surface on which it is adsorbed is called desorption. It is the reverse of adsorption and
can be brought about by heating or by reducing the pressure.
Adsorbent and adsorbate :The substance on the surface of which adsorption occurs is known as
adsorbent. The substances that get adsorbed on the solid surface due to intermolecular attractions are
called adsorbate.Charcoal, silica, gel, alumina gel are good adsorbents because they have highly porous
structures and have large surface area. Colloids on account of their extremely small dimensions possess
enoromous surface area per unit mass and are, therefore, also good adsorbents.
Examples of adsorption :
 Adsorption of a gas by charcoal : Finely divided activated charcoal has a tendency to adsorb a number
of gases like ammonia, sulphur dioxide, chlorine, phosgene, etc. In this case, charcoal acts as an adsorbent
while gas molecules act as adsorbate.
 Adsorption of a dye by charcoal : Animal charcoal is used for decolourising a number of organic
substances in the form of their solutions. The discharge of the colour is due to the fact that the coloured
component (generally an organic dye) gets adsorbed on the surface of the adsorbent (animal charcoal).
Sorption : When both adsorption and absorption take place simultaneously.
Eg : Dyes get adsorbed as well as absorbed in the cotton fibre i.e. sorption takes place.
Difference between adsorption and absorption :
The important points of distinction between adsorption and absorption
Absorption Adsorption
It is the phenomenon in which the particles of gas or It is the phenomenon of higher concentration of gas or
liquid get uniformly distributed throughout the body of liquid on the surface than in the bulk of the solid.
The concentration is the same throughout the The concentration on the surface of the adsorbent is
material. different (has higher concentration) from that in the bulk.
It is a bulk phenomenon. it is a surface phenomenon.
Adsorption is rapid in the beginning and its rate slowly

Absorption occurs at uniform rate.
decreases
It is a slow process It is a fast process
 Thermodynamics of adsorption
1. Adsorption involves attracting molecules of adsorbate on surface of the adsorbent. Due to this energy is
released and thus heat of adsorption is negative i.e. adsorption is always exothemic
2. The molecules of adsorbate are held on surface of the solid adsorbent due to this entropy decreases i.e.
S is negative.
3. G = H - TS, Therefore adsorption will occur only when G is negative and this is possible only if
H| > |TS|
4. As adsorption proceeds H becomes less and less negative hence H becomes equal to TS and G
becomes zero This is the state at which equilibrium is attained.
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Surface Chemistry
 Enthalpy of adsorption Hadsorption : It is the amount of the heat released when 1 mole of an adsorbate
gets adsorbed on a particular adsorbent at adsorption equilibrium. It depends upon the nature of both the
adsorbate as well as adsorbent.
Types of adsorption : The adsorption is classified into two types :
(i) Physical adsorption (i.e. physisorption) : When the particles of the adsorbate are held to the surface of
the adsorbent by the physical forces such as van der Waal’s forces, the adsorption is called physical
adsorption or vanderwaals adsorption.
(ii) Chemical adsorption (i.e. chemisorption) :
When the molecules of the adsorbate are held to the surface of the adsorbent by the chemical forces, the
adsorption is called chemical adsorption.
Differences between Physical and Chemical Adsorption
Property physical Adsorption Chemical Adsorption
Nature of adsorption Weak Strong
Enthalpy of adsorption Low High
Reversibility of adsorption Reversible and occur rapidly Irreversible and occurs slowly
Temp. at which adsorption is

Low temp. High temp.
more pronounced
Effect of change in temp. Decrease with rise in temp. Increase with rise in temp.
Not specific generally take place Highly specific take place on

Specificity of adsorption
on all surface specific surface
Nature of adsorbate layer Multi-layered Mono-layered
Increase with pressure of

Effect of pressure on adsorption adsorbate gas and attain limiting Negative adsorption
value
Energy of activation Very low significant relative high
depends on adsorbate (gas) only Depends on adsorbate as well

Dependence on nature of
easily liquefiable gases are more as adsorbent No correlation be
adsorbate and adsorbent
readily adsorbed can be achieved
easy since Vander Waal force Not easy since chemical forces
Easy of desorption
involved on involved
x
m x
Graph m
Temperature
Temperature
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Surface Chemistry
Shape selective catalysis
Catalysis action depends upon.
1. Shape of the catalyst (Pore structure or cavities)
2. Size of reactant and product.
Zeolites
1. They are honey comb like structure i.e. shape selective catalysis.
2. They are microporous aluminium silicate with 3D silicate in which silicon atom are replaced by aluminum
atoms i.e. Al – O – Si
3. The pore size is generally in range 260-740 pm.
4. General formula of zeolite is Nax/n [(AlO2)x (SiO2)y]. z H2O
Use of Zeolite
1. It is used as catalyst in petrolium industries for cracking hydrocarbon and isomerism i. e. ZSM-5.
ZSM 5
R – OH   gasoline
2. It convert alcohol directly into gasoline by dehydrating them to give a mixture of hydrocarbon.
 Competitive adsorption : When an adsorbent is in contact with more than one species (adsorbate). There
will be competition among them to get adsorbed on to the surface of the adsorbent. The one that is more
strongly adsorbed gets deposited first in preference to the others. Further a strongly adsorbed substance
may displace a weakly adsorbed substance.
Ex. NH3 can displace O2 or N2 from the surface of charcoal.
Adsorption of gases on solids :
The extent of adsorption of a gas on a solid surface is affected by the following factors:
 The nature of the gas (i.e. nature of the adsorbate). The easily liquefiable gases such as HCl, NH3, Cl2
etc. are adsorbed more than the permanent gases such as H2, N2 and O2.
extent of adsorption  critical temperature of gas  ease of liquification
Gas H2 CH4 CO2 SO2
TC 33 190 K 304 K 330K
 Nature of adsorbent. The extent of adsorption of a gas depends upon the nature of adsorbent. Activated
charcoal (i.e. activated carbon), metal oxides (silica gel and aluminium oxide) and clay can adsorb gases
which are easily liquified. Gases such as H2, N2 and O2 are generally adsorbed on finely divided transition
metals Ni and Co.
extent of adsorption  surface area of solid.
 Activation of adsorbent :

(a) Metallic adsorbents are activated by mechanical rubbing or by subjecting it to some chemical reactions.
(b) To increase the adsorbing power of adsorbents, they are sub-divided into smaller pieces. As a results, the
surface area is increased and therefore, the adsorbing power increases.
 Effect of temperature :Mostly the process of adsorption is exothermic and the reverse process or desorption
is endothermic. If the above equilibrium is subjected to increase in temperature, then according to Le-
Chaterlier’s principle, with increase in temperature, the desorption will be favoured. Physical adsorption
decreases continuously with increase in temperature whereas chemisorption increases initially, shows a
maximum in the curve and then it decreases continuously.
x x
m m
Temperature Temperature
The initial increase in chemisorption with increase in temperature is because of activation energy required.
This is why the chemical adsorption is also known as “Activated adsorption”.
A graph between degree of adsorption (x/m) and temperature ‘t’ at a constant pressure of adsorbate gas is
known as adsorption isobar.
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Surface Chemistry
 Effect of pressure. The extent of adsorption of a gas per unit mass of adsorbent
depends upon the pressure of the gas. The variation of extent of adsorption
expressed as x/m (where x is the mole of adsorbate and m is the mass of the
adsorbent) and the pressure is given as below. A graph between the amount of
adsorption and gas pressure keeping the temperature constant is called an
adsorption isotherm.
x
P
m
Where x = mass of adsorbate
M = mass of adsorbent
It is clear from the figure-1 that extent of adsorption (x/m) increases with pressure and becomes maximum
corresponding to pressure Ps called saturation pressure.
Freundlich Adsorption isotherm

The variation of extent of adsorption (x/m) with pressure (P) was given mathematically by Freundlich.
Where n can take any whole number value which depends upon
the nature of adsorbate and adsorbent. The above relationship is
also called Freundlich’s adsorption isotherm.
x
  = kp1/n
m
Pressure G raph R elation
x
At low pressure straight line = kP
m
1/n
(x/m ) = kp
At interm ediate pressure dependent on power of pressure 1
(0< <1)
n
x
At high pressure : Independent of pressure =k
m
where, x = Amount of gas adsorbed, m = Mass of adsorbent, K

and n are adsorption constant, p is adsorption equilibrium pressure. Slope=(1/n)
The constant k and n can be determined as explained below : log(x/m)
Taking logarithms on both sides
Eq. (x/m) = kp1/n we get intercept = log k
log p
log (x/m) = logk + (1/n) log p.
 One of the drawbacks of Freundlich isotherm is that it fails at high pressure of the gas.
 This equation applicable only when adsorbate substance form unimolecular layer on adsorbent
surface.
Langmuir Adsorption Isotherm

Assumptions :
1. Gas is considered to behave ideally.
2. A solid surface is considered as homogenous but contains a fixed number of adsorption sites on surface.
3. Each site adsorb a single molecule; means adsorption is monomolecular.
4. Rate of adsorption = Rate of desorption.
5. There is no lateral overlap between adsorbed molecules.
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Surface Chemistry
Derivation
Rate of desorption  fraction of surface available for adsorption  pressure of gas.
If  is covered fraction of surface covered. (1 – ) is the free surface area.
Rate of adsorption = Ka P(1 –)
Rate of adsorption = Kd 
Ka (1 – ) = Kd 
KaP – Ka P = Kd
K aP KP Ka
K aP  K d  = where K = K
1  KP d
Amount of gas adsorbed ‘x’ by given mass of adsorbent ‘m’ is proportional to 

x

m
x KK a / K dP
= 1 K / K P
m a d
x aP

m 1  bP
Ka
x = man of gas adsorption, m = mass of adsorption, a = Kb, b = K
b
x
 = y = extent of adsorption
m
ap
y=
1  bp
P 1 b
  P
y a a
x ap
It is represented by the relation :  ............ (a)
m 1  bp
where ‘a’ and ‘b’ are Langmuir parameter.
At very high pressure x/m =a/b ..........(b)
At very low pressure : x/m = ap ........ (c)
For determination of the parameters ‘a’ and ‘b’, Eq. (a) may be written in its inverse form.
m 1  bp b 1
   ............ (d)
x ap a ap
A plot of m/x against 1/p gives a straight line with slope and intercept equal to 1/a and b/a respectively.
At low pressure according to Eq. (c) x/m increases linearly with p. At high pressure according to Eq. (b)
x/m becomes constant i.e. the surface is fully covered and change in pressure has no effect and no further
adsorption takes place which is clear from the Figure-1.
Adsorption from solutions :
1. The extent of adsorption increases with increase in the surface area of adsorbent.
2. The extent of adsorption decreases with increase in temp.
3. The extent of adsorption is related to concentration of solution through this equation
Freundlich isotherm : (x/m) = k(c)1/n (n  1)
where c is the equilibrium concentration of the solute in solution.
Temperature dependence here also is similar to that for adsorption of gases and in place of equilibrium
pressure, we use equilibrium concentrations of the adsorbates in the solution.
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Surface Chemistry
Enzyme catalyst: Enzyme are complex nitrogenous organic compound which of emzyme Cl produced by
living plants and animal the chracterstics of enzyme catalyst are .
1. Most highly efficient 2. Highly specific in nature
3. Highly active under optimum temperature 4. Highly active under optimum Ph.
5. Increase activity in presence of coenzyme 6. Influence of induce and poison
Applications of adsorption :
1. In gas masks : Activated charcoal is generally used in gas masks to adsorb poisonous and toxic gases
from air. These masks are commonly used by the miners because there are poisonous gases like CO, CH4
etc. in the atmosphere in coal mines.
2. In dyeing of cloths : Mordants such as alums are used in dyeing of cloths. They adsorb the dye particles
which, otherwise, do not stick to the cloths.
3. In dehumidizers : Silica gel is commonly used to adsorb humidity or moisture from air.
4. Removal of colouring matter : Many substances such as sugar, juice and vegetable oils are coloured due
to the presence of impurities. They can be decolourised by placing them in contact with adsorbents like
activated charcoal or fuller’s earth.
5. Heterogeneous catalysis : The phenomenon of adsorption is useful in the heterogeneous catalysis. The
metals such as Fe, Ni, Pt, Pd, etc. are used in the manufacturing processes such as Contact process,
Haber process and the hydrogenation of oils. Their use is based upon the phenomenon of adsorption.
6. Refining Petroleum : Silica gel is used as adsorbent in petroleum refining.
7. Chromatography : It is a method for separation of component and is based on preferential adsorption
column is very common device used.
8. Creating vacuum : High vacuum can be created by removing gas by adsorption.
9. Adsorption Indicators : In volumetric analysis, adsorption indicator is used Surface of certain precipitates
such as silver halide have the property of adsorbing some dye like eosin, fluorescein, etc In the case of
precipitation titration (AgNO3 vs NaCI) of the indicator is adsorbed at the end point producing a characteristic
colour on the precipitate.
10. In froth floatation process : (in metallurgy).
11. Softening of hard water : Ion exchange resins used for softening of hard water is based upon selective and
competive adsorption of ions on resins.
Na2Z + Ca+2  CaZ + 2 Na+
The organic polymers containing groups like –COOH, –SO3H and –NH2 etc. possess the property of selective
adsorption of ions from solution. These are quite useful in the softening of water.
Example-1 A sample of charcoal weighing 6 g was brought into contact with a gas contained in a vessel of one
litre capacity at 27ºC. The pressure of the gas was found to fall from 700 to 400 mm. Calculate the
volume of the gas (reduced to STP) that is adsorbed per gram of the adsorbent under the condition
of the experiment (density of charcoal sample is 1.5 g cm3).
Solution. The adsorption is taking place in a closed vessel hence if pressure falls there is correspondingly
increase in volume constant, excess of the volume of the gas would be adsorbed.
P1V1 = P2V2
V1 1000
V2 = P1 = 700 × = 1750 mL.
P2 40
6.00
Actual volume of the flask = 1000 – volume of charcoal = 1000 – = 996 mL.
1.50
Volume of the gas adsorbed = 1750 – 996 = 754 mL.
 P1V1 P2 V2  125 .67  400  273
Volume of the gas adsorbed per gram at STP  U sin g T  T  = = 60.19 mL.
 1 2  300  760
 Catalysts : Berzillus in 1835 used the word catalyst first time for some substance which alter rate of chemical
reaction and themselves remain chemically and quantitatively unchanged after the reaction and the phenomenon
is known as catalysis.
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Surface Chemistry
Eg : Potassium chlorate when heated at 653K to 873K, it gives O2, When MnO2 is used in this reaction the
O2 is quickly at the low temperature hence MnO2 is a catalyst
2KCIO3 2KCI + 3O2
 Homogeneous Catalysis : When catalysts and reactants are in same phase then the process is said to be
homogeneous catalysis and
NO( g )
Eg : (i) 2SO 2 (g)  O 2 (g)   2SO3 (g)
HCl(  )
(ii) CH3 COOCH3 ()   CH3 COOH(aq)
H2SO 4 (  )
(iii) C12H22O11(aq.)  H2O()   C 6H12 O 6 (aq.)  C 6H12O 6 (aq.)
Glucose Fructose
 Heterogenous Catalysis : When catalysts and reactants are in different phases, then process a know as
heterogenous catalysis and catalyst is called heterogeneous catalyst
Pt ( s )
Eg : (i) 2SO 3 (g)  O 2 (g)   2SO3 (g)
Fe( s )
(ii) N2 (g)  3H2 (g)   2NH3 (g)
Pt ( s )
(iii) 4NH3 (g)  5O 2 (g)   4NO(g)  6H2O(g)
Ni( s )
(iv) Vegetable oils ()  H2 (g)   Vegetable ghee (s).
 Types of Catalysis
Type of Catalysis
Positive Negative Auto Induced
Substance which Substance which decrease the One of Product behave When one reaction
increase the rate of rate of chemical reaction as catalyst for that catalyst another
chemical reaction 2 2 HO + reaction and increase reaction, than this
2H2O2  2H2O
negative catalyse
Pt the rate of reaction, than phenomena is called
2SO2 + O2  2SO3
this phenomena is called as induced catalyses
autocatalysis Na2SO3  Na2SO4
CH3COOC2H5 + H2O

CH3COOH + C2H5OH
Promotors/Activators : Substance which are not catalyst themselves but its presence can increase the
catalytic activity of catalyst. A promotors increase the number of active sites on the surface Eg :
Fe(catalyst )
(i) N2  3H2     2NH3
Mo(promotor )
Ni(catalyst)
(ii) Vegetable Oil + H2 
Cu(promotor )
 Vegetable ghee.
ZnO ( catalyst )
(iii) CO  2H 2      
 CH 3 OH
Cr2 O 3 (prom otor )
Catalytic Poisons/ Anti catalysts : Substance which are not catalyst themselves but whose presence
decrease the activity of the catalyst. Poisoning is due to preferential adsorption of poison on the surface of
the catalyst.
Fe ( catalyst )
(i) N 2  3H 2         2NH 3
CO / H 2 S ( catalytic poisons )
Platinised asbestos ( catalyst )

(ii) 2SO 2  O 2                 2 SO 3
As 2 S 3 ( catalytic poisons )
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Surface Chemistry
Pd ( catalyst )
(iii) Rosenmund Reactions : RCOCl  H2    RCHO  HCI
BaSO 4 ( poisons catalytst )
 Catalyst Inhibitor: Those substances which reduce the rate of a chemical reactions are known as inhibitor.
e.g. H3PO4 and glycerol decrease the rate of decomposition of hydrogenperoxide.
  Characteristics of Catalysis :
(i) A Catalyst remains unchanged in mass and chemical compositions at the end of reactions. However
its physical state can be changed. Eg :
Granular MnO2 during decomposition of KClO3 is left as powder at the end of the reaction.
(ii) Highly efficient : Finely devided state of catalyst is more efficient for the 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 that practically
a reaction may not start until a catalyst lowers the activation 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.
room temperature
H2 + O2    No reaction
Pt black
H2 + O2   H2O.
(iv) Highly specific : Catalyst are generally specific in nature. A substance which act as a catalyst in a
particular reaction, fails to catalyse other reaction.
(vi) Catalyst cannot change 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 active under optimum temperature : There is a particular temperature at which the
efficiency of a catalyst is maximum, this temperature is known as optimum temperature. On either
side of the optimum temperature, the activity of catalyst decreases.(optimum range : 298 to 310 K).
(ix) Highly active under optimum pH : Range is pH 5 to 7.
(x) Influence of Inhibitor or poison.
 Adsorption Theory of Heterogeneous Catalyst : This theory explains the mechanism of heterogeneous
catalyst. This theory is combination of two theory, intermediate compound formation theory and the old adsorption
theory, the catalytic activity is localised on the surface on the catalyst. The mechanism involvs 5 steps.
(i) Diffusion of reactant to the surface of the catalyst of.
(ii) Adsorption of reactant molecules on the surface of the catalyst.
(iii) Formation of activated intermediate.
(iv) Formation of reactions product on the catalyst surface.
(v) Diffusion of reactions product from the catalyst surface or desorption.
Examples :
Let us consider addition of H2 gas to ethlene in presence of Ni catalyst, the reaction takes places as follows.
ADVSC -8
Surface Chemistry
 Factors Supporting Theory :
(i) This theory explains the role of active centre, more free valency which provides the more space for
more adsorption and concentration increases as a result of increase in rate of reaction.
(ii) Rough surface has more active and pores, there will be more free valency so more will be rate of
reaction.
more strain
(iii) The theory explains the centre action of promotors which occupied H H
the interstial void as a result surface area for the adsorption Ni Ni surface area increase
increases therefore rate of reaction increases .
promoters
inhibitors
(iv) The theory explains the function of poisons or inhibitors. In poisoning
preferential adsorption of poisons takes place on the catalyst,
surface area for the adsorption on the catalyst decreases hence
rate of reaction decreases. catalyst
Some Industrial Catalytic reactions
Colloid Solution :
Colloid State : A substance is said to be in colloidal state when the size of the particle of disperse phase
is greater than particle of true solution and less than that of suspension solution particle, their range of
diameters lie between 1 and 1000 nm (10–9 to 10–6 m).
Colloid solution : It is a heterogeneous system consisting of 2 phase :
(1) Disperse Phase (D.P) : The phase which is dispersed through the medium is called dispersed phase or
discontinuous phase or internal phase.
(2) Dispersion Medium (D.M) : A medium in which colloidal particles are dispersed is called dispersion
medium. It is also known as continuous phase or outer phase or external phase.
Colloidal solution = D.P. + D.M.
Ex. In Gold sol, Gold is D.P and water is D.M.
Differentiating point of colloids :

(1) A colloid is a heterogeneous system in which one substance is dispersed (dispersed phase) as very fine
particles in another substance called dispersion medium.
(2) The solution and colloid essentially differ from one another by particle size.
* In a solution, the particles are ions or small molecules.
* In a colloid, the dispersed phase may consist of particles of a single macromolecule (such as
protein or synthetic polymer) or an aggregate of many atoms, ions or molecules.
(3) Colloidal particles are larger than simple molecules but small enough to remain suspended. They have a
range of diameters between 1 and 1000 nm (10–9 to 10–6 m).
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Surface Chemistry
Classification of colloids :
 1. On the basis of physical state of D.P. and D.M.
On the bases of physical state of D.P. and D.M. colloidal solution may be divided into eight system.
DP DM Type of colloid Examples

Solid Solid Solid Sol Some coloured glasses, and gem stones
Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Liquid Aerosol Fog, mist, cloud, insecticide sprays
Gas Solid Solid Sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather.
* Solution of gas in gas is not a colloidal system because it forms homogeneous mixture.
2. On the basis of D.M. : Colloidal solution are classified as
D.M. Name of colloidal system
Water Hydro sol or aqua sol
Alcohol Alco sols
Benzene Benzo sols
Air Aero sols
* Aquadag & oildag are colloidal solution of graphite in water & oil respectively.
* Colloidal solution are often termed as sol.
3. On the Basis of interaction of D.P. for D.M. : There are two types-
(i) Lyophilic colloids / liquid loving sols / intrinsic colloid. The colloidal solution in which the particles of
the dispersed phase have a great affinity (or love) for the dispersion medium, are called lyophilic colloids.
These solutions are easily formed and the lyophilic colloids are reversible in nature. In case when water acts
as the dispersion medium, the lyophilic colloid is called hydrophilic colloid. The common examples of lyophilic
colloids are glue, gelatin, starch, proteins, egg albumin, rubber, etc.
(ii) Lyophobic colloids / solvent hating colloid / extrinsic colloid. The colloidal solutions in which there
is no affinity between particles of the dispersed phase and the dispersion medium are called lyophobic
colloids. Such solutions are formed with difficulty only by special methods. These sols are readily precipitated
(or coagulated) upon addition of small amounts of electrolytes, by heating or by shaking and hence are not
stable. Further, once precipitated, they do not give back the colloidal sol by simple addition of the dispersion
medium. Hence these sols are also called irreversible sols. They need stabilising agents for their preservation.
In case the dispersion medium is water, the lyophobic sol is called hydrophobic colloid. For example, the
solution of metals like Ag and Au, hydroxides like Al (OH)3, Fe(OH)3, metal sulphides like As2S3 etc.
* Lyophilic sols are more stable than lyophobic sols, the additional stability is due presence of an envelope
of the solvent layer (say water) around the colloidal particle, the process is known as hydration, To coagulate
a hydrophilic sols we have to add a dehydrating agent in addition to electrolyte.
DISTINCTION BETWEEN LYOPHILIC AND LYOPHOBIC COLLOIDS
S.No. Property Lyophilic colloids Lyophobic colloids
There are easily formed by direct
1 Ease of preparation These are formed only by special methods
mixing.
Reversible or
2 These are reversible in nature These are irreversible in nature.
irreversible nature
The particles of colloids are true The particles are aggregates of many
3 Particles nature
molecules but are big in size molecules
These are unstable and require traces of
4 Stability These are very stable
stabilizers
The addition of small amount of
5 Action of electrolytes No effect electrolytes causes precipitation (called
coagulation) of colloidal solution.
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Surface Chemistry
S.No. Property Lyophilic colloids Lyophobic colloids

The particles move in a specific direction
either towards anode or cathode
6 Charge on particles The particles do not carry any charge.
depending upon their charge in an electric
field
The particles of colloids are heavily
The particles of colloids are not
7 Hydration hydrated due to the attraction for the
appreciably hydrated.
solvent.
It is higher than that of dispersion It is nearly same as that of dispersion
8 Viscosity
medium medium
9 Tyndall effect They do not show tyndall effect They show tyndall effect.
It is nearly same as that of dispersion
10 Surface tension Lower than dispersion medium
medium
Coagulation of Precipitated by high concentration of Precipitated by low concentration of
11
precipitation electrolyte electrolyte
Migration in electric May or may not migrate as they may Migrate toward anode or cathode as these
12
field not carry charge particles carry charge
Mostly organic nature; Starch and Inorganic nature; Transition metal salt in
13 Example
Gelatin water, gold etc., Metal solution
4. On the basis of chemical composition:

Inorganic Colloids
(i) Metal sols : Cu, Ag, Au, Pt Sols.
(ii) Non Metal sols : S, I2, Graphite
(iii) Sol of oxide and hydroxide : SnO2, TiO2, Fe2O3, Fe(OH)3, AI(OH)3, Cr(OH)3
(iv) Salt Sol - AgBr, AgI, As2 S3, etc.
Organic Colloids
(i) Homopolar sol - In this type of colloid, particles carry similar type of charge. eg. Sol of rubber in benzene
which contain - ve charge colloidal particle of latex.
(ii) Hydroxy Sol- Starch sol
5. On the basis of charge on particles
(i) positive Sol
(a) Metal Oxide & Hydroxide - SnO2, TiO2, Fe2O3, AI(OH)3, Fe(OH)3, Cr(OH)3.
(b) Basic Dyes Methylene blue, vismark brown.
(ii) negative Sol -
(a) Metal sol - Ag, Au, Pt, Cu (b) Acidic dye - congo red, eosin
(c) Sulphide Sol- CdS, HgS, As2S3, Sb2S3.
(d) Natural sol - Blood, clay, charcoal, latex rubber, dust particle in water, starch carbon particle in smoke, gum.
6. Other type of colloids : Multimolecular, macromolecular and associated colloids
 Multimolecular colloids : In this type, the particles consist of an aggregate of atoms or small molecules
size less than 1 nm. For example, sols of gold atoms and sulphur (S8) molecules. In these colloids, the
particles are held together by van der Waal’s forces.
 Macromolecular colloids : In this types, the particles of the dispersed phase are sufficiently big in size
(macro) to be of colloidal dimensions. These macromolecules forming the dispersed phase are generally
polymers having very high molecular masses. These colloids are quite stable and resemble true solutions in
many respects. Naturally occuring macromolecules are starch, cellulose, proteins, enzymes, gelatin, etc.
 Associated colloids (Micelles): These are the substances which behave as normal strong electrolytes at
low concentration but behave as colloidal particles at higher concentration. These associated particles are
also called micelles. Ex. Soap.
ADVSC - 11
Surface Chemistry
Micelles :
 Micelles are relatively small, spherical structures composed of any where for a few to few thousand
molecule that attract one another to reduce surface tension within a membrane of cell.
The formation of micelles takes place only at particular temp, that temperature is called Kraft temperature.
The concentration above which micelle formation becomes appreciable is termed is critical micelles
concentration. its value depend upon natures of D.P. and D.M. eg. Surface active agent (surfactants, which
decrease the surface tension) like soaps and detergents form micelle beyond CMC (~10–3 mol/litre for soaps).
* Usually longer the hydrophobic chain, smaller is its CMC.
* Also CMC increase with decreasing polarity of the D.M.
* The micelles ‘formation takes place only above a particular temperature called as Kraft Temperature (Tk ).
*At CMC, the micelles are spherical in shape, but that start flattening with increase in concentration and
ultimately form sheet or film like structures which have a thickness of two molecules. These are called
lamelar micelles or McBain Micelles.
Mechanism of micelle formation: Let us take the example of soap solutions. Soap is sodium salt of a
higher fatty acid and may be represented as RCOO–Na+ e.g., sodium stearate viz.CH3(CH2)16COO– Na+
which is a major component of many bar soaps. When dissolved in water, it dissociates into RCOO- and Na+
ions. The RCOO– ions, however, consist of two parts i.e., long hydrocarbon chain R (also called non-polar
'tail') which is hydrophobic (water repelling) and the polar group COO– (also called polar-ionic 'head') which is
hydrophilic (water loving). The RCOO– lons are, therefore, present on the surface with their COO– groups in
water and the hydrocarbon chains R staying away from it, and remain at the surface, but at higher concentration
these are pulled into the bulk of the solution and aggregate in a spherical form with their hydrocarbon chains
pointing towards the centre with COO– part remaining outward on the surface. An aggregate thus formed is
known as ‘Ionic micelle'. These micelles may contain as many as upto 100 such ions.
Aggregation of RCOO– ions to form an ionic micelle.

Similarly, in case of detergents, e.g., sodium lauryl sulphate viz.
CH3(CH2)11SO4– Na+, the polar group is – SO4– along with the long
hydrocarbon chain. Hence, the mechanism of micelle formation is
same as that of soaps.
Example of micelles :
(i) Sodium stearate C17H35COO–Na+(Soap).
(ii) Sodium lauryl sulphate CH3 [CH2]11 SO4– Na+ (Detergent).
(iii) Cetyl trimethyl ammonium bromide (Detergent). CH3(CH2)15N+(CH3)3Br–.
The Cleansing Action of Soaps : It has been mentioned earlier that a micelle consists of a hydrophobic
hydrocarbon like central core. The cleansing action of soap is due to these micelles, because oil and grease
can be solubilised in their hydrocarbon, like centres which are not otherwise soluble in water. This is shown
diagrammatically in Figure The dirt goes out along with the soap micelles.
Sodium stearate (C17H35COO– Na+) Hydrophobic tail

(a) (b)
(c) (d) (e)

Fig. : The cleansing action of soap.
ADVSC - 12
Surface Chemistry
(a) A sodium stearate molecule
(b) The simplified representation of the molecule that shows a hydrophilic head and a hydrophobic tail
(c) Grease (oily substance) is not soluble in water
(d) When soap is added to water, the non-polar tails of soap molecules dissolve in grease
(e) Finally, the grease is removed in the form of micelles containing grease.
*Surfactants : They can be ionic as well as non-ionic. The ionic are soaps and detergent. The surfactant
gets adsorbed at the interface between the dispersed droplets and dispersion medium in the form of mono
molecular layer and lowers the interfacial tension between oil and water so as to facilitate the mixing of two
liquids.
Preparation of lyophobic colloidal sols :
[A] Condensation methods :
In these methods particles of atomic or molecular size are induced to combine to form aggregates having
colloidal dimensions. For this purpose chemical as well as physical methods can be applied.
(a) Chemical methods. 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.
(i) Double decomposition : When a hot aqueous dilute solution of arsenous oxide (As2O3) is mixed with a
saturated solution of H2S in water, a colloidal sol of arsenous sulphide (As2S3) is obtained.
Double decomposit ion
As2O3(in hot water) + 3H2S (saturated solution in H2O)          As2S3(sol) + 3H2O
CHOHCOOK CH OH COOK

| + 3H2S  | + Sb2S3 (orange sol) + 2H2O
CHOHCOOSbO  CH OH COOH
(ii) Oxidation : A colloidal sol of sulphur is obtained by passing H2S into a solution of sulphur dioxide.
SO2 + 2H2S(saturated solution in H2O) Oxidation
  3S(sol) + 2H2O
Sulphur sol can also be obtained when H2S is bubbled through Br2 water or nitric acid (oxidizing agent).
2H2S (aq.) + Br2 (aq.)  2HBr (aq.) + S (sol).
or by bubbling O2 (g) through a solution of H2S : 2H2S (aq.) + O2 (g)  2H2O (l) + 2S (sol).
(iii) Reduction : Colloidal sol of metals like gold, silver solution are obtained by following method.
2 AuCl3 + 3 HCHO + 3H2O  2Au(sol) + 3HCOOH + 6HCl.
(purple of cassius)
Re duction
2 AuCl 3  3 SnCl 2    3 SnCl 4  2Au(sol)
Re duction
AgNO3 + tannic acid    silver sol.
NH2NH2 can also be used as reducing agent. *Sol of gold is also known as purple of cassius.
(iv) Hydrolysis : A colloidal sol of metal hydroxides like Al(OH)3 or Cr(OH)3 is obtained by boiling a dilute
solution of FeCl3 , AlCl3 or CrCl3 .
FeCl3 + 3H2O  Fe(OH)3 (sol) + 3HCl ; AlCl3 + 3H2O  Al(OH)3 (sol) + 3HCl
The colloidal sol of sillicic acid is also obtained by hydrolysis of dilute solution of sodium silicate with
hydrochloric acid. Na4SiO4 + 4HCl  Si(OH)4 (sol) + 4NaCl.
(b) Physical methods : The following physical methods are used to prepare the colloidal solutions.
(i) By Exchange of solvent : When a true solution is mixed with an excess of the other solvent in which the
solute is insoluble but solvent is miscible, a colloidal sol is obtained. For example,
 when a solution of sulphur in alcohol is poured in excess of water, a colloidal sol of sulphur is obtained.
 when a solution of phenolphthalein in alcohol is poured in excess of water a white sol of phenolphthalein is
found.
Phenolphthalein, I , sulphur sol can be prepared by this methods.
2
ADVSC - 13
Surface Chemistry
(ii) Excessive cooling : Molecules of certain substance condense together on excess cooling to form
colloidal size particle. The colloidal sol of ice in an organic solvent such as CHCl3 or ether can be obtained by
freezing a solution of water in the solvent. The molecules of water which can no longer be held in solution
separately combine to form particles of colloidal size.
(iii) By condensing vapours of a substance into solvent : Substance like sulphur and Hg in water are
prepared by passing their vapours in cold water containing small amount of stabilising agent like ammonium
nitrate.
[B] Dispersion Methods : In these methods large particles of the substance are broken into particles of
colloidal dimensions in the presence of dispersion medium. These are stabilized by adding some suitable
stabilizer. Some of the methods employed are given below :
(a) Mechanical dispersion (By colloidal mill):
Substance is first finely powdered.

It is shaken with the D.M. to form a suspension.

This suspension is passed through a colloidal mill.

The simplest type of colloidal mill is disc mill
which consists of two metal discs nearly touching
each other & rotating in opposite.

Direction at a high speed (7,000 revolutions per min.).

The suspended particles are broken to produce colloidal size particle.
* This method is used to prepare printing ink.
(b) Electrical disintegration or Bredig's Arc method : This
process involves dispersion as well as condensation. Colloidal sols
of less reactive metals such as gold, silver, platinum, copper, lead
etc., can be prepared by this method. In this method, electric arc
is struck between electrodes of the metal immersed in the
dispersion medium as shown in fig. The intense heat produced
vaporises the metal, which then condenses to form particles of
colloidal size by surrounding cooling mixture (ice).
*A slight trace of KOH is added in water to stabilized colloidal solutions.
(c) Ultrasonic dispersion : Ultrasonic vibration (having frequency larger than audible range) can bring about
the transformation of coarse suspension or liquids like oil, mercury etc. into colloidal range.
*This is the latest method for preparation of metal oxides and metal sulphide sols from their coarse suspension.
*It is a suitable technique for oils also. This method also comprises both dispersion and condensation.
(d) Peptization: The term has originated from the digestion of proteins by the enzyme pepsin. Peptization
may be defined as (the process of converting a precipitate into colloidal sol by shaking it with dispersion
medium in the presence of a small amount of electrolyte).
The electrolyte used for this purpose is called peptizing agent. This method is applied, generally, to convert
a freshly prepared precipitate into a colloidal sol. During peptization, the precipitate adsorbs one of the ions
of the electrolyte on its surface.
The ion adsorbed on the surface is common either with
the anion or cation of the electrolyte. This causes the
development of positive or negative charge on precipitates
which ultimately break up into smaller particles having
the dimensions of colloids.
ADVSC - 14
Surface Chemistry
For example :
(i) When freshly precipitated Fe(OH)3 is shaken with aqueous solution of FeCl3 (peptizing agent) it adsorbs
Fe3+ ions and thereby breaks up into small-sized particles.
FeCl3  Fe3+ + 3Cl– ; Fe(OH)3 + Fe3+  Fe(OH)3 | Fe3+
+3 +3
+3
+3 +3 +3 +3
+3 +3
+3 +3 +3
3+
+3
+ Fe +3 +3
+3 +3 +3
Peptizing agent +3
+3 +3 +3 +3 +3 +3
ppt of Fe (OH)3 +3
+3 +3
+3 +3
+3 +3 +3 +3
+3 +3
Charge Colloidal particals of Fe (OH)3
(ii) Freshly prepared stannic oxide on treatment with a small amount of dilute hydrochloric acid forms a
stable colloidal sol of stannic oxide, SnO2 ; Sn4+ .
SnO2 + 4HCl  Sn4+ + 2H2O + 4Cl– ; SnO2 + Sn4+  SnO2 / Sn4+ .
(iii) Freshly precipitated silver chloride can be converted into a colloidal sol by adding a small amount of
hydrochloric acid, AgCl : Cl– .
(iv) Cadmium sulphide can be peptised with the help of hydrogen sulphide, CdS : S2– .
Purification of Colloidal Sols : The colloidal sols obtained by various methods are impure and contain
impurities of electrolytes and other soluble substances. These impurities may destabilise the sol. Hence,
they have to be removed. A very important method of removal of soluble impurities from sols by a semipermeable
membrane is known as dialysis.
A. Dialysis : It is a process of removing a dissolved substance from a colloidal solution by means diffusion
through suitable membrane. Since particles in true solution (ions or smaller molecules) can pass through
animal membrane or parchment paper or cellophane sheet but colloidal particle do not, the appratus used for
this purpose is called Dialyser.
A bag of suitable membrane containing the colloidal solutions
is suspended in a vessel through which fresh water
continously flow. The molecules and ions (crystalloids) diffuse
through membrane into the outer water & pure colloidal
solution is left behind.
Movement of ions across the membrane can be expedited
by applying electric potential through two electrodes as shown
in fig.
This method is faster than simple dialysis and is known as
Electrodialysis.
*The most important applications of dialysis is in the purification of blood in the artificial kidney machine. In
case of kidney failure, blood cannot be purified. Under such condition, the blood is separated from dissolved
toxic impurities by dialysis and re-introduced in the bloods stream.
*Dialysis is not applicable for non-electrolytes like glucose, sugar, etc.
B. Ultra Filtration : In this method, colloidal sols are purified by carrying out filtration through special type
of graded filters called ultra-filters. These filter papers allow only the electrolytes to pass through. These filter
papers are made of particular pore size by impregnating with colloidal solution and subsequently hardened
by soaking in formaldehyde collodion. In order to accelerate the filtration through such filter papers, increased
pressure or section is employed.
ADVSC - 15
Surface Chemistry
Example-2 When SO2 is bubbled into H2S gas, colloidal sol is formed. What type of colloidal sol is it ?
Solution. 2H2S + SO2  2H2O + 3S (colloidal).
Lyophobic colloidal sol of sulphur is formed.
Example-3 A reddish brown positively charged sol is obtained by adding small quantity of FeCl3 solution to
freshly prepared and well washed Fe(OH)3 precipitate. How does it take place ?
Solution. It is due to adsorptions of Fe3+ ions on the surface of Fe(OH)3 which gives colloidal sol.
Fe(OH)3 (ppt.) + Fe3+ (ions adsorbed)  [Fe(OH)3]Fe3+ (colloidal sol).
Example-4 Suppose we have a cube of 1.00 cm length. It is cut in all three directions, so as to produce eight
cubes, each 0.50 cm on edge length. Then suppose these 0.50 cm cubes are each subdivided into
eight cubes 0.25 cm on edge length, and so on. How many of these successive subdivisions are
required before the cubes are reduced in size to colloidal dimensions of 100 nm.
Solution. We find that every division in two equal halves also reduces the size of edge lengths to one half.
1
In first subdivision 1 cm is reduceds to 0.5 cm = cm.
2
2
1  1
In second subdivision 0.5 cm is reduced to 0.25 cm = cm =   cm
4 2
n
 1
In n subdivision 1 cm is reduced to   . Size of colloidal particles lies between 1 to 1000 mm.
2
Thus to make n subdivision required particle size may be attained.
n
 1
  = 100 nm = 100 × 10–9 m = 100 × 10–7 cm.
2
 n log 2 = 5
n × 0.3010 = 5.
5
n= = 16.61 = 17 subdivisions are required for dimension of 100 nm.
0.3010
Important properties of colloidal sols :

 Heterogeneous character :
Colloidal sols are heterogeneous in character as they consist of two phases.
(a) dispersed phase and (b) dispersion medium.
 Visibility : Due to scattering caused by the colloidal particles, it will appear as a bright spot moving
randomly.
 Filterability : Colloidal particles pass through an ordinary filter paper. However, the particle do not pass
through other fine membranes.
 Colligative Properties : Colloidal sols show the colligative properties viz. relative lowering of vapour
pressure, elevation in boiling point, depression in freezing point and osmotic pressure. However, 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 the molecular mass of polymers.
   Optical Properties-Tyndall effect : Tyndall, in 1869, observed that if a strong beam of light is
passed through a colloidal sol placed in a dark place, the path of the beam gets illuminated. This phenomenon
is called Tyndall effect, which is due to the scattering of light by the colloidal particles. The illuminated path
of beam is called Tyndall cone. This phenomenon is due to scattering of light from the surface of colloidal
particles. In a true solution there are no particles of sufficiently large diameter to scatter light & hence the
beam is invisible.
ADVSC - 16
Surface Chemistry
Eye
microscope
Tyndall cone
Light source
Scattered light
True solution Colloidal solution
*The intensity of scattered light depends on the difference between the refractive indice of the D.P and D.M.,
In lyophobic colloids, this difference is appreciable and therefore the tyndal effect is quite well defined but in
lyophilic sols the difference is very small and the tyndal effect is very weak. Thus in sols of silicic acid, blood
serum, albumin, etc. there is little or no tyndal effect.
Example of Tyndall Effect
 Blue colour of sky and sea water.
 Visibility of tail of comets.
 Light thrown from a projector in cinema hall.
 Appearance of dust particle in a semi darked room.
Application of Tyndall Effect :
(i) In making ultramicroscopes.
(ii) In finding heterogenity of solution.
Example-5 Under what conditions is Tyndal effect observed ?

Solution. Tydalls effect is applicable when :
(a) The diameter of the dispersed particles is not much smaller than the wavelength of the light used.
(b) The refractive indices of the dispersed phase and the dispersion medium must differ greatly in
magnitude.
Example-6 In the lower layer of the atmosphere, there is a great deal of dust. When the weather is fine, it is
possible to see the magnificent red colour of the setting sun. What have these observation to do with
colloids ?
Solution. Dust in the atmosphere is often colloidal. When the sun is low down on the horizon, light from it has
to pass through a great deal of dust to reach your eyes. The blue part of the light is scattered away
from your eyes. You see the red part of the spectrum, which remains. Red sunsets are the Tyndall
effect on a large scale.
 Mechanical Properties :

Brownian movement: Robert Brown, a botanist, discovered in
1827 that pollen grains placed in water do not remain at rest but
move about continuously and randomly. Later on, this phenomenon
was observed in case of colloidal particles when they were seen
under an ultramicroscope. The particles were seen to be in constant
zig-zag motion as shown in fig. This zig-zag motion is
called Brownian movement.
Brownian movement arises because of the impact of the molecules of the dispersion medium with the
colloidal particles.
ADVSC - 17
Surface Chemistry
Dependence : (i) Size of colloidal particles
1
Mobility 
Size of the particle
(ii) Viscosity of solution
1
Mobility  Vis cos ity
(iii) Temperature
Mobility  Temperature
Factors Affecting Brownian Movement :
(i) If particles is large then brownian movement becomes less.
(ii) Brownian movement increases with increasing temperature.
(iii) The brownian movement does not change with time & remains same for months or even for a year.
 Important :
(i) In confirmation of kinetic energy.
(ii) Determination of Avogadro numbers.
(iii) Stability of colloidal solution : Brownian movement does not allow the colloidal particles to settle
down to gravity & thus is responsible for their stability.
 Electrical Properties (Electrophoresis) :
The existence of charge on colloidal particles is confirmed by electrophoresis experiment. 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 colloidal particles under on applied electric potential is
called electrophoresis.
Positively charged particles move towards the cathode while negatively charged particles move towards the
anode. Depending upon the direction a movement of particles towards cathode or anode electrophoresis can
be called ’cataphoresis‘ or ‘Anaphoresis’
Arsenious sulphide, gold, silver and platinum particles in their respective colloidal sole are negatively charged
while particles of FeCOHL3, Al(OH)3 are positively charged.
(Fig. : A set up for electrophoresis.)

The colloidal solution is placed in a U-tube fitted with platinum electrodes. On passing an electric current, the
charged colloidal particles move towards the oppositely charged electrode. Thus, if arsenic sulphide sol is
taken in the U-tube, in which negatively charge particle of arsenic sulphide move towards the anode.
*Earlier this process was called cataphoresis because most of the colloidal sols studied at that time were
positively charged and moved towards cathode.
 Electro osmosis: When movement of colloidal particles is prevented by some suitable means (porous
diaphragm or semi permeable membrenes), it is observed that the D.M. begins to move in an electric field.
This phenomenon is termed electrosmosis.
 Sedimentation potential or Dorn potential : When the charged colloidal particles are made to settle
down under centrifugal field, there occurs a charge separation and a potential difference is developed. This
effect is called Dorn effect and the potential difference thus developed is called Dorn potential or sedimentation
potential. This process is reverse of electrophoresis.
 Isoelectric point : The H+ concentration at which the colloidal particles have no charge is known as the
isoelectric point. At this point stability of colloidal particles becomes very less & do not move under influence
of electric field.
ADVSC - 18
Surface Chemistry
 Streaming potential : A potential difference is developed across a porous partition when the dispersion
medium of a charged colloid is forced through it. This is called Streaming potential. This process is reverse
of electro-osmosis.
 Charge on colloidal particles : Colloidal particles are either positively charged or negatively charged.
This charge is due to preferential adsorption of either positive or negative ions on their surface. There is
adsorption of common ion present in excess.
Fe(OH)3 sol prepared by the hydrolysis of FeCl3 solution adsorbs Fe3+ and this is positively charged.
–
FeCl3 + 3H2O Fe(OH3) + 3HCl ; Fe(OH)3 + FeCl3  Fe(OH)3 Fe3+ : 3Cl
Fixed part Diffused part.
Positive charge on colloidal sol is due to adsorption of Fe3+ ion (common ion between Fe(OH)3 and FeCl3).
As2S3 colloidal sol is obtained when As2O3 is saturated with H2S :
As2O3 + 3H2S  As2S3 + 3H2O.
As2S3 adsorbs S2– ions (common between H2S and As2S3 and thus is negatively charged).
As2S3 + H2S  As2S3 S2– : 2H+.
AgI in contact with AgNO3 forms positively charged colloidal sol due to adsorption of Ag+ ion.
AgI + AgNO3  [AgI]Ag+ : NO3– , AgI in contact with KI forms negatively charged colloidal sol due to
adsorption of I– ion AgI + KI  AgI I– : K+.
SnO2 in acidic medium forms positively charged colloidal sol due to adsorption of Sn4+ formed.
SnO2 + 4H+  Sn4+ + 2H2O SnO2 + Sn4+  SnO2 Sn4+
SnO2 in alkaline medium forms negatively charged colloidal sol due to adsorption of SnO32– formed.
SnO2 + 2OH–  SnO32– + H2O SnO2 + SnO32–  SnO2 SnO32–
Charge on colloidal particle may be due to some other reasons also e.g.
*Due to electron capture by collidal particle during electro dispersion of metal.
*Due to self dissociation.
 Electric Double Layer Theory or Helm-holtz Electric double layer :
Electric double layer Theory
– –
– –
– Fixed layer
– + + +
– +
+ Colloidal + –
– Particle
of al(on) +
+ –
– + Mobile layer
+ + –
– + +
– –
– –
 The combination of two layer of opposite charges (+ve and –ve charge) around colloidal particle is called
Hebnholtz electrical double layer.
 First layer of ions is firmly held and is termed as fixed layer.
 Secondary layer is mobile and is termed as diffused layer.
 The charges of opposite sign on fixed and diffused parts of double layer result in difference in potential
between these layers.
 This potential difference between the fixed layer and diffused layer of opposite charges is called electrokinetic
potential or zeta potential.
4
Z n = Viscosity cofficunt
D
D = Dielectric constant of medium
 = Velocity of colloidal particle when an electric field is applied.
ADVSC - 19
Surface Chemistry
e.g. AgNO3 + KI  AgI + KNO3
( excess)
Fixed layer
+
K
+
K
+
K
I–
I
– I– K
+
–
I
–
AgI I
–
K+ I I–
–
I I– I
–
K+
Zetapotential K+ +
K
K+ Diffused layer
Example-7 Classify the following sols according to theirs charges :

(a) gold sol (b) ferric hydroxide sol (c) gelatine (d) blood
(e) sulphur (f) arsenious sulphide (g) titanium oxide.
Solution. Negatively charged colloidal sol : (a), (c), (d), (e), (f).
positively charged colloidal sol : (b), (g).
Example-8 SnO2 forms positively charged colloidal sol in acidic medium and negatively charged colloidal sol in
basic medium. Explain ?
Solution. SnO2 is amphoteric reacting with acid and base both. In acidic medium (say HCl) Sn4+ ion is formed
which is preferentially adsorbed on SnO2 giving positively charged colloidal sol :
SnO2 + 4HCl  SnCl4 + 2H2O ;
SnO2 + SnCl4  [SnO2]Sn4+(positively charged) + 4Cl–.
 Coagulation/Flocculation : This process of aggregation of colloidal particles into an insoluble

precipitate by the addition of some suitable electrolyte is known as coagulation. 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. The stability of the lyophobic colloids is due to presence of charge on colloidal particles. If, somehow,
the charge is removed, the particles will come near to each other to form aggregates and settle down under
the force of gravity.
Coagulation value or Flocculation value : It needs to be noted that the coagulation of a colloidal solution
by an electrolyte does not take place until the added electrolyte has certain minimum concentration in the
solution. The minimum concentration of electrolyte in millimoles required to cause coagulation of
one litre of colloidal solution is called coagulation value. It is express in terms of millimoles/litre.
mil lim oles of electrolyte
Coagulation value = volume of sol in litre
+ ++ + +
+ + + + ++ +
++
+ ++ +
+ ++ + + + + +
+ ++ + +
+ ++
+ ++ + +
+ ++ +++ + ++
+ ++ +
+ ++ + +
+ ++
+ ++
+ ++ +
+ + + + + ++ + + + +
+
+ + +
+ ++
+
+
+ +
+ + + + + + ++
+ + ++ + +
+ + ++ + ++ +
+ + + + +
+ + + + +
+ +
+ + +
+++ + + + + + +
+ + + + ++ + +
+ + + + ++ +
+ + + + ++ +
+ + ++
+
++
+ ++ ++
+ ++ +
+ ++ +
+ +++
+ + +
+
+ ++
+ ++
+++
+ ++
+ +
+
+
+
++
Neutralised
sol particles Coagulated sol
ADVSC - 20
Surface Chemistry
Coagulation of lyophobic sols can be carried out by the following methods.
(i) By electrophoresis
(ii) By mutual precipitation : It is a process in which oppositely charged sol are mixed in proper proportion
to neutralise the charge of each other causing coagulation of both the sol.
Example : Positively charged Fe(OH)3 and negatively charged As2S3 colloidal particle containing sol on
mixing get coagulated.
(iii) By Prolonged Dialysis : On prolonged dialysis, traces of the electrolyte present in the sol are removed
almost completely and the colloidal unstable and ultimately coagulate.
(iv) By Boiling : Sols such as sulphur and silver halides dispersed in water may be coagulated by boiling
because increased collisions between sol particle and the water molecule removed the adsorbed electrolytes.
This takes away the charge from the particles and helps them to coagulate.
(v) By cooling : Certain sol can also be coagulated by lowering temperature. For example, accumulation of
cream on the surface of milk on cooling. This is because at lower temperature the dispersion medium
molecules do not exert sufficient force on to the dispersed particles and hence the Brownian motion becomes
less effective.
(vi) By the addition of electrolyte : When excess of an electrolyte is added, the colloidal particles are
precipitated.
 Comparision of relative coagulating power of two electrolyte for the same colloidal solution :
The coagulation value decrease with increase in charge of the coagulating ion.
1
Coagulating power  coagulatio n value .
coagulatin g power of electrolyt e A coagulatio n value B

coagulatin g power of electrolyt e B = coagulatio n value A .
 Factor-Affecting Coagulations : (i) Nature of sols : The lyophobic colloid can easily coagulate because
it is a less stable colloid, but lyophilic colloids coagulate hardly by the addition of electrolyte due to protective
layer of D.M. surrounding the colloidal particle.
(ii) Nature of electrolyte : In equimolar electrolyte, strong electrolyte have greater coagulating power than
weak electrolyte. Example : 0.1M NaCl > 0.1M CH3COOH.
 Hardy-Schulze Rule : According to this rule greater is the valency of coagulating ion, greater its power to
cause precipitation. This is known as Hardy-Schulze rule.
In case of positive charged sol, the coagulating power of anion is in the order of [Fe(CN)6]4– > PO43– > SO42– > Cl–
In case of negative charged sol, the coagulating power of cation is in the order of Al3+ > Ba2+ > Na+.
 The coagulating power of bivalent ion is 20-80 times higher than monovalent ion and coagulating power of
trivalents is many times more than bivalent.
Example-9 The particles of a particular colloidal solution of arsenic trisulphide (As2S3) are negatively charged.
Which 0.0005 M solution would be most effective in coagulating this colloidal solution. KCl, MgCl2,
AlCl3 or Na3PO4? Explain.
Solution. Since As2S3 is a negatively charged colloidal sol hence positively charged ion will cause its coagulation.
By Hardy-Schulze rule “greater the charge on ion, greater the coagulating power to coagulate
oppositely charged colloidal sol”, hence out of K+, Mg2+, Al3+ and Na+, Al3+ would be most effective.
Protective colloidal sols : Lyophilic colloidal sols are much more stable than lyophobic colloidal sols.
This is due to the extensive solvation of lyophilic colloidal sols, which forms a protective layer outside it and
thus prevents it from forming associated colloids. Lyophobic sols can easily precipitate by addition of small
amount of an electrolyte. They can be prevented from coagulation by previous addition of some lyophilic
colloid. This is due to formation of a protective layer by lyophilic sols outside lyophobic sols. Process of
protecting the lyophobic colloid solution from precipitation by an electrolyte due to previous addition of some
lyophilic colloid is called protection of colloid and lyophilic colloidal sols are called protective sols.
Eg : Gelatin, Sodium caseinate, Egg albumin, Gum arabic, Potato starch etc.,
Gelatin (lyophilic) protects gold sol (lyophobic) colloids is expressed in terms of gold number.
ADVSC - 21
Surface Chemistry
Gold Number : Zpsigmondy (1901) introduce a term called gold number it is defined as ‘’the minimum
amount of the protective colloid in milligrams which when added to 10 ml of a standard gold sol is just
sufficient to prevent a colour change from red to blue on the addition of 1 ml of 10% sodium chloride solution.
It may be noted that smaller of the gold number, greater will be protecting power of the protective colloid.
Protecting power  1 .
gold number
weight of lyophilic sol in mg 10

Gold Number = volume of gold sol in mL
Uses of protective action :
(i) Gelatin is added in the preparation of ice cream to protect the particle of ice.
(ii) Protargol and Argyrol, is a silver sol protected by organic material used as eye drop.
Applications of Colloids : Colloids including emulsions find a number of uses in our daily life and
industry. Some of the uses are given below.
1. In medicines : A wide variety of medicinal and pharmaceutical preparations are emulsions. Colloidial
medicines are easily adsorbed by the body tissue because of large surface area.
* Colloidal antimony is used in curing kalaazar.
* Milk of magnesia, an emulsion, is used for stomach disorder.
* Colloidal gold is used for intramuscular injection.
* Colloidal sulphur are used as Germicides.
* Argyrol is a silver sol used as an eye lotion.
* Colloidal Fe(OH)3 is given to arsenic poisoning patients as it adsorbs arsenic and then gets omited out.
2. Tanning
3. Photographic plate & Film
4. Rubber plating
5. Sewage disposal
6. Cottrell smoke precipitator :
Smoke is a dispersion of negatively charged colloidal
particles of carbon in air and can be made free of these
colloidal particles by passing it through cottrell precipitator
as shown in fig. installed in the chimney of an industrial
plant. It consists of two metal discs charged to a high
potential. The carbon particles get discharged and
precipitate, while gases come out from the
chimney.
7. Formation of deltas: The river water contains colloidal particles of sand and clay which carry negative
charge. The sea water contains +ve ions such as Na+, Mg2+, Ca2+, etc. As the river water meets sea water,
these ions discharge the sand or clay particle which are precipitated in the form of delta.
8. Artificial rain
9. Stop bleeding from a cut
10. Stop Screen
11. Preparation of nano-materials
12. In disinfectants : The disinfectants such as dettol and lysol give emulsions of the oil-in-water type when
mixed with water.
STEM TECHNOLOGY : The size and shape of the colloidal particles is determined with the help of an
electron microscope which has much more resolving power (of the order of 10–12m.) The different techniques
used to study the colloidal particles are :
(i) Scanning electron microscope (SEM)
(ii) Transmission electron microscope (TEM) and
(iii) Scanning transmission electron microscope (STEM).
ADVSC - 22
Surface Chemistry
   Emulsions : Pair of immiscible liquid is called emulsion. Emulsion are unstable and some time they are
separated into two layers on keeping still, for the stabilising of an emulsion, a third component is added
called emulsifying-Agent form an interfacial film between D.P. and D.M.
Emulsion droplets are bigger than sol particles and can be seen under an ordinary microscope and sometimes
even with a magnifying glass.
Example : Milk is an emulsion in which liquid fat is D.P. and liquid water is D.M. and casein is emulsifying
agent.
 Demulsification : The separation of an emulsion into its constituent liquids is called demulsification.
Various techniques employed for this are freezing, boiling, centrifugation, electrostatic precipitation or chemical
methods which destroys the emulsifying agents.
Demulsification can be brought about by :
(i) Freezing (ii) Heating
(iii) Centrifugal action (Separation of cream of milk done by centrifugation).
(iv) Removal of emulsifiers by adding a better solvent for them like alcohol, phenol etc, called demulsifiers.
Types of emulsions : Depending on the nature of the dispersed phase, the emulsions are classified as :
(a) Oil in water emulsions (b) Water in oil emulsions
 Inversion of phase : The conversion of emulsion of oil in water (o/w) into water in oil (w/o) or vice versa is
called the inversion of phase.
[A] Identification of the type of emulsion : These two types may be identified by :
 Dilution test : An emulsion can be diluted with any amount of the dispersion medium, while the dispersed
liquid, if added, forms a separate layer. Thus if a few drops of water added to the emulsion are soluble in it,
it is oil in water type and if immiscible, it is water in oil type.
 Dye test : If a small amount of oil soluble dye gives a uniform colour to the emulsion, it is water in oil type
otherwise it is oil in water type.
 Electrical conductivity test : If conductivity of emulsion increases significantly by adding a very small
amount of electrolyte, it is oil in water type and if there is no significant increase in conductivity, it is water in
oil type.
[B] Applications of emulsions :
Disinfactants like phenyl, dettol when mixed with water form emulsion.
 Digestion of fat in small intestine occurs easily due to emulsion.
In metallurgical process the concentration of ore by froath floatation method is based upon emulsion.
 Milk is an emulsion of liquid fat in water in which casein emulsifying agent.
   Cleansing action of soap is due to formation of emulsions. Soaps and detergents emulsify the grease along
with the adhering dirt and carry them away in the wash water.
   For concentrating ores, the finely powdered ore is treated with an oil. Oil forms emulsion with the ore
particles. When air is bubbled into the mixture, emulsion containing the particles of the mineral are carried to
the surface.
Gelation :
Ex : Gelatin dissolved in water forming a colloidal. Sol Which when cooled sets into a gelly.
*Gel have honey-comb structure :
Ex : Sillicic acid, Gum arabic, Sodium oleate, Gelatin, Solid alcohol, etc.
Types of Gel :
(i) Elastic gel : Those gel which have elastic properties. Eg : Gelatin, Starch, Agar-Agar etc.
(ii) Non- elastic gel : Those gel which are rigid. Eg : Silica gel.
Properties of Gel :
1. Syneresis/weeping of gel : The spontaneous liberation of liquid from a gel is called syneresis or weeping
of gels. It is reverse of swelling.
Eg : Gelatin, Agar-Agar show syneresis at low concentration while sillicic acid shows it at high concentration.
2. Imbibition or swelling of gel : When gel is kept in a suitable liquid (water) it absorb large volume of liquid.
The phenomenon is called, imbibition or swelling of gel.
3. Thixotropic : Some gels when shaken to form a sol, on keeping changes into gel are termed as thixotropic
gel and phenomenon is called thixotropy.
Eg : Gelatin and silica liquify on shaking changing into corresponding sol and the sol on keeping changes
back into gel.
ADVSC - 23
Surface Chemistry
MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. Which of the following is (are) lyophobic colloids ?
(A) Gold sol (B) As2S3 sol (C) Starch sol (D) Fe(OH)3 sol
Sol. (ABD) Gold sol, As2S3 and Fe(OH)3 are lyophobic colloid. Therefore, (A, B, D) are correct options.
2. The presence of colloidal particles of dust in air imparts blue colour to the sky. This is due to
(A) Absorption of the light (B) Scattering of the light
(C) Reflection of the light (D) None of these
Sol. (B) Due to scattering of the light. Therefore, (B) is correct option.
3. The volume of nitrogen gas Um (measured at STP) required to cover a sample of silica gel with a mono-
molecular layer is 129 cm3 g–1 of gel. Calculate the surface area per gram of the gel if each nitrogen molecule
occupies 16.2 × 10–20 m2.
Ans. 561.8 cm3
Sol. 22400 cm3 of N2 at STP contain = 6.022 × 1023 molecules
6.022  10 23  129
129 cm3 of N2 at STP will contain = 22400 = 3.468 × 1021 molecules
Area occupied by a single molecule = 16.2 × 10–20 m2
 Area occupied by 3.468 × 1021 molecules of nitrogen = (16.2 × 10–20) × (3.468 × 1021) m2 = 561.8 m2.
4. Which of the following has minimum gold number ?
(A) Potato starch (B) Gum arabic (C) Gelatin (D) Albumin
Sol. (C) Gelatin has minimum gold number. Therefore, (C) is correct option.
5. Which of the following are correctly matched ?
(A) Butter-gel (B) Milk-emulsion (C) Fog-aerosol (D) Dust-solid sol
Sol. (A, B, C) are correct matches.
6. Explain the adsorption of nitrogen on iron.
Sol. When nitrogen gas is brought in contact with iron at 83 K, it is physisorbed on iron surface as nitrogen
molecules, N2.As the temperature is increased the amount of nitrogen adsorbed decreases rapidly and at
room temperature, practically there is no adsorption of nitrogen on iron. At 773 K and above, nitrogen is
chemisorbed on the iron surface as nitrogen atoms.
7. How do size of particles of adsorbent, pressure of gas and prevailing temperature influence the extent of
adsorption of a gas on a solid ?
Sol. (a) Smaller the size of the particles of the adsorbent, greater is the surface area and hence greater is the
adsorption
(b) At constant temperature, adsorption first increases with increase of pressure and then attains equilibrium.
(c) In physical adsorption, it decreases with increase of temperature but in chemisorption, first it increases
and then decreases.
8. How is adsorption of a gas is related to its critical temperature ?
Sol. Higher is the critical temperature of a gas, greater the van der Waal’s forces of attraction and hence greater
is the adsorption.
9. Physical adsorption is essentially quite appreciable :
(A) at room temperature (B) at higher temperature
(C) at lower temperature (D) none of these
Sol. (C) Rate of physical adsorption decreases with increase in temperature (exothermic process). Therefore, (C)
is correct option.
10. What type of colloidal sols are formed in the following ?
(i) Through cooled water, vapours of sulphur are passed.
(ii) White of an egg is mixed with water.
Sol. (i) Sulphur molecules associate together to form molecular sols.
(ii) Macromolecular sol because protein molecules present in the white of the egg are macromolecules & are
soluble in water.
11. What happens when persistent dialysis of a colloidal solution is carried out.
Sol. The stability of a colloidal sol is due to the presence of a small amount of the electrolyte. On persistent
dialysis, the electrolyte is completely removed. As a result, the colloidal sol becomes unstable and gets
coagulated.
ADVSC - 24

(5403) Sheet Surface Chemistry Theory e

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Surface Chemistry

Adsorption is rapid in the beginning and its rate slowly

It is a slow process It is a fast process

Differences between Physical and Chemical Adsorption

Property physical Adsorption Chemical Adsorption

Nature of adsorption Weak Strong

Enthalpy of adsorption Low High

Temp. at which adsorption is

Not specific generally take place Highly specific take place on

Nature of adsorbate layer Multi-layered Mono-layered

Increase with pressure of

Energy of activation Very low significant relative high

depends on adsorbate (gas) only Depends on adsorbate as well

 Activation of adsorbent :

Freundlich Adsorption isotherm

Pressure G raph R elation

where, x = Amount of gas adsorbed, m = Mass of adsorbent, K

Langmuir Adsorption Isotherm

Amount of gas adsorbed ‘x’ by given mass of adsorbent ‘m’ is proportional to 

Positive Negative Auto Induced

Platinised asbestos ( catalyst )

Some Industrial Catalytic reactions

Differentiating point of colloids :

DP DM Type of colloid Examples

S.No. Property Lyophilic colloids Lyophobic colloids

4. On the basis of chemical composition:

Aggregation of RCOO– ions to form an ionic micelle.

Sodium stearate (C17H35COO– Na+) Hydrophobic tail

(c) (d) (e)

CHOHCOOK CH OH COOK

Charge Colloidal particals of Fe (OH)3

Important properties of colloidal sols :

True solution Colloidal solution

Example-5 Under what conditions is Tyndal effect observed ?

 Mechanical Properties :

(Fig. : A set up for electrophoresis.)

Example-7 Classify the following sols according to theirs charges :

 Coagulation/Flocculation : This process of aggregation of colloidal particles into an insoluble

coagulatin g power of electrolyt e A coagulatio n value B

weight of lyophilic sol in mg 10

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